Quantifying groundwater flow variability in a poorly cemented fractured sandstone aquifer to inform in situ remediation.

This study applies innovative methods to characterize and quantify the magnitude of groundwater flow in a fractured and variably cemented sandstone aquifer to inform an in-situ remediation strategy for trichloroethene (TCE) contamination. A modified active-distributed temperature sensing (A-DTS) approach in which fiber optic cables were permanently grouted in the borehole was used to quantify groundwater flow rates. Two additional tracer tests were conducted: 1) fluorescein tracer injection followed by rock coring and sampling for visual mapping and porewater analysis, and 2) deployment of passive flux meters in conventional monitoring wells to evaluate groundwater velocity and mass flux distributions. Forced gradient injection of fluorescein tracer suggests a dual porosity flow system wherein higher rates of groundwater flow occur within discrete features including highly permeable bedding planes and fractures, with slower flow occurring within the rock matrix. Tracer was observed and detected in the unfractured matrix porewater >1.5 m away from the injection well. Beyond this distance, >6 m radially away from the injection hole, tracer was primarily detected within and adjacent to high transmissivity fractures serving as preferential flow paths. The Darcy flux calculated using active distributed temperature sensing (A-DTS) shows depth-discrete values ranging from 7 to 60 cm/day, with average and median values of 23 and 17 cm/day, respectively. Passive Flux Meters (PFMs) deployed in three conventional monitoring wells with slotted screens and sand filter packs showed groundwater flux values ranging from 2 to 11 cm/day, with an overall average of 4 cm/day and are likely biased low due to spreading in the sand pack. The study results were used to inform an in-situ remediation system design including the proposed injection well spacing and the amendment delivery approach. In addition, the results were used to build confidence in the viability of delivering an oxidant to the rock matrix via advective processes. This is important because 1) the matrix is where the majority of the TCE mass occurs, and 2) it provides insights on processes that directly affect remedial performance expectations given advective delivery to preferential pathways and the matrix overcomes diffusion only conditions.

Assessing aquitard integrity in a complex aquifer - aquitard system contaminated by chlorinated hydrocarbons.

This study investigates for the first time the integrity of multiple stacked aquitards with different degrees of contaminant degradation. Aquitard integrity was assessed in a contaminated, multi-layered, alluvial aquifer-aquitard system (Ferrara, northern Italy). The system was contaminated by mixed organic contaminants of industrial origin (mostly chlorinated ethenes) that were illegally disposed in an urban dump four to five decades ago. High spatial resolution profiles of hydraulic head, geochemistry and chlorinated hydrocarbon concentrations were determined through the multi-layered system via discrete interval sampling of continuous cores and multilevel groundwater sampling, at three locations aligned along a transect adjacent to the buried waste to a maximum depth of 53 m below the water table. The profiles revealed that the two shallow aquitards had low integrity with respect to impeding downward migration of dense non-aqueous phase liquid (DNAPL), and provided little protection to the underlying aquifers against DNAPL contamination due to preferential pathways through imperceptible fractures and/or permeable micro-beds. However, both aquitards inhibited downward DNAPL migration to some extent due to DNAPL retention along its flow paths and accumulation at lower permeability interfaces, with decreasing peak concentrations at the top of successively deeper aquitard units. Moreover, both aquitards enhanced contaminant biodegradation due to the occurrence of organic rich sub-layers, influencing the contaminant plume composition, mobility and fate in the underlying and overlying aquifers. The deepest aquitard showed evidence of DNAPL accumulation at the top and slow diffusion-dominated transport consistent with 40 years of transport, suggesting higher integrity compared to the two shallower aquitards. However, the occurrence of micro-fractures and/or discontinuities in the aquitard upgradient under the dump (source) is the most likely explanation for contamination of the deepest aquifer. Analytical 1-D simulations of the diffusion profiles in the deepest aquitard revealed that DNAPL contamination down to the top of this aquitard occurred with minimal delay after DNAPL waste disposal began. The results highlight the necessity of high-resolution vertical profiling for assessing the presence of imperceptible features relevant to DNAPL migration and integrity of individual aquitards affecting organic contaminant source zone mass and phase distributions over decades.

Identification of Degradation Pathways of Chlorohydrocarbons in Saturated Low-Permeability Sediments Using Compound-Specific Isotope Analysis.

