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Monitored natural attenuation of chlorinated solvents: Moving beyond reductive dechlorination

Monitored natural attenuation (MNA), while a remedy of choice for many sites, can be challenging when the contaminants are chlorinated solvents. Even with many high-quality technical guidance references available, there continue to be challenges implementing MNA at some chlorinated solvent sites. The U.S. Department of Energy, as one organization facing such challenges, is leading a project that will incorporate developing concepts and tools into the existing toolbox for selecting and implementing MNA as a remediation option at sites with chlorinated solvent contamination. The structure and goals of this project were introduced in an article in the Winter 2004 issue of Remediation (Sink et al., 2004). This article is a summary of the three technical areas being developed through the project: mass balance, enhanced attenuation, and characterization and monitoring supporting the first two areas.

Remediation Journal

Accumulation of dechlorination daughter products: A valid metric of chloroethene biodegradation

In situ reductive dechlorination of perchloroethene (PCE) and trichloroethene (TCE) generates characteristic chlorinated (cis-dichloroethene [cis-DCE] and vinyl chloride [VC]) and nonchlorinated (ethene and ethane) products. The accumulation of these daughter products is commonly used as a metric for ongoing biodegradation at field sites. However, this interpretation assumes that reductive dechlorination is the only chloroethene degradation process of any significance in situ and that the characteristic daughter products of chloroethene reductive dechlorination persist in the environment. Laboratory microcosms, prepared with aquifer and surface-water sediments from hydrologically diverse sites throughout the United States and amended with [1,2- 14 C] TCE, [1,2- 14 C] DCE, [1,2- 14 C] DCA, or [1,2- 14 C] VC, demonstrated widely variable patterns of intermediate and final product accumulation. In predominantly methanogenic sediment treatments, accumulation of 14 C-DCE, 14 C-VC, 14 C-ethene, and 14 C-ethane predominated. Treatments characterized by significant Fe(III) and/or Mn(IV) reduction, on the other hand, demonstrated substantial, and in some cases exclusive, accumulation of 14 CO 2 and 14 CH 4 . These results suggest that relying on the accumulation of cis-DCE, VC, ethene, and ethane may substantially underestimate overall chloroethene biodegradation at many sites.

Remediation Journal

Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene-contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long-term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's-based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30-m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides -type bacteria within the sulfuric acid/chloroethene co-contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with 14 C-TCE and 14 C-VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co-contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to 14 CO 2 and 14 CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's-based source area treatment) do not necessarily preclude efficient chloroethene degradation.

Florida

Estimated trichloroethene transformation rates due to naturally occurring biodegradation in a fractured-rock aquifer

Rates of trichloroethene (TCE) mass transformed by naturally occurring biodegradation processes in a fractured rock aquifer underlying a former Naval Air Warfare Center (NAWC) site in West Trenton, New Jersey, were estimated. The methodology included (1) dividing the site into eight elements of equal size and vertically integrating observed concentrations of two daughter products of TCE biodegradation– cis -dichloroethene ( cis -DCE) and chloride–using water chemistry data from a network of 88 observation wells; (2) summing the molar mass of cis -DCE, the first biodegradation product of TCE, to provide a probable underestimate of reductive biodegradation of TCE, (3) summing the molar mass of chloride, the final product of chlorinated ethene degradation, to provide a probable overestimate of overall biodegradation. Finally, lower and higher estimates of aquifer porosities and groundwater residence times were used to estimate a range of overall transformation rates. The highest TCE transformation rates estimated using this procedure for the combined overburden and bedrock aquifers was 945 kg/yr, and the lowest was 37 kg/yr. However, hydrologic considerations suggest that approximately 100 to 500 kg/yr is the probable range for overall TCE transformation rates in this system. Estimated rates of TCE transformation were much higher in shallow overburden sediments (approximately 100 to 500 kg/yr) than in the deeper bedrock aquifer (approximately 20 to 0.15 kg/yr), which reflects the higher porosity and higher contaminant mass present in the overburden. By way of comparison, pump-and-treat operations at the NAWC site are estimated to have removed between 1,073 and 1,565 kg/yr of TCE between 1996 and 2009.

