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Emily H. Majcher

Publications and source records attributed to Emily H. Majcher.

14 recordsLinked to original sources

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↗

Tracking status and trends in seven key indicators of river and stream condition in the Chesapeake Bay watershed

Freshwater streams and rivers are recognized as vital habitats within the Chesapeake Bay watershed, which has been undergoing extensive restoration efforts for more than 30 years. Resource managers need to understand stream and river condition and how these conditions are changing over time to determine whether regional long-term restoration and conservation goals are being met. The objective of this report was to document the spatial and temporal variability of conditions for seven indicators of river and stream health across the nontidal Chesapeake Bay watershed. The framework for the U.S. Geological Survey’s Nontidal Network (NTN), a network of more than 100 nutrient and suspended sediment monitoring locations, was extended to assess conditions for six additional indicators of stream health: temperature, salinity, toxic contaminants, streamflow, hydromorphology, and biological aquatic communities. For each indicator, the latest available data from multiple sources were compiled and harmonized, and key metrics were identified to describe indicator conditions across space and time. A status condition was defined for each indicator to describe overall spatial variability in recent condition, and trend analyses were used to describe changes in each indicator metric over time. The analysis revealed clear differences in spatial and temporal data coverage across the seven indicators, so individual indicator trend analyses were not constrained to a common time interval. However, a status snapshot was conducted across all indicators for the 2015–17 period to simultaneously explore spatial variability across all indicators. The status snapshot highlighted general degraded conditions across multiple indicators in large metropolitan regions, such as the Baltimore–Washington, D.C., metropolitan area. Regression analysis between indicator status metrics and major land cover for the sites suggest urbanization as a potential driver of degraded conditions for many of the indicator metrics, including total phosphorus, salinity, temperature, high-flow frequency, and metrics of habitat and biological assemblage quality. A final analysis exploring the spatial representation of each indicator network showed that some indicator monitoring networks did not cover certain settings, such as small watersheds. These results provided an initial assessment of stream health status and trends and will continue to be leveraged to describe conditions across the Chesapeake Bay watershed to help inform local and regional management decisions. These results also highlighted the need for improved coordination among monitoring organizations to support long-term multi-indicator monitoring and assessment.

Chesapeake Bay watershed↗

Municipal and industrial wastewater treatment plant effluent contributions to per- and polyfluoroalkyl substances in the Potomac River: A basin-scale measuring and modeling approach

Managing per- and polyfluoroalkyl substances (PFAS) in water resources requires a basin-scale approach. Predicted environmental concentrations (PEC) and stream-vulnerability scores for PFAS were determined for the Potomac River watershed in the eastern United States. Approximately 15% of stream reaches contained municipal and/or industrial wastewater treatment plant (WWTP) discharges that are presumptive PFAS sources, comprising from <1 to >90% of streamflow. Mean annual PEC, based on the summed concentrations of eight PFAS detected in WWTP effluents (ΣPFAS PEC ), for all stream reaches in the watershed was 3.8 ng L –1 , and stream reaches impacted by WWTP had perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) PEC of 0.39 and 0.14 ng L –1 . For locations where measured-environmental concentrations (MEC) were determined, municipal and industrial WWTP contributed 7.8% (0 to 65%) of the total annual streamflow and MEC were greater than PEC in 99% of the samples, indicating additional potential PFAS sources. The mean ΣPFAS PEC was 9.1 ng L –1 compared to a mean sum of PFAS MEC of 34 ng L –1 . Under mean-August low-flow, 17% and 9.4% of the water-supply intakes had maximum PFOA and PFOS PEC exceeding drinking water maximum contaminant levels.

Maryland, Pennsylvania, Virginia, West Virginia↗

Contaminated stormwater sediment source tracking for polychlorinated biphenyls in an urban watershed of the Chesapeake Bay, United States

Fine-grained sediment in stormwater acts as a vector for persistent organic pollutants, like polychlorinated biphenyls (PCBs), through mobilization from sources within drainage areas of impacted urban watersheds. This study implemented a novel approach to identify the relative contributions of various landscape and stream sources of sediment from the Back River watershed in eastern Baltimore, Maryland, and investigated the applicability of using trace PCBs found in an urban environment as discriminants between each source type. Trace PCBs were found to be poor discriminants when identifying the relative sediment contributions of watershed-scale land use categories. When excluding PCBs in the development of a sediment fingerprinting model and instead utilizing trace elements and carbon only, sediment fingerprint modeling successfully differentiated green spaces and eroding streambanks as the most significant contributors to stormwaters sediment (37.1 % and 44.0 %, respectively) of the total sediment contributions of all considered source categories. In all samples collected from various landscape sources, storms, and cores detectable concentrations of PCBs were measured. The results of this study indicate that sediment fingerprinting may not be an effective method in predicting where PCBs may be found within an impacted watershed.

