Evaluation of Long-Term Flow Controller for Monitoring Gases and Vapors in Buildings Impacted by Vapor Intrusion.

This study evaluated the use of a long-term capillary flow controller paired with an evacuated canister for indoor air exposure monitoring in a vapor intrusion (VI) environment with trichloroethylene in comparison to the traditional method utilizing a diaphragm flow controller. Traditionally, air sampling with 6 L evacuated canisters equipped with diaphragm flow controllers has been best suited for 8 to 24 h samples. New advances in capillary flow controllers can extend sampling to up to 3 weeks by reducing flow rates to 0.1 milliliters min-1. During six 2 wk sampling events, conventional diaphragm flow controller canisters were used to collect 24 h samples simultaneously with capillary flow controllers collecting 2 wk samples. Testing was performed at four indoor locations in buildings impacted by VI with co-located samples for each method at each location. All samples were analyzed using GC/MS, and the results were statistically analyzed to produce a direct comparison of the two sampling systems. Ninety-two percent of the 14 d capillary samples were within the 95% levels of agreement of the average concentration of the diaphragm flow controllers. The ability to collect 14 days of data, with less occupant disturbance, allows for improved exposure assessments and thus improved risk management decisions.

Enhanced Recovery of Per- and Polyfluoroalkyl Substances (PFASs) from Impacted Soils Using Heat Activated Persulfate.

Varying transport potential of cationic, zwitterionic, and anionic per- and polyfluoroalkyl substances (PFASs) may pose challenges for remediation of aqueous film forming foam (AFFF) impacted sites, particularly during groundwater extraction. Slow desorption of stronger sorbing, zwitterionic, and cationic PFASs may cause extended remediation times and rebound in aqueous PFAS concentrations. Persulfate oxidation has the potential to convert a complex mixture of PFASs into a simpler and more recoverable mixture of perfluoroalkyl acids (PFAAs). AFFF-impacted soils were treated with heat-activated persulfate in batch reactors and subjected to 7-day leaching experiments. Soil and water were analyzed using a combination of targeted and high resolution liquid chromatography mass spectrometry techniques as well as the total oxidizable precursors assay. Following oxidation, total PFAS composition showed the expected shift to a higher fraction of PFAAs, and this led to higher total PFAS leaching in pretreated reactors (108-110%) vs control reactors (62-90%). In both pretreated and control soils, precursors that remained following leaching experiments were 61-100% cationic and zwitterionic. Results suggest that persulfate pretreatment of soils has promise as an enhanced recovery technique for remediation of total PFASs in impacted soils. They also demonstrate that PFAS distribution may have been altered at sites where in situ chemical oxidation was applied to treat co-occurring contaminants of concern.

Slow-release permanganate versus unactivated persulfate for long-term in situ chemical oxidation of 1,4-dioxane and chlorinated solvents.

The objective of this research was to evaluate slow-release permanganate and unactivated persulfate for in situ treatment of dioxane and associated chlorinated solvents. Laboratory batch studies with unactivated persulfate in deionized water or in soil and groundwater demonstrated dioxane removal with pseudo second-order rate constants ranging from 10-5 to 10-3 M-1 s-1. Flow-through column studies demonstrated over 99% dioxane removal with slow-release unactivated persulfate but not with slow-release permanganate. The slow-release permanganate cylinders became coated with a rind that limited oxidant mass transfer and dioxane oxidation. A field study was conducted with slow-release persulfate cylinders transverse to groundwater flow. Over 99% removal of dioxane and chlorinated solvents was observed 2.5 m downgradient of the cylinders. Density-driven flow associated with the released persulfate was observed and was attributed to a low horizontal hydraulic gradient. Thus, most of the contaminant and persulfate flux was thought to be isolated to a deep aquifer zone that was bound by an underlying silt aquitard. Contaminant reductions were also observed in shallow groundwater samples, albeit at a lesser extent. The longevity of the persulfate oxidant cylinders was estimated to be 6-12 months. Results of this study demonstrate that dioxane and co-mingled chlorinated solvents can be effectively treated using slow-release persulfate cylinders. Careful consideration to cylinder placement during the design phase is essential to prevent the contaminant plume from bypassing and not coming into contact with the released oxidant.

Evaluation and Management Strategies for Per- and Polyfluoroalkyl Substances (PFASs) in Drinking Water Aquifers: Perspectives from Impacted U.S. Northeast Communities.