This study aims to investigate whether compound-specific carbon isotope analysis (CSIA) can be used to differentiate the degradation pathways of chlorohydrocarbons in saturated low-permeability sediments. For that purpose, a site was selected, where a complex mixture of chlorohydrocarbons contaminated an aquifer-aquitard system. Almost 50 years after contaminant releases, high-resolution concentration, CSIA, and microbial profiles were determined. The CSIA profiles showed that in the aquitard cis-dichloroethene (cDCE), first considered as a degradation product of trichloroethene (TCE), is produced by the dichloroelimination of 1,1,2,2-tetrachloroethane (TeCA). In contrast, TeCA degrades to TCE via dehydrohalogenation in the aquifer, indicating that the aquifer-aquitard interface separates two different degradation pathways for TeCA. Moreover, the CSIA profiles showed that chloroform (CF) is degraded to dichloromethane (DCM) via hydrogenolysis in the aquitard and, to a minor degree, produced by the degradation of carbon tetrachloride (CT). Several microorganisms capable of degrading chlorohydrocarbons were detected in the aquitard, suggesting that aquitard degradation is microbially mediated. Furthermore, numerical simulations reproduced the aquitard concentration and CSIA profiles well, which allowed the determination of degradation rates for each transformation pathway. This improves the prediction of contaminant fate in the aquitard and potential magnitude of impacts on the adjacent aquifer due to back-diffusion.

DFN-M field characterization of sandstone for a process-based site conceptual model and numerical simulations of TCE transport with degradation.

Plumes of trichloroethene (TCE) with degradation products occur at a large industrial site in California where TCE as a dense non-aqueous phase liquid (DNAPL) entered the fractured sandstone bedrock at many locations beginning in the late 1940s. Groundwater flows rapidly in closely spaced fractures but plume fronts are strongly retarded relative to groundwater flow velocities owing largely to matrix diffusion in early decades and degradation processes in later decades and going forward. Multiple data types show field evidence for both biotic and abiotic dechlorination of TCE and its degradation products, resulting in non-chlorinated compounds. Analyses were conducted on groundwater samples from hundreds of monitoring wells and on thousands of rock samples from continuous core over depths ranging from 6 to 426 metres below ground surface. Nearly all of the present-day mass of TCE and degradation products resides in the water-saturated, low-permeability rock matrix blocks. Although groundwater and DNAPL flow primarily occur in the fractures, DNAPL dissolution followed by diffusion and sorption readily transfers contaminant mass into the rock matrix. The presence of non-chlorinated degradation products (ethene, ethane, acetylene) and compound specific isotope analysis (CSIA) of TCE and cis-1,2-dichloroethene (cDCE) indicate at least some complete dechlorination by both biotic and abiotic pathways, consistent with the observed mineralogy and hydrogeochemistry and with published results from crushed rock microcosms. The rock matrix contains abundant iron-bearing minerals and solid-phase organic carbon with large surface areas and long contact times, suggesting degradation processes are occurring in the rock matrix. Multiple, high-resolution datasets provide strong evidence for spatially heterogeneous distributions of TCE and degradation products with varying degrees of degradation observed only when using new methods that achieve better detection of dissolved gases (i.e., Snap Sampler™) and contaminant mass stored in the low permeability rock matrix (i.e., CORE-DFN™). Simulations using a discrete fracture-matrix (DFN-M) numerical model capable of rigorously simulating flow and transport in both the fractures and matrix, including interactions, show that even slow, first-order degradation rates (i.e., 5- to 20-year half-lives) informed by site-derived parameters can contribute strongly to natural attenuation, resulting in TCE plumes that become stationary in space and might even retreat after 50 to 100 years, if the DNAPL sources become depleted due to the combination of diffusion and degradation processes.

Determination of Cr(III) solids formed by reduction of Cr(VI) in a contaminated fractured bedrock aquifer: Evidence for natural attenuation of Cr(VI).