Maryland↗

Evaluation and review of best management practices for the reduction of polychlorinated biphenyls to the Chesapeake Bay

Polychlorinated biphenyls (PCBs) continue to impact the environment due to historic and ongoing anthropogenic sources (for example, industrial and agricultural), despite their ban. Contaminated stormwater has been identified as a vector for PCB transport to many estuaries impaired by PCBs. Management of these regulated discharges is typically achieved by best management practices (BMPs). This review focuses on PCB reduction practices and BMPs to assist management decision making and provide information on the current state of the science. Studies have quantitatively demonstrated the efficacy of green infrastructure BMPs and gray infrastructure improvements to reduce PCB loads, and other studies have demonstrated qualitative reductions for other BMP types. This review also highlights the disconnect between PCB load reduction and PCB bioavailability when selecting a remediation strategy. Additionally, the review evaluates modeling approaches to assess PCB load reduction to inform management decisions and suggests why there are still significant barriers to implementation.

Chesapeake Bay watershed↗

Tracking status and trends in seven key indicators of stream health in the Chesapeake Bay watershed

“The Bay Connects us, the Bay reflects us” writes Tom Horton in the book “Turning the Tide—Saving the Chesapeake Bay”. The Chesapeake Bay watershed contains the largest estuary in the United States. The watershed stretches north to Cooperstown, New York, south to Lynchburg and Virginia Beach, Virginia, west to Pendleton County, West Virginia, and east to Seaford, Delaware, and Scranton, Pennsylvania. The watershed is more than 64,000 square miles that contain 150 major rivers and streams, hereafter referred to collectively as streams, that total more than 100,000 miles in length. The watershed contains thousands of smaller creeks and tributaries, large numbers of plants and animals, and, in 2020, more than 18.4 million people. As changes occur in population, land use, and climate within the watershed, so too do the diversity and health of the Bay's ecosystems.

Chesapeake Bay watershed↗

Refining sources of polychlorinated biphenyls in the Back River watershed, Baltimore, Maryland, 2018–2020

