Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D‐CSIA Approach

An optimized “Three‐Dimensional Compound Specific Isotope Analysis (3D‐CSIA)'' investigation was conducted at a chlorinated hydrocarbon–contaminated site in order to (1) determine if multiple onsite sources of groundwater contamination existed and (2) demonstrate the cost‐effectiveness of applying isotope fingerprinting at such a complex contaminated site. Previous groundwater investigations identified chlorinated hydrocarbons at levels that significantly exceed drinking‐water standards but failed to determine the source(s) of contamination due to the lack of vadose‐zone contamination and the absence of groundwater contaminants in shallow portions of the surficial aquifer. To better understand the contaminant source(s), groundwater samples were taken and tested for both the presence of chlorinated hydrocarbons and their isotopic signatures of ¹³C/¹²C, ³⁷Cl/³⁵Cl, and ²H/¹H. A site investigation with an optimized 3D‐CSIA approach revealed multiple chlorinated hydrocarbon releases from different sources, which was also cost‐effective considering the new lines of evidence of target contaminants obtained with the 3D‐CSIA approach instead of any traditional fingerprinting approaches. In addition, the 3D‐CSIA results inferred in situ bioremediation of chlorinated hydrocarbons would be feasible at the site. © 2013 Wiley Periodicals, Inc.     

Successful solid-phase bioremediation of petroleum-contaminated soil

Biological processes have been used to remediate petroleum hydrocarbons, pesticides, chlorinated solvents, and halogenated aromatic hydrocarbons. Biological treatment of contaminated soils may involve solid-phase, slurry-phase, or in situ treatment techniques. This article will review the general principle of solid-phase bioremediation and discuss the application of this technique for the cleanup of total petroleum hydrocarbons on two sites. These remedial programs will reduce total petroleum hydrocarbon contamination from the mean concentration of 2,660 ppm to under the 200-ppm cleanup criteria for soil and under the 15-ppm cleanup criteria for groundwater. Over 32,000 yards of soil have been treated by solid-phase treatment to date. The in situ system operation is effectively producing biodegradation in the subsurface. The project is approximately one-third complete.     

1,4‐Dioxane Treatment Technologies

The chlorinated solvent stabilizer 1,4‐dioxane (DX) has become an unexpected and recalcitrant groundwater contaminant at many sites across the United States. Chemical characteristics of DX, such as miscibility and low sorption potential, enable it to migrate at least as far as the chlorinated solvent from which it often originates. This mobility and recalcitrance has challenged remediation professionals to redesign existing treatment systems and monitoring networks to accommodate widespread contamination. Furthermore, remediation technologies commonly applied to chlorinated solvent co‐contaminants, such as extraction and air stripping or in situ enhanced reductive dechlorination, are relatively ineffective on DX removal. These difficulties in treatment have required the industry to identify, develop, and demonstrate new and innovative technologies and approaches for both ex situ and in situ treatment of this emerging contaminant. Great strides have been made over the past decade in the development and testing of remediation technologies for removal or destruction of DX in groundwater. This article briefly summarizes the fate and transport characteristics of DX that make it difficult to treat, and presents technologies that have been demonstrated to be applicable to groundwater treatment at the field scale.  ©2016 Wiley Periodicals, Inc.     

Isotope applications in environmental investigations: Theory and use in chlorinated solvent and petroleum hydrocarbon studies

Isotope applications are gaining acceptance for use in surface water and groundwater investigations, complementing traditional geochemistry and physical hydrology techniques. Recent developments in analytical methodologies and in the understanding of isotope dynamics now allow the use of isotopes to investigate sources and fate of common groundwater contaminants such as chlorinated solvents and petroleum hydrocarbons. Contaminants with unique isotopic signatures may facilitate the determination of contaminant sources in complex plumes. Degradation of chlorinated solvents and some petroleum hydrocarbons impart unique isotopic signatures on both the original contaminant and the degradation product or products that provide verification of degradation. Use of a Rayleigh‐type model may allow determination of degradation extent. Coupled with models of contaminant fate and transport, degradation extent may be useful for determining degradation rates. © 2001 John Wiley & Sons, Inc.     

Effective low-temperature thermal aeration of soils

Low-temperature thermal aeration (LTTA) is a remedial technology developed by Canonie Environmental Services Corp. (Canonie) for use on soils containing nonchlorinated hydrocarbons, chlorinated solvents, volatile organic compounds (VOCs), chlorinated pesticides, and low levels of polynuclear aromatic hydrocarbons (PAHs). The LTTA system separates these hazardous constituents from excavated soils and allows the treated soils to be redeposited on-site without restriction. This article describes the various components and operation of LTTA systems for the remediation of soils contaminated with chlorinated and nonchlorinated constituents. The article also details the results of projects completed to date, principally for soil impacted with chlorinated hydrocarbons, and discusses the general characteristics and results of systems used for soils contaminated with nonchlorinated hydrocarbons (gasoline, etc.).     