Hexavalent chromium Cr(VI) is toxic and can be highly mobile in many aquifer systems. Redox reactions with naturally occurring minerals and organic compounds can reduce Cr(VI) to Cr(III), forming labile Cr(III) oxyhydroxide precipitates, which is a natural attenuation process. In fractured bedrock aquifers, reduction of Cr(VI) in the rock matrix can enhance attenuation beyond that from matrix diffusion only, and potentially reduce back diffusion if concentrations in fractures decline following source reduction via natural processes or engineered remediation. In this study, we develop an extraction method for labile Cr(III) precipitates from Cr(VI) reduction using 5% hydrogen peroxide (H2O2). Combining Cr(III) extractions with an established sodium hydroxide (NaOH) method for determination of Cr(VI) concentrations in rock porewater, a measure of the labile Cr(III) and Cr(VI) fractions in geologic samples is achieved. The methods were applied to cores from a contaminated groundwater system in fractured porous bedrock in order to assess the effectiveness of natural attenuation and whether Cr(VI) mass that diffused into the bedrock matrix was undergoing reduction. Detailed vertical distributions display two depth intervals with corresponding elevated concentrations of Cr(VI) in the porewater and extractable total Cr. The correspondence of Cr(VI) and labile Cr(III) provides evidence for reduction of Cr(VI) contamination in the bedrock matrix. Mineralogical analysis suggests that Fe(II)-bearing minerals, chlorite and biotite are the most likely candidates for natural reductants. This study provides evidence for the natural attenuation of anthropogenic Cr(VI) contamination in the porewater of a fractured bedrock aquifer, and it outlines a quantitative method for evaluating the effectiveness of natural attenuation in groundwater systems.

Quantification of Degradation of Chlorinated Hydrocarbons in Saturated Low Permeability Sediments Using Compound-Specific Isotope Analysis.

This field and modeling study aims to reveal if degradation of chlorinated hydrocarbons in low permeability sediments can be quantified using compound-specific isotope analysis (CSIA). For that purpose, the well-characterized Borden research site was selected, where an aquifer-aquitard system was artificially contaminated by a three component chlorinated solvent mixture (tetrachloroethene (PCE) 45 vol %, trichloroethene (TCE) 45 vol %, and chloroform (TCM) 10 vol %). Nearly 15 years after the contaminant release, several high-resolution concentration and CSIA profiles were determined for the chlorinated hydrocarbons that had diffused into the clayey aquitard. The CSIA profiles showed large shifts of carbon isotope ratios with depth (up to 24‰) suggesting that degradation occurs in the aquitard despite the small pore sizes. Simulated scenarios without or with uniform degradation failed to reproduce the isotope data, while a scenario with decreasing degradation with depth fit the data well. This suggests that nutrients had diffused into the aquitard favoring stronger degradation close to the aquifer-aquitard interface than with increasing depth. Moreover, the different simulation scenarios showed that CSIA profiles are more sensitive to different degradation conditions compared to concentration profiles highlighting the power of CSIA to constrain degradation activities in aquitards.

Testing high resolution numerical models for analysis of contaminant storage and release from low permeability zones.

It is now widely recognized that contaminant release from low permeability zones can sustain plumes long after primary sources are depleted, particularly for chlorinated solvents where regulatory limits are orders of magnitude below source concentrations. This has led to efforts to appropriately characterize sites and apply models for prediction incorporating these effects. A primary challenge is that diffusion processes are controlled by small-scale concentration gradients and capturing mass distribution in low permeability zones requires much higher resolution than commonly practiced. This paper explores validity of using numerical models (HydroGeoSphere, FEFLOW, MODFLOW/MT3DMS) in high resolution mode to simulate scenarios involving diffusion into and out of low permeability zones: 1) a laboratory tank study involving a continuous sand body with suspended clay layers which was 'loaded' with bromide and fluorescein (for visualization) tracers followed by clean water flushing, and 2) the two-layer analytical solution of Sale et al. (2008) involving a relatively simple scenario with an aquifer and underlying low permeability layer. All three models are shown to provide close agreement when adequate spatial and temporal discretization are applied to represent problem geometry, resolve flow fields and capture advective transport in the sands and diffusive transfer with low permeability layers and minimize numerical dispersion. The challenge for application at field sites then becomes appropriate site characterization to inform the models, capturing the style of the low permeability zone geometry and incorporating reasonable hydrogeologic parameters and estimates of source history, for scenario testing and more accurate prediction of plume response, leading to better site decision making.

Role of back diffusion and biodegradation reactions in sustaining an MTBE/TBA plume in alluvial media.