Older urban landscapes present unique and complex stressors to urban streams and their habitats through the introduction of legacy and emerging toxic contaminants. Contaminant sources are often associated with various developed land uses such as older residential areas, active and former industrial sites, contaminated sites, and effluents from municipal wastewater treatment plant discharges. These landscapes have a history of legacy contaminant use such as polychlorinated biphenyls (PCBs) resulting in impacts to sediment and water in these complex environments. Despite the ban of PCBs in new commercial use in 1979, PCB contamination is still widespread in the environment, with many fish consumption advisories throughout the Chesapeake Bay region based on elevated PCBs. Several watersheds in the Baltimore region have mandated reductions in PCBs per total maximum daily loads in tidal waters of the watersheds in order to promote compliance with water quality standards. Some of these mandated reductions (for example, regulated watershed runoff) specified in the total maximum daily loads are the responsibility of the local jurisdictions as part of their phase 1 National Pollutant Discharge Elimination System municipal separate storm sewer system permit. In cooperation with the Baltimore City Department of Public Works and Maryland Department of the Environment, the U.S. Geological Survey and University of Maryland, Baltimore County conducted a study from 2018 to 2020 to refine the sources of PCBs from the City of Baltimore into Back River and to use the results to improve the conceptual site model of PCBs in the Back River watershed. PCB concentrations in the water column of the nontidal streams in Back River watershed are relatively consistent throughout both tributaries, with greater concentrations detected in samples collected from Moores Run but greater loads estimated in samples collected from Herring Run. PCB concentrations measured in the bed sediments and analysis of the flux between sediment porewater (hereafter porewater) and surface water within the tributaries suggest that there are no stationary legacy sources within the stream channels. The bulk of PCB mass entering the system from these nontidal tributaries appears to be introduced primarily during storm events. While only one storm event was sampled and concentrations were quantified only in Herring Run, solids captured during the storm were characterized by increases in PCB mass and overall suspended solids concentrations. Although the bioavailability of the PCB-associated sediment is unknown, this mechanism appears to warrant additional attention to better understand how concentrations vary under different storm conditions and temporally. The importance of contaminated stormwater in loading to Herring Run is further supported by the PCB concentrations in storm drain sediments collected near the tributary, which were present in higher concentrations and were characterized by different homolog signatures compared to that in bed sediments. The observations in the tributaries differed from PCB concentrations and sediment characteristics downstream from the City of Baltimore boundary, in the upper tidal area of the main stem of Back River, particularly at the passive sampler locations BRT–1 and BRT–3. This depositional environment is characterized by higher organic content in sediments and higher concentrations of PCBs in porewater, which result in the possible flux of contaminants from sediment to the water column. This flux is generally opposite of that observed in the nontidal tributaries and the farthest upstream tidal site (BRT–2) and may be a result of the possible settling of sediment particles introduced via suspended solids in stormwater. Despite an observed considerable reduction in overall PCB mass loading to and from the Back River Wastewater Treatment Plant (BRWWTP) (and similar reductions observed in biosolids) compared to the estimates previously reported from 2015, effluent from the BRWWTP continues to be a primary source of PCBs to Back River. The current study confirmed the likeliness of fat, oil, and grease deposits within the miles of sewer pipe as a source of PCBs to the BRWWTP influent. The differences between PCB concentrations in fat, oil, and grease deposits found in pipes (during replacement) compared to that of the BRWWTP suggest that legacy deposits may contain higher PCB concentrations and may act as a source of PCBs to passing sewage, eventually entering the BRWWTP. Variation in freely dissolved concentrations in the sewer system was apparent through the analysis of PCBs in the primary pump stations using passive sampling, with the largest contribution to the influent attributed to a single pump station and associated piping. The contribution of PCBs to Herring Run and Moores Run via sanitary sewer overflows compared to the BRWWTP effluent is negligible, similar to reports from another large urban wastewater treatment plant. Therefore, decreased occurrence of sanitary sewer overflows is not expected to largely decrease PCB loads. Results of this study suggest that targeted, sediment-capture best management practices in Back River watershed could be an effective way to reduce PCB mass loading assuming that deposited contaminated sediments are effectively isolated. Recent studies of some common urban best management practices such as bioretention have shown removal of PCBs within the stormwater control structures. In addition, appropriately timed street sweeping practices with appropriate collection equipment may be an effective way to reduce contaminants such as PCBs from road runoff sources. Reductions in concentrations and mass loading within the sewer system measured in this study compared to that estimated 5 years prior reflect the possible success of ongoing gray infrastructure management actions. Reductions may be attributable to enhanced nutrient reduction upgrades to the BRWWTP and extensive capital improvements and maintenance to the sewer system. This study employed a combined sampling approach and a variety of sampling methods to include low-density polyethylene passive samplers, high-volume water samples, and grab samples of both water and sediment to characterize the PCB inputs to Herring Run, Moores Run, and Back River. Incorporating the passive samplers provided a time-weighted average of the freely dissolved concentration in the surface water, porewater, WWTP influent and effluent, and pump station influent over the deployment period with picogram per liter detection limits. A similar monitoring approach from this study could be implemented within other subwatersheds or municipal separate storm sewer system jurisdictions to assist in refining primary sources of PCBs in order to inform appropriate mitigation approaches.