BACKGROUND: Multiple Northeast U.S. communities have discovered per- and polyfluoroalkyl substances (PFASs) in drinking water aquifers in excess of health-based regulatory levels or advisories. Regional stakeholders (consultants, regulators, and others) need technical background and tools to mitigate risks associated with exposure to PFAS-affected groundwater. OBJECTIVES: The aim was to identify challenges faced by stakeholders to extend best practices to other regions experiencing PFAS releases and to establish a framework for research strategies and best management practices. METHODS AND APPROACH: Management challenges were identified during stakeholder engagement events connecting attendees with PFAS experts in focus areas, including fate/transport, toxicology, and regulation. Review of the literature provided perspective on challenges in all focus areas. Publicly available data were used to characterize sources of PFAS impacts in groundwater and conduct a geospatial case study of potential source locations relative to drinking water aquifers in Rhode Island. DISCUSSION: Challenges in managing PFAS impacts in drinking water arise from the large number of relevant PFASs, unconsolidated information regarding sources, and limited studies on some PFASs. In particular, there is still considerable uncertainty regarding human health impacts of PFASs. Frameworks sequentially evaluating exposure, persistence, and treatability can prioritize PFASs for evaluation of potential human health impacts. A regional case study illustrates how risk-based, geospatial methods can help address knowledge gaps regarding potential sources of PFASs in drinking water aquifers and evaluate risk of exposure. CONCLUSION: Lessons learned from stakeholder engagement can assist in developing strategies for management of PFASs in other regions. However, current management practices primarily target a subset of PFASs for which in-depth studies are available. Exposure to less-studied, co-occurring PFASs remains largely unaddressed. Frameworks leveraging the current state of science can be applied toward accelerating this process and reducing exposure to total PFASs in drinking water, even as research regarding health effects continues. https://doi.org/10.1289/EHP2727.

Field demonstration of polymer-amended in situ chemical oxidation (PA-ISCO).

The methods and results of the first field-scale demonstration of polymer-amended in situ chemical oxidation (PA-ISCO) are presented. The demonstration took place at MCB CAMLEJ (Marine Corps Base, Camp Lejeune) Operable Unit (OU) 15, Site 88, in Camp Lejeune, North Carolina between October and December 2010. PA-ISCO was developed as an alternative treatment approach that utilizes viscosity-modified fluids to improve the in situ delivery and distribution (i.e. sweep-efficiency) of chemical oxidants within texturally heterogeneous contaminated aquifers. The enhanced viscosity of the fluid mitigates the effects of preferential flows, improving sweep-efficiency and enhancing the subsurface contact between the injected oxidant and the target contamination within the treatment zone. The PA-ISCO fluid formulation used in this demonstration included sodium permanganate as oxidant, xanthan gum biopolymer as a shear-thinning viscosifier, and sodium hexametaphosphate (SHMP) as an anti-coagulant. It was the goal of this demonstration to validate the utility of PA-ISCO within a heterogeneous aquifer. An approximate 100% improvement in sweep-efficiency was achieved for the PA-ISCO fluid, as compared to a permanganate-only injection within an adjacent control plot.

Release of chromium from soils with persulfate chemical oxidation.

An important part of the evaluation of the effectiveness of persulfate in situ chemical oxidation (ISCO) for treating organic contaminants is to identify and understand its potential impact on metal co-contaminants in the subsurface. Chromium is a redox-sensitive and toxic metal the release of which poses considerable risk to human health. The objective of this study was to investigate the impact of persulfate chemical oxidation on the release of chromium from three soils varying in physical-chemical properties. Soils were treated with unactivated and activated persulfate [activated with Fe(II), Fe(II)-EDTA, and alkaline pH] at two different concentrations (i.e., 41 mM and 2.1 mM persulfate) for 48 h and 6 months and were analyzed for release of chromium. Results show that release of chromium with persulfate chemical oxidation depends on the soil type and the activation method. Sandy soil with low oxidant demand released more chromium compared to soils with high oxidant demand. More chromium was released with alkaline pH activation. Alkaline pH and high Eh conditions favor oxidation of Cr(III) to Cr(VI), which is the main mechanism of release of chromium with persulfate chemical oxidation. Unactivated and Fe(II)-activated persulfate decreased pH and at low pH in absence of EDTA chromium release is not a concern. These results indicate that chromium release can be anticipated based on the given site and treatment conditions, and ISCO system can be designed to minimize potential chromium release when treating soils and groundwater contaminated with both organic and metal contaminants.

Comparative study on oxidative treatments of NAPL containing chlorinated ethanes and ethenes using hydrogen peroxide and persulfate in soils.