New Jersey

Perils of categorical thinking: "Oxic/anoxic" conceptual model in environmental remediation

Given ambient atmospheric oxygen concentrations of about 21 percent (by volume), the lower limit for reliable quantitation of dissolved oxygen concentrations in groundwater samples is in the range of 0.1–0.5 mg/L. Frameworks for assessing in situ redox condition are often applied using a simple two-category (oxic/anoxic) model of oxygen condition. The "oxic" category defines the environmental range in which dissolved oxygen concentrations are clearly expected to impact contaminant biodegradation, either by supporting aerobic biodegradation of electron-donor contaminants like petroleum hydrocarbons or by inhibiting anaerobic biodegradation of electron-acceptor contaminants like chloroethenes. The tendency to label the second category "anoxic" leads to an invalid assumption that oxygen is insignificant when, in fact, the dissolved oxygen concentration is less than detection but otherwise unknown. Expressing dissolved oxygen concentrations as numbers of molecules per volume, dissolved oxygen concentrations that fall below the 0.1 mg/L field detection limit range from 1 to 1017 molecules/L. In light of recent demonstrations of substantial oxygen-linked biodegradation of chloroethene contaminants at dissolved oxygen concentrations well below the 0.1–0.5 mg/L field detection limit, characterizing "less than detection" oxygen concentrations as "insignificant" is invalid.

Remediation Journal

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH-extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO 2 production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems.

Remediation Journal

Distributional patterns of arsenic concentrations in contaminant plumes offer clues to the source of arsenic in groundwater at landfills

The distributional pattern of dissolved arsenic concentrations from landfill plumes can provide clues to the source of arsenic contamination. Under simple idealized conditions, arsenic concentrations along flow paths in aquifers proximal to a landfill will decrease under anthropogenic sources but potentially increase under in situ sources. This paper presents several conceptual distributional patterns of arsenic in groundwater based on the arsenic source under idealized conditions. An example of advanced subsurface mapping of dissolved arsenic with geophysical surveys, chemical monitoring, and redox fingerprinting is presented for a landfill site in New Hampshire with a complex flow pattern. Tools to assist in the mapping of arsenic in groundwater ultimately provide information on the source of contamination. Once an understanding of the arsenic contamination is achieved, appropriate remedial strategies can then be formulated.

Remediation Journal

Phytoremediation of a petroleum-hydrocarbon contaminated shallow aquifer in Elizabeth City, North Carolina, USA

A former bulk fuel terminal in North Carolina is a groundwater phytoremediation demonstration site where 3,250 hybrid poplars, willows, and pine trees were planted from 2006 to 2008 over approximately 579,000 L of residual gasoline, diesel, and jet fuel. Since 2011, the groundwater altitude is lower in the area with trees than outside the planted area. Soil-gas analyses showed a 95 percent mass loss for total petroleum hydrocarbons (TPH) and a 99 percent mass loss for benzene, toluene, ethylbenzene, and xylenes (BTEX). BTEX and methyl tert-butyl ether concentrations have decreased in groundwater. Interpolations of free-phase, fuel product gauging data show reduced thicknesses across the site and pooling of fuel product where poplar biomass is greatest. Isolated clusters of tree mortalities have persisted in areas with high TPH and BTEX mass. Toxicity assays showed impaired water use for willows and poplars exposed to the site's fuel product, but Populus survival was higher than the willows or pines on-site, even in a noncontaminated control area. All four Populus clones survived well at the site.

North Carolina

Effect of wastewater treatment facility closure on endocrine disrupting chemicals in a Coastal Plain stream