Maryland↗

Effective solubility assessment for organic analytes in liquid samples, BKK class I landfill, West Covina, California, 2014–16

Executive Summary The U.S. Geological Survey assessed the effective solubilities of organic analytes at the BKK Class Ⅰ Landfill site, West Covina, California, in cooperation with the California Department of Toxic Substances Control, using available data for liquid samples collected within (in-waste) and below (sub-waste) the landfill in 2014–16. The primary purpose of the effective solubility calculations was to determine the likely presence or absence of dense non-aqueous phase liquids (DNAPLs), which is important for understanding the sources, persistence, and movement of the leachate contaminants. Percent effective solubility (a measure of the degree of deviation of a measured liquid concentration of a compound from the aqueous effective solubility) greater than 1 percent is the threshold that commonly has been used to infer the presence of DNAPLs or mixed DNAPLs in aqueous monitoring results. In the present study, however, thresholds higher than 1 percent were used because of elevated temperatures and concentrations of cosolvents in the liquid samples—thresholds of 10 percent or 100 percent, respectively, were used for liquid and solid (at 25 degrees Celsius) organic compounds for potential non-aqueous phase liquid presence. Overall, the effective solubility calculations indicate the likely presence of DNAPLs or mixed DNAPLs in some samples for a range of compounds, including tetrachloroethene, trichloroethene, 1,1-dichloroethene, vinyl chloride, 1,2,4-trichlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, naphthalene, toluene, ethylbenzene, and xylenes. Samples with the highest calculated percent effective solubilities for chlorinated ethenes, ethanes, and benzenes were from a location where liquid in the waste prism is known to be in contact with the groundwater beneath the landfill. Trends in the effective solubilities for the chlorinated ethenes and ethanes were generally consistent between the in-waste and sub-waste samples, supporting a similar source composition for these liquids. Percent effective solubilities were less than 10 for the chlorinated ethanes in all the in-waste and sub-waste samples, indicating that DNAPL of these compounds is not present. Percent effective solubilities of chlorinated benzenes, ethylbenzene, and xylenes exceeded the 10-percent effective solubility threshold in more of the sub-waste samples than the in-waste liquid samples. Volatilization also may influence the patterns in the calculated effective solubilities but were not included in this study.

California↗

Changes in long-term water quality of Baltimore streams are associated with both gray and green infrastructure

The steadily rising global urban population has placed substantial strain on urban water quality, and this strain is projected to increase for the foreseeable future. Considerable attention has been given to the hydrological and physico-chemical effects of urbanization on stream ecosystems. However, due to the relative infancy of the field of urban ecology, long-term water quality analyses in urban streams are sparse. Using a 15-year stream chemistry monitoring record from Baltimore, MD, USA, we quantified long-term trends in nitrate, phosphate, total nitrogen, total phosphorus, chloride, and sulfate export at several sites along a rural-urban gradient. We found no significant change in solute export at most sites, although we did find specific patterns of interest for certain solutes. For example, nitrogen export declined at the most headwater urban site, while phosphorus export declined at the most downstream urban site. Coupling long-term monitoring with data on gray and green infrastructure management throughout the landscape, we established relationships between solute export at the most downstream urban monitoring site and sanitary sewer overflows (SSOs), best management practice (BMP) implementation, and road salt application rates. Phosphorus export was correlated with BMP implementation in the watershed, whereas nitrogen export was related to SSOs. Despite highly urbanized watersheds, water quality does not appear to be declining at most of these sites, suggesting that current management may have limited further impairment. Results of our study suggest that both gray and green infrastructure are key for maintaining and improving water quality in this highly urbanized watershed.

Maryland↗

Factors affecting long-term trends in surface-water quality in the Gwynns Falls watershed, Baltimore City and County, Maryland, 1998–2016

