The in situ treatment of PFAS within porewater at the air–water interface of a PFAS source zone

The treatment of per- and polyfluoroalkyl substances (PFAS) within groundwater is an emerging topic, with various technologies being researched and tested. Currently, PFAS-impacted groundwater is typically treated ex situ using sorptive media such as activated carbon and ion exchange resin. Proven in situ remedial approaches for groundwater have been limited to colloidal activated carbon (CAC) injected into aquifers downgradient of the source zones. However, treatment of groundwater within the source zones has not been shown to be feasible to date. This study evaluated the use of CAC to treat dissolved PFAS at the air–water interface within the PFAS source zone. Studies have shown that PFAS tends to preferentially accumulate at the air–water interface due to the chemical properties of the various PFAS. This accumulation can act as a long-term source for PFAS, thus making downgradient treatment of groundwater a long-term requirement. A solution of CAC was injected at the air–water interface within the source zone at a site with PFAS contamination using direct push technology. A dense injection grid that targeted the interface between the air and groundwater was used to deliver the CAC. Concentrations of PFAS within the porewater and groundwater were collected using a series of nine lysimeters installed within the vadose and saturated water columns. A total of six PFAS were detected in the porewater and groundwater including perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). Detectable concentrations of PFAS within the pore and groundwater before treatment ranged from values greater than 300 µg/L for PFPeA to less than 3 µg/L for PFNA. Following the injection of the CAC, monitoring of the porewater and groundwater for PFAS was conducted approximately 3, 6, 9, 12, and 18 months postinjection. The results indicated that the PFAS within the porewater and groundwater at and near the air–water interface was effectively attenuated over the 1.5-year monitoring program, with PFAS concentrations being below the method detection limits of approximately 10 ng/L, with the exception of PFPeA, which was detected within the porewater during the 18-month sampling event at concentrations of up to 55 ng/L. PFPeA is a five carbon-chained PFAS that has been shown to have a lower affinity for sorption onto activated carbon compared to the longer carbon-chained PFAS such as PFOA. Examination of aquifer cores in the zone of injection indicated that the total organic carbon concentration of the aquifer increased by five orders of magnitude postinjection, with 97% of the samples collected within the target injection area containing activated carbon, indicating that the CAC was successfully delivered into the source zone.     

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 the 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. Afterward, 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 (nonhydraulically stressed) sampling negates the need to extract water and potentially dewater the test zone. The authors 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. The testing was performed at the former Pease Air Force Base (PAFB) in Portsmouth, New Hampshire. Bedrock at the former PAFB consists of fractured metasedimentary rocks where the authors investigated back diffusion of cis‐1,2‐dichloroethylene (cis‐1,2‐DCE), a CVOC. Postsparging concentrations of cis‐1,2‐DCE showed initial rebounding followed by declines, excluding an episodic spike in concentrations from a groundwater recharge event. The authors theorize that there are three processes that controlled concentration responses in the test zones postsparging. First, the limited back diffusion of CVOCs from a halo or thin zone of rock around the borehole contributes to the initial rebounding. Second, aerobic degradation of cis‐1,2‐DCE occurred causing declines in concentrations in the test zone. Third, microflow from microfractures contributed to the episodic spike in concentrations following the groundwater recharge event. In active flow zones, the latter two processes are not measurable due to equilibration from groundwater transport between the borehole and active flowing fractures.     

Development of Layered Sediment Structure and its Effects on Pore Water Transport and Hyporheic Exchange

Hyporheic exchange is known to provide an important control on nutrient and contaminant fluxes across the stream-subsurface interface. Similar processes also mediate interfacial transport in other permeable sediments. Recent research has focused on understanding the mechanics of these exchange processes and improving estimation of exchange rates in natural systems. While the structure of sediment beds obviously influences pore water flow rates and patterns, little is known about the interplay of typical sedimentary structures, hyporheic exchange, and other transport processes in fluvial/alluvial sediments. Here we discuss several processes that contribute to local-scale sediment heterogeneity and present results that illustrate the interaction of overlying flow conditions, the development of sediment structure, pore water transport, and stream-subsurface exchange. Layered structures are shown to develop at several scales within sediment beds. Surface sampling is used to analyze the development of an armor layer in a sand-and-gravel bed, while innovative synchrotron-based X-ray microtomography is used to observe patterns of grain sorting within sand bedforms. We show that layered bed structures involving coarsening of the bed surface increase interfacial solute flux but produce an effective anisotropy that favors horizontal pore water transport while limiting vertical penetration.     