Wastewater treatment facility (WWTF) closures are rare environmental remediation events; offering unique insight into contaminant persistence, long-term wastewater impacts, and ecosystem recovery processes. The U.S. Geological Survey assessed the fate of select endocrine disrupting chemicals (EDC) in surface water and streambed sediment one year before and one year after closure of a long-term WWTF located within the Spirit Creek watershed at Fort Gordon, Georgia. Sample sites included a WWTF-effluent control located upstream from the outfall, three downstream effluent-impacted sites located between the outfall and Spirit Lake, and one downstream from the lake's outfall. Prior to closure, the 2.2-km stream segment downstream from the WWTF outfall was characterized by EDC concentrations significantly higher ( α = 0.05) than at the control site; indicating substantial downstream transport and limited in-stream attenuation of EDC, including pharmaceuticals, estrogens, alkylphenol ethoxylate (APE) metabolites, and organophosphate flame retardants (OPFR). Wastewater-derived pharmaceutical, APE metabolites, and OPFR compounds were also detected in the outflow of Spirit Lake, indicating the potential for EDC transport to aquatic ecosystems downstream of Fort Gordon under effluent discharge conditions. After the WWTF closure, no significant differences in concentrations or numbers of detected EDC compounds were observed between control and downstream locations. The results indicated EDC pseudo-persistence under preclosure, continuous supply conditions, with rapid attenuation following WWTF closure. Low concentrations of EDC at the control site throughout the study and comparable concentrations in downstream locations after WWTF closure indicated additional, continuing, upstream contaminant sources within the Spirit Creek watershed. 

Georgia

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

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

Remediation Journal

Phytoremediation of slightly brackish, polycyclic aromatic hydrocarbon‐contaminated groundwater from 250 ft below land surface: A pilot‐scale study using salt‐tolerant, endophyte‐enhanced hybrid poplar trees at a Superfund site in the Central Valley of California, April‒November 2019

Slightly brackish groundwater contaminated by polycyclic aromatic hydrocarbons (PAHs) at a Superfund site in the Central Valley of California was pumped from 250 feet below land surface to a water storage tank using solar power and then gravity‐fed into 18, 330‐gallon intermediate bulk containers (totes) as follows: (1) Five totes contained planting medium with three salt‐tolerant hybrid poplar trees per tote ( n = 15); (2) Seven totes contained planting medium with three salt‐tolerant hybrid poplar trees per tote and inoculated with the naturally occurring, PAH‐degrading endophyte Pseudomonas putida PD1 ( n = 21); (3) Three totes contained planting medium only ( n = 0); (4) One tote contained groundwater with three PD1‐inoculated trees ( n = 3) and one tote contained groundwater with three regular trees ( n = 3); and (5) One tote contained groundwater only ( n = 0). All trees grew well during the 7‐month growing season in spite of the area's hot, dry air temperature, little precipitation, tote‐influent chloride concentrations of 290 mg/L, and tote‐influent naphthalene concentrations that ranged from 650 to 5100 mg/L. PD1‐inoculated trees initially had 56% larger tree area (tree height × tree width) than regular trees and up to 69% larger tree area by the end of the growing season, indicating some conferred phytoprotection to the PAH contamination. All trees had similar trunk caliper (diameter) and leaf chlorophyll content by the end of the growing season. Total naphthalene removal ranged from 88% to 100% across all totes. The lowest naphthalene removal of 88% was observed in a tote that contained only planting medium and indicates substantial adsorption of naphthalene onto the high organic content of the planting medium. Contaminant removal due to uptake by the hybrid poplar trees was confirmed by the detection of naphthalene in in vivo passive samplers placed in tree trunks. Benzene, toluene, ethylbenzene, total xylenes, 2‐methylnaphthalene, 1,2,4‐trimethylbenzene, and isopropylbenzene were also detected. These results from the pilot‐scale study indicate that a full‐scale application of using salt‐tolerant hybrid poplar trees at this site could effectively decrease naphthalene concentrations in groundwater pumped from the deep aquifer. These initial results provide hope for similar application at other contaminated sites characterized by groundwater at considerable depths, especially at Superfund sites where costly pump‐and‐treat systems have been used long term to treat low levels of groundwater contamination.

California

Dynamics of fecal indicator bacteria, bacterial pathogen genes, and organic wastewater contaminants in the Little Calumet River: Portage Burns Waterway, Indiana