The goal of this study was to assess the oxidation of NAPL in soil, 30% of which were composed of chlorinated ethanes and ethenes, using catalyzed hydrogen peroxide (CHP), activated persulfate (AP), and H(2)O(2)-persulfate (HP) co-amendment systems. Citrate, a buffer and iron ligand, was amended to the treatment system to enhance oxidative treatment. Four activation/catalysis methods were employed: (1) oxidant only, (2) oxidant-citrate, (3) oxidant-iron(II), and (4) oxidant-citrate-iron(II). The NAPL treatment effectiveness was the greatest in the CHP reactions, the second in HP, and the third in AP. The effective activation and catalysis methods depended on the oxidant types; oxidant only for CHP and HP and oxidant-citrate-iron for AP. The treatability trend of chlorinated ethanes and ethenes in the soil mixture was as follows: trichloroethene > tetrachloroethene > dichloroethane > trichloroethane > tetrachloroethane. A significant fraction of persulfate remained in the oxidation systems after the 2-day reaction period, especially in the citrate-iron(II) AP. In general, oxidation systems that included citrate maintained a post-treatment pH in the range of 7-9. A final pH of AP oxidation systems was acidic (pH 2-3), where a molar ratio of citrate-iron(II) was less than 1.8 and where no citrate was amended.

Experimental design of diffusion and desorption of contaminant in heterogeneous media.

Storage of contaminants in low permeability media (LPM) presents a great challenge for prediction of remediation effectiveness and efficiency. The reason lies in the contaminants' complex behaviors within heterogeneous media. Both interparticle and intraparticle diffusion contribute to the difficulty of precise site assessment. Sorption of contaminants--especially within LPM--may sequester the contaminants from active treatment, while desorption over a long period of time leads to contaminant release from storage and consequent re-contamination. Research has been conducted toward better understanding of contaminant diffusion and sorption/desorption processes to better predict contaminant response to site treatment. However, most of the research has been carried out within homogeneous media, while real scenarios in environmental problems feature media whose permeability and other characteristics vary significantly over the treatment volume. Further, few efforts have combined the interparticle/intraparticle diffusion and sorption/desorption processes together. This research aims at a feasible experimental design of diffusion and desorption of contaminant in heterogeneous media to address the gaps in previous research. A 2-D experimental system was designed to evaluate interparticle/intraparticle diffusion processes of trichloroethylene (TCE) in heterogeneous media. The 2-D system was modified to include organic matter in media for simulation of sorption/desorption processes. Results of the research will improve the understanding of how these different transport processes act together within heterogeneous media. Results will also allow for the evaluation of the impact of contaminant mass transport from within low permeability media at a potential treatment site and can support the development of mathematical tools/models combining interparticle/intraparticle and sorption/desorption processes. Such a model will promote more accurate site assessment and provide more confidence in the choice of an effective, economically optimized remediation strategy.

Control of manganese dioxide particles resulting from in situ chemical oxidation using permanganate.

In situ chemical oxidation using permanganate is an approach to organic contaminant site remediation. Manganese dioxide particles are products of permanganate reactions. These particles have the potential to deposit in the subsurface and impact the flow-regime in/around permanganate injection, including the well screen, filter pack, and the surrounding subsurface formation. Control of these particles can allow for improved oxidant injection and transport and contact between the oxidant and contaminants of concern. The goals of this research were to determine if MnO(2) can be stabilized/controlled in an aqueous phase, and to determine the dependence of particle stabilization on groundwater characteristics. Bench-scale experiments were conducted to study the ability of four stabilization aids (sodium hexametaphosphate (HMP), Dowfax 8390, xanthan gum, and gum arabic) in maintaining particles suspended in solution under varied reaction conditions and time. Variations included particle and stabilization aid concentrations, ionic content, and pH. HMP demonstrated the most promising results, as compared to xanthan gum, gum arabic, and Dowfax 8390 based on results of spectrophotometric studies of particle behavior, particle filtration, and optical measurements of particle size and zeta potential. HMP inhibited particle settling, provided for greater particle stability, and resulted in particles of a smaller average size over the range of experimental conditions evaluated compared to results for systems that did not include HMP. Additionally, HMP did not react unfavorably with permanganate. These results indicate that the inclusion of HMP in a permanganate oxidation system improves conditions that may facilitate particle transport.

Enhanced permanganate in situ chemical oxidation through MnO2 particle stabilization: evaluation in 1-D transport systems.