Factors affecting water-quality trends in urban streams are not well understood, despite current regulatory requirements and considerable ongoing investments in gray and green infrastructure. To address this gap, long-term water-quality trends and factors affecting these trends were examined in the Gwynns Falls, Maryland, watershed during 1998–2016 in cooperation with Blue Water Baltimore. Data on water-quality constituents and potential factors of influence were obtained from multiple sources and compiled for analysis, with a focus on data collected as part of the National Science Foundation funded Long-Term Ecological Research project, the Baltimore Ecosystem Study. Variability in climate (specifically, precipitation) and land cover can overwhelm actions taken to improve water quality and can present challenges for meeting regulatory goals. Analysis of land cover during 2001–11 in the Gwynns Falls watershed indicated minimal change during the study time frame; therefore, land-cover change is likely not a factor affecting trends in water quality. However, a modest increase in annual precipitation and a significant increase in winter precipitation were apparent in the region. A higher proportion of runoff producing storms was observed in the winter and a lower proportion in the summer, indicating that climate change may affect water quality in the watershed. The increase in precipitation was not reflected in annual or seasonal trends of streamflow in the watershed. Nonetheless, these precipitation changes may exacerbate the inflow and infiltration of water to gray infrastructure and reduce the effectiveness of green infrastructure. For streamflow and most water-quality constituents examined, no discernable trends were noted over the timeframe examined. Despite the increases in precipitation, no trends were observed for annual or seasonal discharge at the various sites within the study area. In some locations, nitrate, phosphate, and total nitrogen show downward trends, and total phosphorus and chloride show upward trends. Sanitary sewer overflows (gray infrastructure) and best management practices (green infrastructure) were identified as factors affecting water-quality change. The duration of sanitary sewer overflows was positively correlated with annual loads of nutrients and bacteria, and the drainage area of best management practices was negatively correlated with annual loads of phosphate and sulfate. Results of the study indicate that continued investments in gray and green infrastructure are necessary for urban water-quality improvement. Although this outcome is not unexpected, long-term datasets such as the one used in this study, allow the effects of gray and green infrastructures to be quantified. Results of this study have implications for the Gwynns Falls watershed and its residents and Baltimore City and County managers. Moreover, outcomes are relevant to other watersheds in the metropolitan region that do not have the same long-term dataset. Further, this study has established a framework for ongoing statistical analysis of primary factors affecting urban water-quality trends as regulatory programs mature.

Maryland↗

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↗

Microbial consortia development and microcosm and column experiments for enhanced bioremediation of chlorinated volatile organic compounds, West Branch Canal Creek wetland area, Aberdeen Proving Ground, Maryland

Chlorinated solvents, including 1,1,2,2-tetrachloroethane, tetrachloroethene, trichloroethene, carbon tetrachloride, and chloroform, are reaching land surface in localized areas of focused ground-water discharge (seeps) in a wetland and tidal creek in the West Branch Canal Creek area, Aberdeen Proving Ground, Maryland. In cooperation with the U.S. Army Garrison, Aberdeen Proving Ground, Maryland, the U.S. Geological Survey is developing enhanced bioremediation methods that simulate the natural anaerobic degradation that occurs without intervention in non-seep areas of the wetland. A combination of natural attenuation and enhanced bioremediation could provide a remedy for the discharging ground-water plumes that would minimize disturbance to the sensitive wetland ecosystem. Biostimulation (addition of organic substrate or nutrients) and bioaugmentation (addition of microbial consortium), applied either by direct injection at depth in the wetland sediments or by construction of a permeable reactive mat at the seep surface, were tested as possible methods to enhance anaerobic degradation in the seep areas. For the first phase of developing enhanced bioremediation methods for the contaminant mixtures in the seeps, laboratory studies were conducted to develop a microbial consortium to degrade 1,1,2,2-tetrachloroethane and its chlorinated daughter products under anaerobic conditions, and to test biostimulation and bioaugmentation of wetland sediment and reactive mat matrices in microcosms. The individual components required for the direct injection and reactive mat methods were then combined in column experiments to test them under groundwater- flow rates and contaminant concentrations observed in the field. Results showed that both direct injection and the reactive mat are promising remediation methods, although the success of direct injection likely would depend on adequately distributing and maintaining organic substrate throughout the wetland sediment in the seep area. For bioaugmentation, two mixed anaerobic cultures, named the 'West Branch Consortia' (WBC-1 and WBC-2), were developed by enrichment of wetland sediment collected from two contaminated sites in the study area where rapid and complete reductive dechlorination naturally occurs. WBC are capable of degrading 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, 1,2-dichloroethane, tetrachloroethene, trichloroethene, cis- and trans-1,2-dichloroethene, and vinyl chloride to the non-chlorinated end-products ethene and ethane. In addition, the column experiments showed that the consortia could completely degrade carbon tetrachloride and chloroform, although they were not grown on these contaminants. No other cultures are known that can degrade the broad mixture of chlorinated alkanes, alkenes, and methanes as shown for WBC. WBC-2 (suspended in the culture media) is capable of complete dechlorination of 50 micromolar 1,1,2,2-tetrachloroethane to ethene in 1 to 2 days with little transient accumulation of chlorinated daughter products. Only about 5 percent of the clones sequenced from WBC-1 and WBC-2 were related to dechlorinating bacteria that have been studied previously in culture, indicating the presence of unknown dechlorinators. Dehalococcoides spp. comprised about 1 percent of WBC-1 and WBC-2, which is minor compared to the population size of about 30 percent in other dechlorinating consortia for chlorinated alkenes. Although both WBC-1 and WBC-2 showed efficient degradation in laboratory tests in this study, long-term cultivation of WBC-1, which was developed using hydrogen as the organic substrate, was determined to be infeasible. Thus, WBC-2, cultivated with lactate as the organic substrate, would be used in future tests. Nutrient (ammonia and phosphate mixture) addition to anaerobic microcosms constructed with wetland sediment and ground water collected from the study area showed some enhancement in the degradation rate of 1,1,2,2-tetrachloroethane, but degrada