Alternative method of groundwater sparging for petroleum hydrocarbon remediation

An alternative method of in-situ groundwater sparging, termed density-driven convection (patent pending), is presented. This method has been successfully used to remediate eight underground storage tank releases involving a wide distillation range of petroleum hydrocarbons (gasoline to waste oil) and in a variety of site soils (clay to sandy gravel). Application of the density-driven convection method is detailed in a case study. The system, installed to remediate a gasoline and diesel release from an underground storage tank, was operated and monitored for a period of one year. Monitoring data indicate reductions in total petroleum hydrocarbon concentrations in groundwater and in soil. Concentrations of aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylenes, and naphthalene) also decreased in both media. Stimulation of natural biodegradation, the primary mechanism of removal, occurred rapidly. Natural biological activity gradually declined over the subsequent 150 days. After one year of operation, the sparging system has achieved or is rapidly approaching the regulatory cleanup goals for both soil and groundwater, including reduction of dissolved concentrations below maximum contaminant levels established under the Safe Drinking Water Act.     

Applications of mulch biowalls—three case studies

Mulch biowalls are proving to be an effective means of generating reducing conditions for the in situ anaerobic reduction of contaminants in groundwater that are amenable to the reduction process. Mulch is an inexpensive and readily available substrate that provides a long‐lasting carbon and electron donor source for the stimulation of the anaerobic reduction process in groundwater. Examples of contaminants that are amenable to the biotic anaerobic reduction process include: chlorinated alkenes and alkanes, explosives, perchlorate, some metals, and petroleum hydrocarbons. The microbial degradation of cellulose fibers (mulch) is arguably the oldest reduction process known and is evident anywhere that plant material, soil, and water are present together. This article presents three case studies discussing three different uses of mulch biowalls to stimulate the anaerobic bioremediation of contaminants in shallow soils and groundwater. © 2009 Wiley Periodicals, Inc.     

Examining the economics of remediation by fluid injection with vacuum extraction

Enhanced methods of in-situ remediation based on patented technology involving fluid injection with vacuum extraction have been used successfully at the Sand Creek Superfund Site in Commerce City, Colorado. Approximately 177,000 pounds of volatile organic compounds (VOCs) were removed from the subsurface in six months, two months ahead of schedule. Remediation goals were achieved on this thermally enhanced soil vapor extraction project by using vertical and horizontal wells interchangeably in vacuum or pressure service for vapor extraction, dual vacuum extraction, heated vapor reinjection, and air sparging. Although VOCs consisted of mixed chlorinated and petroleum hydrocarbons, the petroleum hydrocarbons, some in the form of nonaqueous phase liquids, had not been fully characterized. This article examines the evolution of the remedial design from that conceptualized in the Record of Decision (ROD) of the U.S. EPA, presents the rationale for the selection of alternative system components, and provides a cost analysis of the selected remedial technology, with comparisons to that of alternatives considered for use at Sand Creek.     

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.     

Combined thermal and zero‐valent iron In Situ soil mixing remediation technology

Thermal remediation of contaminated soils and groundwater by injection of hot air and steam using large‐diameter auger in situ soil mixing effectively remediates volatile and semivolatile organic compounds. This technology removes large amounts of contamination during the early treatment stages, but extended treatment times are needed to achieve high removal percentages. Combining thermal treatment with another technology that can be injected and mixed into the soil, and that continues to operate after removal of the drilling equipment, improves removal efficiency, and reduces cost. Using field‐determined pseudo first‐order removal rates, the cost of the combined remediation of chlorinated volatile organic compounds (CVOCs) by thermal treatment followed by reductive dechlorination by iron powder has been estimated as 57 percent of the cost of thermal treatment alone. This analysis was applied to a case‐study remediation of 48,455 cubic yards, which confirmed the cost estimate of the combined approach and showed over 99.8 percent removal of trichloroethene and other chlorinated VOCs. © 2010 Wiley Periodicals, Inc.     

ART in‐well technology proves effective in treating 1,4‐dioxane contamination

A common industrial solvent additive is 1,4‐dioxane. Contamination of dissolved 1,4‐dioxane in groundwater has been found to be recalcitrant to removal by conventional, low‐cost remedial technologies. Only costly labor and energy‐intensive pump‐and‐treat remedial options have been shown to be effective remedies. However, the capital and extended operation and maintenance costs render pump‐and‐treat technologies economically unfeasible at many sites. Furthermore, pump‐and‐treat approaches at remediation sites have frequently been proven over time to merely achieve containment rather than site closure. A major manufacturer in North Carolina was faced with the challenge of cleaning up 1,4‐dioxane and volatile organic compound–impacted soil and groundwater at its site. Significant costs associated with the application of conventional approaches to treating 1,4‐dioxane in groundwater led to an alternative analysis of emerging technologies. As a result of the success of the Accelerated Remediation Technologies, LLC (ART) In‐Well Technology at other sites impacted with recalcitrant compounds such as methyl tertiarybutyl ether, and the demonstrated success of efficient mass removal, an ART pilot test was conducted. The ART Technology combines in situ air stripping, air sparging, soil vapor extraction, enhanced bioremediation/oxidation, and dynamic subsurface groundwater circulation. Monitoring results from the pilot test show that 1,4‐dioxane concentrations were reduced by up to 90 percent in monitoring wells within 90 days. The removal rate of chlorinated compounds from one ART well exceeded the removal achieved by the multipoint soil vapor extraction/air sparging system by more than 80 times. © 2005 Wiley Periodicals, Inc.     

Radiolytic decomposition of environmental contaminants and site remediation using an electron accelerator

Halogenated and nonhalogenated hydrocarbon contaminants are currently found in natural waterways, groundwater, and soils as a result of spills and careless disposal practices. The development of proper treatment methodologies for the waste streams producing this environmental damage is now a subject of growing concern. A significant number of these waste stream compounds are chemically stable and are thus resistant to environmental degradation. Numerous researchers have investigated the use of ionizing radiation to decompose chlorinated hydrocarbons in diverse matrices and have proposed various free-radical-induced reaction mechanisms. This article is divided into two sections. First, we present data on experimentally measured, radiolytically induced decomposition of hazardous wastes and toxic substances using accelerator-generated bremsstrahlung sources and gamma radiation from cobalt-60. Data are presented on the radiolytically induced reduction in concentration of volatile organic compounds (VOCs) dissolved in water and in air, polychlorinated biphenyls (PCBs) dissolved in oil, high explosives dissolved in groundwater, and chemical weapon surrogates. The results of these studies suggest the potential use of ionizing radiation as a method of hazardous waste treatment. The second section of this article describes the technical aspects of a field-scale radiolytic decomposition site cleanup demonstration using an electron accelerator. A portable, commercially available electron accelerator was set up at the Lawrence Livermore National Laboratory's (LLNL's) Site 300, a Superfund site, where vacuum extraction wells were removing trichloroethylene (TCE) vapor from a ground spill into the unsaturated soil zone. The accelerator was retrofitted into the existing vacuum extraction system such that the extracted TCE-containing vapor passed through the accelerator beam for treatment. The concentration of TCE in the vapor was reduced by an amount dependent on the accelerator beam power. Production of reaction products in the vapor was measured as a function of absorbed dose.     

Evaluation of in situ steam‐injection processes for reduction of petroleum compounds within an abandoned canal

A conceptual approach of a novel application of in‐situ thermal processes that would either use a steam injection process or a steam/surfactant injection process was considered to remediate petroleum contaminated sediment residing in an abandoned canal. Laboratory tests were conducted in an attempt to volatilize or mobilize contaminants of concern (selected polycyclic aromatic hydrocarbons [PAHs]) from the contaminated sediment into a phase that could be physically removed. The processes were operated above ambient temperature and pressure in an attempt to increase the removal of the contaminants of concern from the sediment. The ability of both the steam injection process and the steam/surfactant process to remove PAHs from the sediment was considered ineffective; as only two of the seventeen selected PAHs (naphthalene and C1 naphthalene) were associated with a percentage mass reduction greater than 34% for both treatments (four trials). The steam/surfactant injection process generally resulted in higher reductions than the steam injection process, but had larger variances within the two trials using the treatment type. This preliminary evaluation suggests that steam‐based injection processes for removing petroleum contamination from this canal sediment, using the surfactants selected, equipment set‐up, and operating conditions studied, would be considered ineffective. © 2010 Wiley Periodicals, Inc. *

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

     

The Origin And Fate Of Volatile Trace Components In Municipal Solid Waste Landfills

The content of readily volatile halogenated hydrocarbons (chlorinated and chlorinated, fluorinated hydrocarbons (VCCs/CFCs)) and the BTEX aromatic substances (benzene, toluene, ethylbenzene and xylene) in municipal solid waste (MSW) was determined by two different methods. Moreover, the emission potential of these substances via the gas and leachate phase was investigated during the different biological degradation phases in the landfill. Trichlorofluoromethane (R11), dichlorodifluoromethane (R12) and dichloromethane (R30) were the dominating halogenated trace substances detected in the MSW. In the acid phase, with some VCCs/CFCs the emittance may take place up to 30% via the water phase. Hexane, benzene, and toluene could be detected in all tests. Toluene often occurred in relatively high concentrations in MSW. It could be shown that R11 degraded into dichlorofluoromethane (R21).     