Modeling of water quality downgradient of a mulch biowall

Groundwater treatment biowalls may be located close to a surface water body to prevent contaminant discharge from a groundwater plume into the surface water. Groundwater contaminants passing through the biowall are treated within the biowall or immediately downgradient of the biowall. Biowalls designed and constructed for the treatment of chlorinated solvents typically contain either a solid and/or liquid source of organic carbon to promote contaminant degradation by enhanced anaerobic reductive dechlorination. Common solid organic materials in biowalls include wood mulch or similar waste plant material, and common liquid organic materials are vegetable oil (possibly emulsified) or other long‐chain fatty acids. Such biowalls then develop anaerobic conditions in the constructed biowall volume, and potentially downgradient, as dissolved oxygen originally present in the aquifer is consumed. This groundwater condition can lead to the appearance of sulfide if groundwater influent to the biowall contains moderate to high sulfate concentrations. Other researchers have presented evidence for groundwater conditions downgradient of a biowall or a permeable reactive barrier (PRB) that are altered in relation to groundwater quality, besides the desired effect of contaminant degradation or removal by precipitation. The objective of this work was to investigate with modeling the changes in downgradient groundwater species chemistry as a result of a constructed biowall. This was accomplished with a chemical species model to predict levels of sulfate and sulfide present in groundwater in close downgradient proximity to the biowall. The results indicate that downgradient chemical changes could impact a surface water body to which groundwater discharges. The model described could be enhanced by incorporating additional design variables that should be considered in biowall feasibility assessments.     

Landfill leachate assessment by hydrological and geophysical data: case study NamSon,Hanoi, Vietnam

The main objective of this study was to assess the impact of the NamSon landfill on subsurface geological structure and hydrological environment by geophysical techniques and hydrochemical analysis of surface and groundwater. The electrical resistivity tomography (ERT), self-potential (SP) and very low frequency (VLF) methods were used for the investigation of geological structure near the landfill. Three profiles (900 m long in total) of the two-dimensional ERT, VLF density sections and 180 SP data points scattered throughout the study area near the disposal site constituted the basis of the data used in analysis. Additionally, surface water and groundwater samples were collected from six sites in the area for the chemical analysis. Interpretations of geophysical data show a low resistivity zone (< 15 Ωm), which appears to be a fully saturated zone with leachate from landfill. The results of the geophysical investigations are not always fully confirmed by the results of hydrochemical analysis. The quality of water in the vicinity of the landfill dramatically decreased over the year (2015–2016) and actions should be taken to inverse this negative trend.

     

Stratigraphic flux—A method for determining preferential pathways for complex sites

Experience with groundwater remediation over several decades has demonstrated that successful outcomes depend on quantitative conceptual site models (CSMs). Over the last 30 years, we have progressed from groundwater pump‐and‐treat remedies, which were largely designed based on a water supply perspective, to in situ and combined remedy strategies, which are only beginning to benefit from understanding the aquifer architecture and distribution of contaminant mass to assess plume maturity, mass flux, and more reliable means of fate and transport assessment. The U.S. Air Force funded the development of the Stratigraphic Flux approach to provide a framework for understanding contaminant transport pathways at its complex sites and enable more reliable and cost‐effective remediation. Stratigraphic Flux enables the development of quantitative, flux‐based CSMs that are founded in sequence stratigraphy, and high‐resolution hydraulic conductivity and contaminant distribution measurements. The result is a three‐dimensional graphical mapping of relative contaminant flux and classification of transport potential that is easy for all stakeholders to understand. The Stratigraphic Flux graphical model is based on a hydrofacies classification system that describes transport potential in three segments of the aquifer: transport zones—where the majority of groundwater flow occurs and transport rates are measured in feet per day; slow advection zones—where transport rates are measured in feet per year; and storage zones—where typically less than 1% of flow occurs, and diffusion dominates contaminant transport. The hydrofacies architectures are based on stratigraphy and transport potential is defined by grouping facies by orders of magnitude classes in hydraulic conductivity. By combining the hydrofacies architecture with contaminant concentration distributions, one can map relative contaminant flux to define and target the complex pathways that control contaminant transport and cleanup behavior. In this article, we describe the Stratigraphic Flux framework, focusing on the key information needed and the methods of analysis. We illustrate the results of its application to evaluate migration pathways for trichlorethylene and chromium at a former chrome pit at Air Force Plant 4 in Fort Worth, Texas. A comprehensive guidance document that describes the approach with a broad spectrum of tools and several site examples can be requested from the authors.     