In situ chemical oxidation using permanganate is an increasingly employed approach to organic contaminant remediation at hazardous waste sites. Manganese dioxide (MnO2) particles form as a by-product of the reaction of permanganate with contaminants and naturally-reduced subsurface materials. These particles are of interest because they have the potential to deposit in the subsurface and impact the flow regime in/around permanganate injection, including the well screen, filter pack, and the surrounding subsurface formation. Control of these particles can allow for improved oxidant injection and transport, and contact between the oxidant and contaminants of concern. Sodium hexametaphosphate (HMP) has previously been identified as a promising aid to stabilize MnO2 in solution when included in the oxidizing solution, increasing the potential to inhibit particle deposition and impact subsurface flow. The goal of the experimental studies described herein was to investigate the ability of HMP to prevent particle deposition in transport studies using four different types of porous media. Permanganate was delivered to a contaminant source zone (trichloroethylene) located within four different media types with variations in sand, clay, organic carbon, and iron oxides (as goethite) content. Deposition of MnO2 within the columns was quantified with distance from the source zone. Experiments were repeated in replicate columns with the inclusion of HMP directly with the oxidant delivery solution, and MnO2 deposition was again quantified. While total MnO2 deposition within the 60 cm columns did not change significantly with the addition of HMP, deposition within the contaminant source zone decreased by 25-85%, depending on the specific media type. The greatest differences in deposition were observed in the goethite-containing and clay-containing columns. Columns containing these two media types experienced completely plugged flow in the oxidant-only delivery systems; however, the addition of HMP prevented this plugging within the columns, increasing the oxidant throughput.

Coupling permanganate oxidation with microbial dechlorination of tetrachloroethene.

For sites contaminated with chloroethene non-aqueous-phase liquids, designing a remediation system that couples in situ chemical oxidation (ISCO) with potassium permanganate (KMnO4) and microbial dechlorination may be complicated because of the potentially adverse effects of ISCO on anaerobic bioremediation processes. Therefore, one-dimensional column studies were conducted to understand the effect of permanganate oxidation on tetrachloroethene (PCE) dechlorination by the anaerobic mixed culture KB-1. Following the confirmation of PCE dechlorination, KMnO4 was applied to all columns at a range of concentrations and application velocities to simulate varied distances from oxidant injection. Immediately following oxidation, reductive dechlorination was inhibited; however, after passing several pore volumes of sterile growth medium through the columns after oxidation, a rebound of PCE dechlorination activity was observed in every inoculated column without the need to reinoculate. The volume of medium required for a rebound of dechlorination activity differed from 1.1 to 8.1 pore volumes (at a groundwater velocity of 4 cm/d), depending on the specific condition of oxidant application.

Association of cadmium with MnO2 particles generated during permanganate oxidation.

Particle filtration and cadmium sorption studies were performed at selected time points during reaction of potassium permanganate with trichloroethylene under varied reaction matrix conditions. The purpose of the studies was to determine the potential impact of manganese oxides particle generation, a by-product of the permanganate reaction, on subsurface metal mobility, with cadmium serving as a representative metal of interest in the environment. Results of the studies indicate that the association of cadmium with the manganese oxides is a function of (1) particle concentration, (2) pH, (3) the presence of calcium in the reaction matrix, and (4) the rate of particle generation and agglomeration. Based on these findings, it is important to give careful consideration to subsurface conditions that can potentially impact the mobility of metals present naturally or as co-contaminants. If subsurface conditions are not appropriately characterized and planned for, deleterious effects could result, including long-term release of metals initially sorbed onto generated particles. Alternatively, the generated manganese oxides may serve as a long-term means of immobilizing metals within the subsurface.

Geochemical effects on metals following permanganate oxidation of DNAPLs.

The application of in situ chemical oxidation for dense, nonaqueous phase liquid (DNAPL) remediation requires delivery of substantial levels of oxidant chemicals into the subsurface to degrade target DNAPLs and to satisfy natural oxidant demand. This practice can raise questions regarding changes in subsurface conditions, yet information regarding potential effects, especially at the field scale, has been lacking. This paper describes an evaluation of the effects on metals associated with in situ chemical oxidation using potassium permanganate at Launch Complex 34 (LC34), Cape Canaveral Air Station, Florida. At LC34, high concentrations of permanganate (1 to 2 wt%) were injected into the subsurface as part of a demonstration of DNAPL remediation technologies. In a companion experimental effort at the Colorado School of Mines, field samples were characterized and laboratory batch and mini-column studies were completed to assess effects of permanganate oxidation on metals in the subsurface one year after completion of the field demonstration. Results indicated there was potential for long-term immobilization of a portion of introduced manganese and no treatment-induced loss in subsurface permeability due to deposition of manganese oxides particles, which are a product of the oxidation reactions. Permanganate treatment did cause elevated manganese, chromium, and nickel concentrations in site ground water within the treated region. Some of these metals effects can be attenuated during downgradient flow through uncontaminated and untreated aquifer sediments.