A methyl tert-butyl ether (MTBE) / tert-butyl alcohol (TBA) plume originating from a gasoline spill in late 1994 at Vandenberg Air Force Base (VAFB) persisted for over 15 years within 200 feet of the original spill source. The plume persisted until 2010 despite excavation of the tanks and piping within months after the spill and excavations of additional contaminated sediments from the source area in 2007 and 2008. The probable history of MTBE concentrations along the plume centerline at its source was estimated using a wide variety of available information, including published details about the original spill, excavations and monitoring by VAFB consultants, and our own research data. Two-dimensional reactive transport simulations of MTBE along the plume centerline were conducted for a 20-year period following the spill. These analyses suggest that MTBE diffused from the thin anaerobic aquifer into the adjacent anaerobic silts and transformed to TBA in both aquifer and silt layers. The model reproduces the observation that after 2004 TBA was the dominant solute, diffusing back out of the silts into the aquifer and sustaining plume concentrations much longer than would have been the case in the absence of such diffusive exchange. Simulations also suggest that aerobic degradation of MTBE or TBA at the water table in the overlying silt layer significantly affected concentrations of MTBE and TBA by limiting the chemical mass available for back diffusion to the aquifer.

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation.

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.

Groundwater-surface water interaction and its role on TCE groundwater plume attenuation.

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.

Pump-and-treat remediation of chlorinated solvent contamination at a controlled field-experiment site.

Pump-and-treat (P&T) remediation and associated concentration tailing are investigated at the field scale in a mildly heterogeneous sandy aquifer through the extraction of dissolved chlorinated solvent plumes that had developed over 475 d from a multicomponent dense nonaqueous-phase liquid (DNAPL) source intentionally emplaced in the aquifer at the Borden (ON) research site. Extraction was accomplished via a source-containment well located 25 m from the source and two further downgradient plume-centerline wells to remove the advancing high-concentration dissolved plumes. The 550 days of detailed P&T field data demonstrated the following: remediation, albeit slowly, of the leading 25-60 m plume section to around typical drinking water standard concentrations; concentration tailing (reduction) over 4 orders of magnitude in the plume; a steady-state concentration "plateau" in the source-containment well capturing the steadily dissolving DNAPL source; influences of extraction rate changes (concentration rebounds); and, lengthy tailing from inter-well stagnation-zone areas. Much of the contaminant behavior during the P&T appeared to be "ideal" in the sense that with appropriate specification of the source term and pumping regime, it was reasonably predicted by 3-dimensional numerical model (HydroGeoSphere) simulations that assumed ideal (macrodispersion, linear sorption, etc.) transport. Supporting lab studies confirmed nonideal sorption was, however, important at the point sample scale with enhanced PCE (tetrachloroethene) sorption to low- and high-permeability strata and moderate nonlinear and competitive sorption influences. Although there was limited evidence of nonideal tailing contributions to the field data (underprediction of some tailing curve gradients), such contributions to P&T tailing were not easily discerned and appeared to play a relatively minor role within the mildly heterogeneous aquifer studied.

Field study of TCE diffusion profiles below DNAPL to assess aquitard integrity.

An area where a free-product accumulation of trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) occurs at the bottom of a 10-m-thick surficial sand aquifer was studied to determine the integrity of the underlying, 20-m-thick, clayey silt aquitard formed of glaciolacustrine sediment. TCE concentration-versus-depth profiles determined from aquitard cores collected at five locations indicated penetration of detectable TCE 2.5 to 3.0 m into the aquitard. Two of the profiles show persistent DNAPL at the aquitard interface, while two others indicate that DNAPL, present initially, was completely dissolved away producing concentration declines at the aquitard interface. The fifth profile suggests shallow DNAPL penetration (<0.5 m) into the aquitard, however, this penetration, which was likely caused by cross-contamination during core collection or cone penetrometry (CPT) of the aquitard interface, did not increase the maximum depth of TCE penetration. Combining the field profiles with one-dimensional model simulations, downward migration of the aqueous TCE front, defined as the EPA MCL of 5 microg/l, which was below the analytical detection limit, was projected to a distance between 4 and 5 m below the top of the aquitard. Using a single set of estimated aquitard parameter values, simulations of aqueous TCE migration into the aquitard provided a good fit to four of the field profiles with a migration time of 35 to 45 years, consistent with the history of TCE use at the site. These simulations indicate aqueous TCE migration is diffusion-dominated with only small advective influence by the downward groundwater velocity of 2 to 3 cm/year or less in the aquitard due to pumping of the underlying aquifer to supply water to the facility in the past 50 years. The applicability of the parameter values was confirmed by in situ diffusion experiments of 1-year duration, in which stainless steel cylinders containing DNAPL were inserted into the aquitard. The diffusion-dominated nature of the profiles indicates that the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells, concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after the breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells , concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard.