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Groundwater hydrology, groundwater and surface-water interactions, water quality, and groundwater-flow simulations for the Wet Mountain Valley alluvial aquifer, Custer and Fremont Counties, Colorado, 2017–19

In 2017, the U.S. Geological Survey, in cooperation with the Upper Arkansas Water Conservancy District, began a study to provide a comprehensive analysis of the Wet Mountain Valley alluvial aquifer, Custer and Fremont Counties, Colorado. The study included collection of data pertaining to groundwater hydrology, groundwater and surface-water interactions, and water quality in the alluvial aquifer. In addition to providing foundational information on the hydrology of the alluvial aquifer, a numerical groundwater-flow model was developed to estimate the potential effects of additional storage of groundwater in the alluvial aquifer. Groundwater-level elevation data from 30 wells were used to estimate groundwater-flow directions in the alluvial aquifer, which were generally from the southwest to northeast, away from the Sangre de Cristo Mountains and towards perennial streams in the center of the valley. Although some seasonal variation was apparent in groundwater-level elevation records, no statistically significant seasonal trends were indicated. Statistically significant long-term trends were indicated in groundwater-level elevation records for 8 of the 30 wells, and of these wells with statistically significant trends, all but 1 indicated a negative trend of groundwater-level elevations. Spatial evaluation of wells with statistically significant negative groundwater-level elevation trends showed many are in areas of denser well drilling for domestic or other uses, indicating increasing groundwater use could potentially be causing groundwater-level elevation declines. There were instances of wells with no statistically significant groundwater-level elevation trends also located in areas of greater density of well completions. Additional investigations may be necessary to more fully characterize the processes responsible for negative groundwater-level elevation trends. Streamflow gain or loss calculations were completed for low flow in 2017–19 and for high flow in 2018 in nine reaches of streams within the study area. Stream reaches of the upper Texas Creek, upper Grape Creek, upper-middle Grape Creek, and Taylor Creek displayed consistent streamflow loss in each period from 2017 to 2019. These stream reaches represent long-term sources of recharge to the alluvial aquifer. Streamflow gain or loss varies through time in other stream reaches (lower Texas Creek, lower-middle Grape Creek, lower Grape Creek below Westcliffe, and lower Grape Creek above DeWeese Reservoir). The temporally variable behavior indicates these stream reaches may be sources of groundwater recharge or areas of groundwater discharge, likely depending on temporal dynamics between the elevation of the water table and the stream. Water-quality samples were collected from 10 groundwater wells and 10 stream sites during September through November 2019. All groundwater and stream samples were analyzed for major and trace elements and stable isotopes of water. A subset of groundwater samples was also analyzed for the environmental tracers sulfur hexafluoride, tritium, and noble gases. Comparison of water-quality results to U.S. Environmental Protection Agency drinking water-quality standards indicated no constituents exceeded primary standards for human health. Spatial evaluation of water quality indicated the concentrations of various constituents are likely controlled by groundwater and surface-water interactions and by spatial variability in bedrock geology underlying the alluvial aquifer. Specifically, streams shown to gain from groundwater had water chemistry constituent compositions similar to groundwater, whereas streams exiting the Sangre de Cristo Mountains tended to have compositions consistent with snowmelt. Groundwater geochemistry appeared to be partially controlled by oxidation-reduction processes and by proximity to igneous rocks in the Wet Mountains. Environmental tracers used to estimate groundwater age indicated all sampled groundwater contained tracers representing modern recharge (approximately less than 65 years old) but mixing of premodern recharge (approximately more than 65 years old) also occurs. Spatial evaluation of environmental tracers indicated large faults may be conduits for upwelling of older groundwater. No trends were observed in groundwater age with well depth, indicating all sampled wells are located within the zone of active groundwater flow. The presence of modern groundwater in wells with statistically significant negative groundwater-level elevation trends indicates groundwater storage depletions may be partially offset by capture of modern recharge. Repeated sampling of groundwater age would be necessary, however, to determine if any trends in groundwater age exist, which may indicate changing groundwater recharge, storage, or discharge. Additional investigations could also consider quantifying groundwater age in deeper wells to more fully define the depth of active groundwater flow. A numerical groundwater-flow model was developed to estimate components of the water budget, simulate groundwater and surface-water interactions, and evaluate the potential effects of aquifer storage and recovery. Simulated groundwater-level elevations from the calibrated groundwater-flow model are similar to the observed pattern of groundwater-level elevations with higher elevations in the western part of the study area along the Sangre de Cristo Mountains. Simulated water-budget components indicate most of the recharge to the alluvial aquifer is derived from streamflow losses, which is consistent with observations of losing streams along the mountain front. The largest groundwater discharge component of the alluvial aquifer was to streams in the center of the valley, where observations of stream gain or loss indicated the predominance of gaining conditions. Comparison of groundwater and surface-water interactions between the calibrated groundwater-flow model for 2000-19 (the base-case model) and a simulation including additional recharge, representing potential aquifer storage and recovery operations, indicated the additional recharge distributed throughout the area had minimal effects on streamflow in the nearby Grape Creek. An analysis of subregional groundwater budgets showed approximately 54 percent of the additional recharge flowed back to nearby Grape Creek, and the other 46 percent was distributed laterally into adjacent cells in the alluvial aquifer. The comparison of simulations and subregional water budget show the additional recharge did not substantially alter groundwater-level elevations or basin wide groundwater storage. Although the analysis of additional recharge provided in the numerical groundwater-flow model considers only one of many possible recharge scenarios, the model provides a useful tool that could be modified for various scenarios to understand potential effects of managed aquifer recharge.