Maryland↗

Characterization of Preferential Ground-Water Seepage From a Chlorinated Hydrocarbon-Contaminated Aquifer to West Branch Canal Creek, Aberdeen Proving Ground, Maryland, 2002-04

Wetlands act as natural transition zones between ground water and surface water, characterized by the complex interdependency of hydrology, chemical and physical properties, and biotic effects. Although field and laboratory demonstrations have shown efficient natural attenuation processes in the non-seep wetland areas and stream bottom sediments of West Branch Canal Creek, chlorinated volatile organic compounds are present in a freshwater tidal creek at Aberdeen Proving Ground, Maryland. Volatile organic compound concentrations in surface water indicate that in some areas of the wetland, preferential flow paths or seeps allow transport of organic compounds from the contaminated sand aquifer to the overlying surface water without undergoing natural attenuation. From 2002 through 2004, the U.S. Geological Survey, in cooperation with the Environmental Conservation and Restoration Division of the U.S. Army Garrison, Aberdeen Proving Ground, characterized preferential ground-water seepage as part of an ongoing investigation of contaminant distribution and natural attenuation processes in wetlands at this site. Seep areas were discrete and spatially consistent during thermal infrared surveys in 2002, 2003, and 2004 throughout West Branch Canal Creek wetlands. In these seep areas, temperature measurements in shallow pore water and sediment more closely resembled those in ground water than those in nearby surface water. Generally, pore water in seep areas contaminated with chlorinated volatile organic compounds had lower methane and greater volatile organic compound concentrations than pore water in non-seep wetland sediments. The volatile organic compounds detected in shallow pore water in seeps were spatially similar to the dominant volatile organic compounds in the underlying Canal Creek aquifer, with both parent and anaerobic daughter compounds detected. Seep locations characterized as focused seeps contained the highest concentrations of chlorinated parent compounds, relatively low concentrations of chlorinated daughter compounds, and insignificant concentrations of methane in shallow pore water samples. These seeps were primarily along the creek edge or formed a dendritic-like pattern between the wetland and creek channel. In contrast, seep locations characterized as diffuse seeps contained relatively high concentrations of chlorinated daughter compounds (or a mixture of daughter and parent compounds) and detectable methane concentrations in shallow pore water samples. These seeps were primarily along the wetland boundary. Qualitative thermal infrared surveys coupled with quantitative verification of temperature differences, and screening for volatile organic compound and methane concentrations proved to be effective tools in determining the overall extent of preferential seepage. Hydrologic and physical properties of wetland sediments were characterized at two focused and one diffuse seep location. In the seeps with focused discharge, measured seepage was consistent over the tidal cycle, whereas more variability with tidal fluctuation was measured in the diffuse seep location. At all locations, areas were identified within the general seep boundaries where discharge was minimal. In all cases, the geometric mean of non-zero vertical flux measurements was greater than those previously reported in the non-seep wetland sediments using flow-net analysis. Flux was greater in the focused discharge areas than in the diffuse discharge area, and all fluxes were within the range reported in the literature for wetland discharge. Vertical hydraulic conductivity estimated from seepage flux and a mean vertical gradient at seeps with focused discharge resulted in a minimum hydraulic conductivity two orders of magnitude greater than those estimated in the non-seep sediment. In contrast, vertical conductivity estimates at a diffuse seep were similar to estimates along a nearby line of section through a non-seep area.

Scientific Investigations Report↗