Little information exists on the co-occurrence of fecal indicator bacteria (FIB), bacterial pathogens, and organic wastewater-associated chemicals (OWCs) within Great Lakes tributaries. Fifteen watershed sites and one beach site adjacent to the Little Calumet River–Portage Burns Waterway (LCRPBW) on Lake Michigan were tested on four dates for pH, dissolved oxygen, specific conductance, chloride, color, ammonia- and nitrate-nitrogen, soluble phosphorus, sulfate, turbidity, and atrazine; for concentrations of FIB; and for genes indicating the presence of human-pathogenic enterococci (ENT) and of Shiga-toxin producing Escherichia coli (EC) from various animal sources. Nineteen samples were also tested for 60 OWCs. Half of the watershed samples met EC recreational water quality standards; none met ENT standards. Human-wastewater-associated OWC detections were correlated with human-influence indicators such as population/km 2 , chloride concentrations, and the presence of WWTP effluents, but EC and ENT concentrations were not. Bacterial pathogen genes indicated rural human and several potential animal sources. OWCs of human or ecosystem health concern (musk fragrances AHTN and HHCB, alkylphenols, carbamazepine) and 3 bacterial pathogen genes were detected at the mouth of the LCRPBW, but no such OWCs and only 1 pathogen gene were detected at the beach. The LCRPBW has significant potential to deliver FIB, potential bacterial pathogens, and OWCs of human or ecosystem health concern to the nearshore of Lake Michigan, under conditions enhancing nearshore transport of the river plume. Nearshore mixing of lake and river water, and the lack of relationship between OWCs and FIB or pathogen genes, pose numerous challenges for watershed and nearshore assessment and remediation.

Indiana

Degradation of 1,1,2,2-tetrachloroethane and accumulation of vinyl chloride in wetland sediment microcosms and in situ porewater: Biogeochemical controls and associations with microbial communities

The biodegradation pathways of 1,1,2,2-tetrachloroethane (TeCA) and 1,1,2-trichloroethane (112TCA) and the associated microbial communities in anaerobic wetland sediments were evaluated using concurrent geochemical and genetic analyses over time in laboratory microcosm experiments. Experimental results were compared to in situ porewater data in the wetland to better understand the factors controlling daughter product distributions in a chlorinated solvent plume discharging to a freshwater tidal wetland at Aberdeen Proving Ground, Maryland. Microcosms constructed with wetland sediment from two sites showed little difference in the initial degradation steps of TeCA, which included simultaneous hydrogenolysis to 112TCA and dichloroelimination to 1,2-dichloroethene (12DCE). The microcosms from the two sites showed a substantial difference, however, in the relative dominance of subsequent dichloroelimination of 112TCA. A greater dominance of 112TCA dichloroelimination in microcosms constructed with sediment that was initially iron-reducing and subsequently simultaneously iron-reducing and methanogenic caused approximately twice as much vinyl chloride (VC) production as microcosms constructed with sediment that was methanogenic only throughout the incubation. The microcosms with higher VC production also showed substantially more rapid VC degradation. Field measurements of redox-sensitive constituents, TeCA, and its anaerobic degradation products along flowpaths in the wetland porewater also showed greater production and degradation of VC with concurrent methanogenesis and iron reduction. Molecular fingerprinting indicated that bacterial species [represented by a peak at a fragment size of 198 base pairs (bp) by MnlI digest] are associated with VC production from 112TCA dichloroelimination, whereas methanogens (190 and 307 bp) from the Methanococcales or Methanobacteriales family are associated with VC production from 12DCE hydrogenolysis. Acetate-utilizing methanogens (acetotrophs) appear to be involved in the biodegradation of VC. The relative abundance of Methanosarcinaceae, the only methanogen group with acetotrophic members, doubled in microcosms in which degradation of VC was observed. In addition, molecular analyses using primers specific for known dehalorespiring bacteria in the Dehalococcoides and Desulfuromonas groups showed the presence of these bacteria in microcosm slurry from the site that showed the highest VC production and degradation. Determination of biogeochemical controls and microbial consortia involved in TeCA degradation is leading to a better understanding of the heterogeneity in biodegradation rates and daughter product distribution in the wetland, improving capabilities for developing remediation and monitoring plans.

Journal of Contaminant Hydrology

The use of historical imagery in the remediation of an urban hazardous waste site

The information derived from the interpretation of historical aerial photographs is perhaps the most basic multitemporal application of remote-sensing data. Aerial photographs dating back to the early 20th century can be extremely valuable sources of historical landscape activity. In this application, imagery from 1918 to 1927 provided a wealth of information about chemical weapons testing, storage, handling, and disposal of these hazardous materials. When analyzed by a trained photo-analyst, the 1918 aerial photographs resulted in 42 features of potential interest. When compared with current remedial activities and known areas of contamination, 33 of 42 or 78.5% of the features were spatially correlated with areas of known contamination or other remedial hazardous waste cleanup activity.