Colorado

Treatability study to evaluate bioremediation of trichloroethene at Site K, former Twin Cities Army Ammunition Plant, Arden Hills, Minnesota, 2020–22

Executive Summary Chlorinated solvents, including trichloroethene (TCE) and other chlorinated volatile organic compounds (cVOCs), are widespread contaminants that can be treated by bioremediation approaches that enhance anaerobic reductive dechlorination. Reductive dechlorination can be enhanced either through the addition of an electron donor (biostimulation) or the addition of a known dechlorinating culture (bioaugmentation) along with an electron donor. Although bioremediation has been applied at many TCE-contaminated groundwater sites, application in source zones at sites where residual dense nonaqueous phase liquid (DNAPL) is present is more limited. In this study, laboratory and field treatability tests were completed to evaluate the potential application of anaerobic bioremediation for a shallow groundwater plume containing TCE in a perched alluvial aquifer at Site K, former Twin Cities Army Ammunition Plant, Arden Hills, Minnesota, which was on the National Priorities List as the New Brighton/Arden Hills Superfund site until 2019. In addition to the presence of residual DNAPL at the site, temporal variability in groundwater flow directions and input of oxygenated recharge were possible complicating factors for the application of enhanced anaerobic biodegradation in the shallow plume. The Site K plume extends beneath the footprint of Building 103, which was demolished in 2006, and soil excavations to a maximum depth of 6 feet (ft) below ground surface in 2014 were known to leave some deeper contaminated soil in place in the TCE source area. Groundwater treatment at the site, formalized as part of the 1997 Record of Decision, has been in operation since 1986 and consists of an extraction trench at the downgradient edge of the plume to collect groundwater, which is then pumped to an on-site air stripper. Groundwater concentrations in the plume have been relatively stable since treatment began, indicating a continued source of TCE in the aquifer. The desire for a destructive remedy that would enhance the removal of cVOCs in the aquifer at Site K and shorten the remediation timeframe led the U.S. Army to request that the U.S. Geological Survey conduct a groundwater treatability study to assess bioremediation. This report describes the U.S. Geological Survey bioremediation treatability study conducted during 2020–22, including pre-design site characterization to assist in formulating the bioremediation approach, laboratory experiments to support the design of the field pilot test, and implementation and 1-year performance monitoring results for the pilot test. Pre-design site characterization included the collection of soil cores for cVOC analysis and lithologic descriptions and the re-installment of three wells to obtain hydrologic measurements and initial groundwater chemistry. Relatively flat head gradients were measured at the site, and substantial decreases in water-level elevations occurred from spring to summer (May–July 2021). Continuous water-level monitoring indicated a rapid response to precipitation. Groundwater flow velocities were consistently less than 0.5 foot per day, and the pilot bioremediation test was therefore designed with short lateral distances (about 5 ft) between injection and individual monitoring points. Soil analyses confirmed that high volatile organic compound contamination was left in place in the source area. The highest concentrations were near or in clay at the base of the perched aquifer. Concentrations of cVOCs measured in the replaced wells were consistent with historical data and had a maximum TCE concentration of 57,700 micrograms per liter (μg/L), indicative of nearby residual DNAPL based on the general rule of observed concentrations exceeding 1 percent of solubility. The primary TCE daughter product detected was 1,2-cis-dichloroethene (cisDCE), which indicated limited reductive dechlorination in the plume. Groundwater in both the source and downgradient areas was relatively reducing during the pre-design characterization, particularly in the source area where methane concentrations greater than 400 μg/L were measured. Initial laboratory tests conducted using native aquifer microorganisms from the three replacement wells showed that anaerobic TCE biodegradation rates were low when biostimulated with the addition of sodium lactate as an electron donor, also known as a carbon donor, and resulted in the production of only cisDCE. Addition of a known dechlorinating culture, WBC-2, however, resulted in rapid biodegradation and production of ethene, verifying complete reductive dechlorination of TCE. Microcosms constructed with aquifer soil collected from the site were used to evaluate other electron donors besides lactate to support reductive dechlorination by WBC-2, including corn syrup as an alternative fast-release compound and whey, soy-based vegetable oil, and 3-D Microemulsion (Regenesis, San Clemente, California) as slow-release compounds. First-order rate constants for total organic chlorine removal in these WBC-2 amended microcosms were greatest with either lactate or vegetable oil as the donor, ranging between 0.061 and 