The Use of Oxygen Release Compound for the Accelerated Bioremediation of Aerobically Degradable Contaminants: The Advent of Time-Release Electron Acceptors

Oxygen Release Compound (ORC®) is a patented formulation of intercalated magnesium peroxide that releases oxygen slowly when hydrated. ORC treatment represents a “low intensity” approach to site remediation. It provides a simple, passive, low-cost and long-term acceleration of aerobic natural attenuation and has been shown to cost-effectively reduce time to site closure. ORC is now a proven technology as evidenced by its five years of use on over 5,000 sites in 50 states and 11 countries, and the existence of a full body of independent, peer reviewed literature on its performance. The first applications of ORC were for the treatment of benzene, toulene, ethylbenzene, and xylene (BTEX) and other light petroleum hydrocarbon fractions. Use has now expanded to the treatment of heavier fractions such as heating oil and some of the Polycyclic aromatic hydrocarbons (PAHs). More recently. ORC has been used to bioremediate the highly mobile and problematic gasoline oxygenate methyl tertiary butyl ether (MTBE) and has been applied to sites impacted with nitroaromatics, chloroaromatics, and some of the lower-order chlorinated hydrocarbons that can be treated aerobically—most notably vinyl chloride. Since ORC is an insoluble powder, it can be packaged in material composed of a specially designed filter fabric. These “filter socks” are then contacted with contaminated groundwater via an array of wells or trenches. ORC can also be mixed directly with water to form a slurry for permanent injection applications in the saturated zone or dispersed in powdered form for the in-situ or ex-situ treatment of soil. A broad array of treatment points, in which ORC slurry is backfilled or injected, can be implemented with low-cost, small-bore push-point technologies to directly treat dissolved phase plumes and moderate levels of sorbed contaminants. Powder or slurry is traditionally used in the remediation of residual contamination at the bottom of contaminated soil excavations. © 1999 John Wiley & Sons, Inc.     

Creosote DNAPL Recovery‐Well Design for Mass Removal

Sites with dense nonaqueous‐phase liquid (DNAPL) contamination present significant remediation challenges in terms of technical practicability and cost. Remedial approaches to DNAPL sites often follow a management approach rather than removal or eradication approaches, particularly due to the uncertainties associated with the benefits of partial source mass removal, as complete source removal is unlikely. Mass‐removal technologies should be evaluated for all DNAPL sites, although implementation of recovery technologies will be limited to a few sites based upon site‐specific factors. Sitewide remedial strategies that employ source reduction, where applicable, and incorporate associated risk‐reduction technologies, including monitored natural attenuation, are advised. Creosote DNAPL sites are particularly challenging, as they are predominantly composed of low‐solubility polycyclic aromatic hydrocarbons that form long‐term continuing sources. Additionally, the physical properties of creosote DNAPL, including high viscosity and relatively low density, result in significant migration potential and considerable dissolved‐phase groundwater impacts. An innovative creosote DNAPL source recovery well design was developed to achieve separate‐phase removal of pooled creosote DNAPL. The design presented herein employs modified circulation‐well technology to mobilize DNAPL to the engineered recovery well, where it is gravity‐settled into a sump to permit separate‐phase mass removal of the emplaced DNAPL source without groundwater production or treatment. A discharge mass flux protocol was developed to verify dissolved‐phase plume stability and the benefit of the source mass removal. © 2013 Wiley Periodicals, Inc.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