Assessment of in situ thermal treatment for chlorinated organic source zones

The East Gate Disposal Yard (EGDY) at Fort Lewis is the source of a large trichloroethene (TCE) plume at this military installation. Source reduction using thermal treatment was applied using electrical resistance heating. A total of about 5,800 kg of TCE‐equivalent volatile organic compounds (VOCs; TCE and dichloroethene) was extracted during thermal treatment of the three zones selected for source reduction. Pretreatment groundwater TCE concentrations were measured up to 100 ppm. Posttreatment groundwater TCE concentrations within the treatment zones averaged less than 100 ppb. Posttreatment soil TCE concentrations decreased by over 96 percent compared to pretreatment soil concentrations. The overall contaminant flux from EGDY was reduced by an estimated 60 to 90 percent by the source reduction effort. The traditional and new techniques for site characterization and remediation performance monitoring applied at EGDY provide insight for installing, operating, monitoring, and assessing thermal treatment. © 2009 Wiley Periodicals, Inc.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 2. Results From Three Sites

The data mining/groundwater modeling methodology developed in McDade et al. (2013) was performed to determine if matrix diffusion is a plausible explanation for the lower‐concentration but persistent chlorinated solvent plumes in the groundwater‐bearing units at three different pump‐and‐treat systems. Capture‐zone maps were evaluated, and eight wells were identified that did not draw water from any of the historical source areas but captured water from the sides of the plume. Two groundwater models were applied to study the persistence of the plumes in the absence of contributions from the historical source zones. In the wells modeled, the observed mass discharge generally decreased by about one order of magnitude or less over 4 to 10 years of pumping, and 1.8 to 17 pore volumes were extracted. In five of the eight wells, the matrix diffusion model fit the data much better than the advection dispersion retardation model, indicating that matrix diffusion better explains the persistent plume. In the three other wells, confounding factors, such as a changing capture zone over time (caused by changes in pumping rates in adjacent extraction wells); potential interference from a high‐concentration unremediated source zone; and limited number of pore volumes removed made it difficult to confirm that matrix diffusion processes were active in these areas. Overall, the results from the five wells indicate that mass discharge rates from the pumping wells will continue to show a characteristic “long tail'' of mass removal from zones affected by active matrix diffusion processes. Future site management activities should include matrix diffusion processes in the conceptual site models for these three sites. © 2013 Wiley Periodicals, Inc.     

Remediation and review: Developing groundwater strategy at the hanford site

The U.S. Department of Energy's (US DOE's) environmental challenges include remediation of the Hanford Site in Washington State. The site's legacy from nuclear weapons “production” activities includes approximately 80 square miles of contaminated groundwater, containing radioactive and other hazardous substances at levels above drinking water standards. In 1998, the U.S. General Accounting Office (US GAO), the auditing arm of Congress, concluded that groundwater remediation at Hanford should be integrated with a comprehensive understanding of the “vadose zone,” the soil region between the ground surface and groundwater. The US DOE's Richland Operations Office adjusted its program in response, and groundwater/vadose‐zone efforts at Hanford have continued to develop since that time. Hanford provides an example of how a federal remediation program can be influenced by reviews from the US GAO and other organizations, including the US DOE itself. © 2008 Wiley Periodicals, Inc.     

The use of zero‐valent iron injection to remediate groundwater: Results of a pilot test at the Marshall Space Flight Center

In situ treatability studies are being conducted to evaluate various in situ technologies to manage groundwater contamination at the NASA Marshall Space Flight Center in Huntsville, Alabama. The focus of these studies is to evaluate remediation options for contaminated (mostly aerobic) groundwater occurring within the basal portion of a clayey residuum called the rubble zone. The tension‐saturated media and unsaturated media lying above the rubble zone are also being treated where they make up a significant component of the contaminant mass. An in situ chemical reduction field pilot test was implemented (following bench‐scale tests) during July and August 2000. The test involved the injection of zero‐valent iron powder in slurry form, using the Ferox^SM process patented by ARS Technologies, Inc. The pilot test focused on trichloroethene (TCE)‐contaminated groundwater within the rubble zone. Maximum pre‐injection concentrations of about 72,800 micrograms per liter (μg/l) were observed and no secondary sources are believed to exist beneath the area. The potential presence of unexploded ordnance forced an implementation strategy where source area injections were completed, as feasible, followed by overlapping injections in a down gradient alignment to create a permeable reactive zone for groundwater migration. Eight post‐injection rounds of groundwater performance monitoring were completed. The results are encouraging, in terms of predicted responses and decreasing trends in contaminant levels. © 2003 Wiley Periodicals, Inc.     

Chlorinated Solvent Treatment Wetland

A first‐of‐its‐kind wetland restoration project was completed in October 2000 to treat trichloroethene‐(TCE‐)impacted groundwater from a former manufacturing facility prior to discharge into a highly valued recreational surface water body in the upper Midwest. This article summarizes the design, construction, operation, and effectiveness of the restored wetland. The groundwater‐surface water discharge zone at the site was restored as a wetland to improve the natural degradation of TCE and subsequent degradation by‐products. For the past 11 years, the treatment wetland performance was evaluated by monitoring the wetland vegetation, wetland hydraulics, and water chemistry. Water quality data have been used to assess the wetland geochemistry, TCE and TCE‐degradation by‐product concentrations within the wetland, and the surface water quality immediately downgradient of the wetland. The treatment wetland has been performing according to design, with TCE and TCE‐degradation by‐products not exceeding surface water criteria. The monitoring results show that TCE and TCE‐degradation by‐products are entering the treatment wetland via natural hydraulic gradients and that the geochemistry of the wetland supports both reductive dechlorination (anaerobic degradation) and cometabolic degradation (aerobic degradation) of TCE and TCE‐degradation by‐products: cis‐ and trans‐1,2‐dichloroethene and vinyl chloride. © 2013 Wiley Periodicals, Inc.     

Limitations on infiltration and reinjection of treated groundwater to remove trace amounts of pesticides in groundwater and soil

Infiltration and reinjection of treated groundwater have been used to increase the recovery of pesticide-related constituents at a pesticide formulation plant that produces consumer pesticide products. The stratigraphy at the site consists of silty and sandy clay deposits overlying a shallow silt, sand, and gravel aquifer. The groundwater and soils in two areas in the northwest portion of the property have been identified as being significantly affected by pesticide and pesticide-related compounds. An integrated system of soil removal, recovery wells, injection wells, an infiltration gallery, and a cut-off wall was selected as the best remedial alternative. Groundwater modeling, column tests, biological jar tests, and a pilot test demonstrated the feasibility of the system. The affected groundwater is treated to drinking-water quality by a system of filtering and carbon adsorption. Approximately 75 percent of the treated water is reinjected or allowed to infiltrate through the vadose zone, and the remainder is discharged to the local sewer system. Initially, the system was effective in removing the dissolved, suspended, and weakly adsorbed constituents. Subsequently, the recovery rate of the chemical constituents became dependent on chemical and physical processes related to the presence of residual amounts of dense, nonaqueous phase liquids and the clay content of the strata. The rate of pesticide recovery has decreased because of the retarding effect of the clay and the low solubility of the pesticides.     

Smoldering Combustion (STAR) for the Treatment of Contaminated Soils: Examining Limitations and Defining Success

Smoldering combustion, commercially available as the Self‐sustaining Treatment for Active Remediation (STAR) technology, is an innovative technique that has shown promise for the remediation of contaminant source zones. Smoldering combustion is an exothermic reaction (net energy producing) converting carbon compounds and an oxidant (e.g., oxygen in air) to carbon dioxide, water, and energy. Thus, following ignition, the smoldering combustion reaction can continue in a self‐sustaining manner (i.e., no external energy or added fuel input following ignition) as the heat generated by the reacting contaminants is used to preheat and initiate combustion of contaminants in adjacent areas, propagating a combustion front through the contaminated zone provided a sufficient flux of air is supplied. The STAR technology has applicability across a wide‐range of hydrocarbons in a variety of hydrogeologic settings; however, there are limitations to its use. Impacted soils must be permeable enough to allow a sufficient flux of air to the combustion front and there exists a minimum required concentration of contaminants such that the soils contain sufficient fuel for the reaction to proceed in a self‐sustaining manner. Further limitations, as well as lessons learned and methods to mitigate these limitations, are presented through a series of case studies. In summary, the successful implementation of STAR will result in >99 percent reduction in contaminant concentrations in treated areas, limited residual contaminant mass, reduced groundwater contaminant mass flux which can be addressed through monitored natural attenuation; and an enhanced site exit strategy, reduced lifecycle costs, and reduced risk. ©2016 Wiley Periodicals, Inc.     