0.047 per day or corresponding half-lives of 11–15 days. Testing of commercial products in other WBC-2-bioaugmented microcosms led to selection for the field pilot test of an emulsified vegetable oil product that also contained some sodium lactate as a fast-release donor. Delaying the addition of WBC-2 relative to the donor in the microcosms resulted in the most rapid overall biodegradation rates. The selected design for the pilot test utilized three separate test plots, each about 30-ft wide and 60-ft long: plots GS1 and GS2 in the source area of the plume and plot GS3 in the downgradient area of the plume near the excavation trench. Each test plot had one injection well, one monitoring well upgradient from the injection point, and 12 surrounding monitoring wells in a grid to capture variable groundwater flow directions. Donor injections, which included a bromide tracer, were completed in October 2021, immediately following baseline sampling, and the WBC-2 culture was injected about 40 days later, between November 30 and December 2, 2021. Performance monitoring conducted until December 2022 included hydrologic measurements and analyses of cVOCs, redox-sensitive constituents, dissolved organic carbon, bromide, volatile fatty acids, compound-specific carbon isotopes, and microbial communities. The biogeochemical data collected during the pilot tests in the three treatment plots showed that enhanced, complete reductive dechlorination of cVOCs in the groundwater was achieved in the GS1 and GS3 plots. In contrast, evidence of distribution of the injected amendments and subsequent biodegradation was limited in GS2, which was in an area of more heterogeneous soil lithology and low water table elevations. The molar composition of volatile organic compounds in the GS1 and GS3 plots was dominated by ethene in wells that were reached by the injected amendments by the end of the monitoring period. In the GS1 and GS3 plots, similar patterns were observed of cVOC concentrations decreasing to near detection levels, or below, at some wells sampled in July and October 2022, whereas ethene became dominant and indicated sustained complete reductive dechlorination. Baseline cVOC concentrations were more than a factor of 10 higher in the groundwater in the GS1 plot than in GS3, but no apparent inhibition of complete dechlorination occurred. As expected from the initial pre-design site data and the laboratory experiments, enhanced dissolution of residual DNAPL coupled to biodegradation was evident in the GS1 plot, where a marked increase in dichloroethene (DCE) above the initial baseline and upgradient TCE and DCE concentrations occurred. DCE concentrations subsequently declined where DNAPL dissolution was evident, concurrent with production of vinyl chloride and then predominantly ethene. Thus, overall biodegradation rates outpaced the DNAPL dissolution and desorption and DCE production in the source area. This success in complete degradation to predominantly ethene was achieved even in areas where the DCE concentrations reached a maximum of about 30,000 μg/L. Compound specific isotope analysis of carbon in TCE, cisDCE, trans-1,2-dichloroethene, and vinyl chloride was conducted to provide another line of evidence of the occurrence and extent of anaerobic biodegradation. Along a flow path in each plot that was affected by the injected amendments, carbon isotopes in the TCE and daughter cVOCs in the groundwater became isotopically heavier, indicating biodegradation. Enhanced biodegradation rates calculated from the field tests in GS1 and GS3 showed half-lives of 36.9–75.3 days for DCE degradation and 9.48–38.5 days for ethene production. Notably, these ethene production rates calculated from the field tests are consistent with the results of WBC-2-bioaugmented microcosms amended with either lactate or vegetable oil, which had half-lives for total organic chlorine removal that ranged from 11 to 15 days. These rates indicated rapid enhanced biodegradation, which is promising for application of a full-scale bioremediation remedy. Ultimately, however, the mass of residual or sorbed TCE in the aquifer that remains accessible for dissolution and biodegradation would likely control the time required for a full-scale bioremediation effort to achieve performance goals for TCE and cisDCE specified in the Record of Decision for Site K. The field pilot tests showed that the relatively low hydraulic head gradients and temporal changes in groundwater flow directions in the shallow aquifer would add complexity to a full-scale bioremediation effort. The radius of influence (ROI) at GS1 and GS3 (16.3 ft and 12.7 ft, respectively) were close to the design ROI of 15 ft. The estimated ROI at GS2 was about four times the design ROI, but may be less reliable at this location owing to groundwater flow direction. In addition, the low temperatures following WBC-2 injection in late November to early December 2021, in combination with the low hydraulic head gradients, were probably major factors in the delay observed before the onset of enhanced biodegradation following injection of the culture. Additional test injections could be beneficial to optimize the timing of donor and culture injections with the variable temperatures and hydraulic head in the shallow aquifer.

Minnesota