IEEE Journal of Selected Topics in Applied Earth O

Monitoring the effect of poplar trees on petroleum-hydrocarbon and chlorinated-solvent contaminated ground water

At contaminated groundwater sites, poplar trees can be used to affect ground-water levels, flow directions, and ultimately total groundwater and contaminant flux to areas downgradient of the trees. The magnitude of the hydrologic changes can be monitored using fundamental concepts of groundwater hydrology, in addition to plant physiology-based approaches, and can be viewed as being almost independent of the contaminant released. The affect of poplar trees on the fate of groundwater contaminants, however, is contaminant dependent. Some petroleum hydrocarbons or chlorinated solvents may be mineralized or transformed to innocuous compounds by rhizospheric bacteria associated with the tree roots, mineralized or transformed by plant tissues in the transpiration stream or leaves after uptake, or passively volatilized and rapidly dispersed or oxidized in the atmosphere. These processes also can be monitored using a combination of physiological- or geochemical-based field or laboratory approaches. When combined, such hydrologic and contaminant monitoring approaches can result in a more accurate assessment of the use of poplar trees to meet regulatory goals at contaminated groundwater sites, verify that these goals continue to be met in the future, and ultimately lead to a consensus on how the performance of plant-based remedial strategies (phytoremediation) is to be assessed.

International Journal of Phytoremediation

Non-invasive flow path characterization in a mining-impacted wetland

Time-lapse electrical resistivity (ER) was used to capture the dilution of a seasonal pulse of acid mine drainage (AMD) contamination in the subsurface of a wetland downgradient of the abandoned Pennsylvania mine workings in central Colorado. Data were collected monthly from mid-July to late October of 2013, with an additional dataset collected in June of 2014. Inversion of the ER data shows the development through time of multiple resistive anomalies in the subsurface, which corroborating data suggest are driven by changes in total dissolved solids (TDS) localized in preferential flow pathways. Sensitivity analyses on a synthetic model of the site suggest that the anomalies would need to be at least several meters in diameter to be adequately resolved by the inversions. The existence of preferential flow paths would have a critical impact on the extent of attenuation mechanisms at the site, and their further characterization could be used to parameterize reactive transport models in developing quantitative predictions of remediation strategies.

Colorado

Nodal failure index approach to groundwater remediation design

Computer simulations often are used to design and to optimize groundwater remediation systems. We present a new computationally efficient approach that calculates the reliability of remedial design at every location in a model domain with a single simulation. The estimated reliability and other model information are used to select a best remedial option for given site conditions, conceptual model, and available data. To evaluate design performance, we introduce the nodal failure index (NFI) to determine the number of nodal locations at which the probability of success is below the design requirement. The strength of the NFI approach is that selected areas of interest can be specified for analysis and the best remedial design determined for this target region. An example application of the NFI approach using a hypothetical model shows how the spatial distribution of reliability can be used for a decision support system in groundwater remediation design. ?? 2008 ASCE.

Journal of Geotechnical and Geoenvironmental Engin

Helping Students make the transition from novice learner of ground-water concepts to expert using the Plume Busters software

Environmental and earth science students are novice learners and lack the experience needed to rise to the level of expert. To address this problem we have developed the prototype Plume Busters?? software as a capstone educational experience, in which students take on the role of an environmental consultant. Following a pipeline spill, the environmental consultant is hired by the pipeline owner to locate the resulting plume created by spill and remediate the contaminated aquifer at minimum monetary and time cost. The contamination must be removed from the aquifer before it reaches the river and eventually a downstream public water supply. The software consists of an interactive Java application and accompanying HTML linked pages. The application simulates movement of a plume from a pipeline break throug h a shallow alluvial aquifer towards the river. The accompanying web pages establish the simulated contamination scenario and provide students with background material on ground-water flow and transport principles. To make the role-play more realistic, the student must consider cost and time when making decisions about siting observation wells and wells for the pump-and-treat remediation system.

Journal of Geoscience Education