Forum

The State of Washington's Model Toxics Control Act cleanup standards, argues the author, provide the best available strategy for setting and achieving cleanup goals. Besides Protecting human health and the natural environnment, Washington's guidelines, which took effect March 1, 1991, incorporate enough flexibility to handle site-specific, finaical, and tehnological considerations. This column outlines the law's three approaches for defining cleanup levels for groundwater, surface water, air, industrial soils, and nonindustrial soils, comparing these methods with related methods in California, New Jersey, and New York.     

An Assessment of Management Practices to Control Nutrient and Pesticide Levels in Vegetable Production Areas in the Rattaphum Catchment, Thailand

The over-use of agrochemicals may have adverse effects on soils along with surface and groundwater. An assessment of alternative management practices to reduce the application of agrochemicals and minimise the pollution of water resources was carried out in the vegetable agro-ecosystem in the Rattaphum Catchment. This paper details the factors that govern the volume of agrochemicals used on high intensity crops in this area, covering the choice of crop and cropping patterns, level of pest and weed infestation and the socio-economic status of farmers such as capital, size of holding and labour availability. Alternative management practices tested included (i) a reduction in the use of pesticides and chemical fertilisers; (ii) the use of bio-insecticides and bio-fertilisers; and (iii) the development of buffer zones near streams to reduce nutrient leaching into surface water systems. The results showed that when compared with bio-insecticides, synthetic insecticides were more effective in controlling major insect pests during chaisim vegetable production and were associated with higher net incomes. The high rate of application of chemical fertilisers in home gardens and commercial farms led to the accumulation of phosphorous and potassium in the top soil, with the traditional method of combining organic and chemical fertilisers producing the highest total nitrogen soil content. A fifty percent reduction in chemical fertilisers in the commercial farms produced the lowest total nitrogen soil content, without any apparent change in crop yield. The three types of tested buffers seem to be effective in reducing runoff and sediment load and were particularly efficient in lowering nutrient leaching to streams; the best results were obtained with an effective length of 2.5 m.     

Field Performance of Point Velocity Probes at a Tidally Influenced Site

Conventional methods to estimate groundwater velocity that rely on Darcy's Law and average hydrogeologic parameter values are insensitive to local‐scale heterogeneities and anisotropy that control advective flow velocity and direction. Furthermore, at sites that are tidally influenced or have extraction wells with variable pumping schedules, infrequent water‐level measurements may not adequately characterize the range and significance of transient hydraulic conditions. The point velocity probe (PVP) is a recently developed instrument capable of directly measuring local‐scale groundwater flow velocity and direction. In particular, PVPs may offer distinct advantages for sites with complex groundwater–surface water interactions and/or with spatially and temporally variable groundwater flow conditions. The PVP utilizes a small volume of saline tracer and inexpensive sensors to directly measure groundwater flow direction and velocity in situ at the centimeter‐scale and discrete times. The probes are installed in conventional direct‐push borings, rather than in wells, thus minimizing the changes and biases in the local flow field caused by well installation and construction. Six PVPs were installed at a tidally influenced site in North Carolina to evaluate their implementability, performance, and potential value as a new site characterization tool. For this study, a new PVP prototype was developed using a rapid prototyping machine (i.e., a “three‐dimensional printer'') and included both horizontally and vertically oriented tracer detectors. A site‐specific testing protocol was developed to account for the spatially and temporally variable hydraulic conditions and groundwater salinity. The PVPs were tested multiple times, and the results were compared to the results of several different groundwater flux and velocity estimation tools and methods, including a heat‐pulse flowmeter, passive flux meters, single‐well tracer tests, and high‐resolution hydraulic gradient analysis. Overall, the results confirmed that the PVP concept is valid and demonstrated that reliable estimates of groundwater velocity and direction can be obtained in simple settings. Also, PVPs can be successfully installed by conventional methods at sites where the formation consists primarily of noncohesive soils and the water table is relatively shallow. Although some PVP tests yielded consistent and reliable results, several tests did not. This is likely due to the highly transient flow conditions and limitations associated with the PVP design and testing procedures. PVPs offer particular advantages over, and can effectively complement, other groundwater flow characterization techniques for certain conditions, and objectives may be useful for characterizing complex flow patterns under steady conditions; however, this study suggests that PVPs are best suited for conditions where the flow hydraulics are not highly transient. For sites where the hydraulic conditions are highly transient, the most reliable approach for understanding groundwater flow behavior and groundwater–surface water interactions would generally involve both a high‐resolution hydraulic gradient analysis and another local‐scale method, such as tracer testing. This study also highlighted some aspects of the current PVP design and testing protocol that can be improved upon, including a more robust connection between the PVP and injection line and further assessment of tracer solution density effects on vertical flow. © 2013 Wiley Periodicals, Inc.     

Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes

Simulation of back‐diffusion remediation timeframe for thin silt/clay layers, or when contaminant degradation is occurring, typically requires the use of a numerical model. Given the centimeter‐scale vertical grid spacing required to represent diffusion‐dominated transport, simulation of back‐diffusion in a 3‐D model may be computationally prohibitive. Use of a local 1‐D model domain approach for simulating back‐diffusion is demonstrated to have advantages but is limited to only some applications. Incorporation of a local domain approach for simulating back‐diffusion in a new model, In Situ Remediation‐MT3DMS (ISR‐MT3DMS) is validated based on a benchmark with MT3DMS and comparisons with a highly discretized finite difference numerical model. The approach used to estimate the vertical hydrodynamic dispersion coefficient is shown to have a significant influence on the simulated flux into and out of silt/clay layers in early time periods. Previously documented back‐diffusion at a Florida site is modeled for the purpose of evaluating the sensitivity of the back‐diffusion controlled remediation timeframe to various site characteristics. A base case simulation with a clay lens having a thickness of 0.2 m and a length of 100 m indicates that even after 99.96 percent aqueous TCE removal from the clay lens, the down‐gradient concentrations still exceed the MCL in groundwater monitoring wells. This shows that partial mass reduction from a NAPL source zone via in situ treatment may have little benefit for the long‐term management of contaminated sites, given that back‐diffusion will sustain a groundwater plume for a long period of time. Back‐diffusion model input parameters that have the greatest influence on remediation timeframe and thus may warrant more attention during field investigations, include the thickness of silt/clay lenses, retardation coefficient representing sorbed mass in silt/clay, and the groundwater velocity in adjacent higher permeability zones. Therefore, pump‐and‐treat systems implemented for the purpose of providing containment may have an additional benefit of reducing back‐diffusion remediation timeframe due to enhanced transverse advective fluxes at the sand/clay interface. Remediation timeframes are also moderately sensitive to the length of the silt/clay layers and transverse vertical dispersivity, but are less sensitive to degradation rates within silt/clay, contaminant solubility, contact time, tortuosity coefficient, and monitoring well‐screen length for the scenarios examined. ©2015 Wiley Periodicals, Inc.     

Successfully applying sparging technologies

Air sparging is an innovative methodology for remediating organic compounds present in contaminated, saturated soil zones. In the application of the technology, sparging (injection) wells are used to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below or within the areas of contamination. Two major mechanisms of remediation are engaged/enhanced due to the sparging process. First, volatile organic compounds are dissolved in the groundwater and sorbed on the soil partition into the advective air phase, effectively simulating an in-situ air stripping system. The stripped contaminants are transported in the air phase to the vadose zone, generally within the radius of influence of a standard vapor extraction and vapor treatment system. Second, with optimal environmental conditions, volatile and semivolatile organic compounds may be biodegraded by utilizing the sparging process to oxygenate the groundwater, thereby enhancing the growth and activity of the indigenous bacterial community. Air sparging is a complex multifluid phase process which has been applied successfully in Europe since the mid-1980s. Major design considerations include site geology, contaminant type, gas injection pressures and flow rates, injection interval (areal and vertical), and site-specific biofeasibility parameters. Site-specific geology and biofeasibility are the dominant design parameters. Pilot testing and full-scale design considerations should also be addressed. Mathematical models have been developed to simulate the air flow field during the sparging process and to examine the limitations imposed by site geology. Correct design and operation of this technology have been demonstrated to achieve groundwater cleanup to low part-per-billion contaminant levels. Incorrect design and operation can introduce significant pollution liability through undesirable contaminant migration in both the dissolved and vapor phases.     

Evaluation of surface water quality impacts of hazardous chemical sites

Common deficiencies in the typical evaluation of the surface water quality impacts of hazardous chemical sites are discussed. Particular attention is given to deficiencies in monitoring stormwater runoff, as well as the input of contaminated groundwaters that lead to impairment of the beneficial uses of nearby surface waters because of site-derived hazardous and deleterious chemicals. An alternative approach, Evaluation Monitoring, is presented in this paper. Evaluation Monitoring shifts the monitoring program from periodic sampling and analysis of stormwater runoff and ambient waters for a suite of chemical parameters, to examining the receiving waters to determine what, if any, water quality use impairments are occurring in surface waters due to the runoff-associated constituents and shallow groundwater input.