Established groundwater contaminants such as chlorinated solvents and hydrocarbons have impacted groundwater at hundreds of thousands of sites around the United States and have been responsible for multibillion dollar remediation expenditures. An important question is whether groundwater remediation for the emerging contaminant class comprised of per‐ and polyfluoroalkyl substances (PFAS) will be a smaller, similar, or a larger‐scale problem than the established groundwater contaminants. A two‐pronged approach was used to evaluate this question in this paper. First, nine quantitative scale‐of‐remediation metrics were used to compare PFAS to four established contaminants: chlorinated solvents, benzene, 1,4‐dioxane, and methyl tert‐butyl ether. These metrics reflected the prevalence of the contaminants in the U.S., attenuation potential, remediation difficulty, and research intensity. Second, several key challenges identified with PFAS remediation were evaluated to see similar situations (qualitative analogs) that have been addressed by the remediation field in the past. The results of the analysis show that four out of nine of the evaluated quantitative metrics (production, number of potential sites, detection frequency, required destruction/removal efficiency) indicate that the scale of PFAS groundwater remediation may be smaller compared to the current scale of remediation for conventional groundwater contaminants. One attenuation metric, median plume length, suggests that overall PFAS remediation could pose a greater challenge compared to hydrocarbon sites, but only slightly larger than chlorinated volatile organic compounds sites. The second attenuation metric, hydrophobic sorption, was not definitive regarding the potential scale of PFAS remediation. The final three metrics (regulatory criteria, in‐situ remediation capability, and research intensity) all indicate that PFAS remediation might end up being a larger scale problem than the established contaminants. An assessment of the evolution of groundwater remediation capabilities for established contaminants identified five qualitative analogs for key PFAS groundwater remediation issues: (a) low‐level detection analytical capabilities; (b) methods to assess the risk of complex chemical mixtures; (c) nonaqueous phase dissolution as an analog for partitioning, precursors, and back diffusion at PFAS sites; (d) predictions of long plume lengths for emerging contaminants; and (e) monitored natural attenuation protocols for other non‐degrading groundwater contaminants. Overall the evaluation of these five analogs provided some comfort that, while remediating the potential universe of PFAS sites will be extremely challenging, the groundwater community has relevant past experience that may prove useful. The quantitative metrics and the qualitative analogs suggest a different combination of remediation approaches may be needed to deal with PFAS sites and may include source control, natural attenuation, in‐situ sequestration, containment, and point‐of‐use treatment. However, as with many chlorinated solvent sites, while complete restoration of PFAS sites may be uncommon, it should be possible to prevent excessive exposure of PFAS to human and ecological receptors.     

Groundwater Impacts on Surface Water and Sediment—Gowanus Canal,Brooklyn, New York

The Gowanus Canal Superfund Site in Brooklyn, New York, is an approximately 1.5‐mile (1.61‐km) long estuary that was historically converted into a canal for industrial and commercial purposes. Three manufactured gas plants (MGPs) were formerly located on the Gowanus Canal and discharged waste into it. Surface sediments remain highly contaminated with polycyclic aromatic hydrocarbons (PAHs) long after the MGPs were razed. A hydrogeologic assessment indicates that groundwater passes through the deeper coal tar–contaminated sediment prior to discharging to the canal. This study was undertaken to investigate if groundwater passing through coal tar–contaminated sediment could be responsible for the ongoing contamination of both surface sediments and surface water in the canal. PAH compound distributions in surface water samples collected from the tidal canal at low tide were compared with PAH compounds found in adjacent groundwater‐monitoring wells, point sources (combined sewer overflows [CSOs]), and surface sediments. The results indicate a strong correlation between PAH contaminant distributions in groundwater, sediment, and surface water, indicating that contaminated groundwater passing through the deeper coal tar–contaminated sediments is the primary mechanism contributing to the contamination of both surface sediment and surface water in the canal. Therefore, any sediment remediation efforts in the Gowanus Canal that fail to evaluate and control the upward transport processes have a high chance of failure due to recontamination from below.  ©2016 Wiley Periodicals, Inc.     

In Situ flushing of contaminated soils from a refinery: Organic compounds and metal removals

This article demonstrates the applicability of in situ flushing for the remediation of soil contaminated with petroleum hydrocarbons at a Mexican refinery. The initial average total petroleum hydrocarbon (TPH) concentration for the demonstration field test was 55,156 g/kg. After six weeks of in situ flushing with alternate periods of water and water/surfactant, an average concentration of 1,407 mg/kg was reached, achieving a total removal efficiency of 98 percent. At the end of the process, no hydrocarbons such as diesel; gasoline; benzene, toluene, ethyl benzene, and xylene (BTEX); or petroleum aromatic hydrocarbons (PAHs) were found. Iron washing achieved a removal efficiency of 70 percent, and for vanadium, the removal efficiency was 94.4 percent. The volume of soil treated was 41.6 m³ (38 m²), equivalent to 69.5 tons of soil. A rough calculation of the process costs estimated a total cost of $104.20/m³ ($114.00/m²). Our research indicates that there are a few studies demonstrating in situ flushing experiences under field conditions where both organic (TPH, diesel, gasoline, PAHs, BTEX) and metal (iron and vanadium) removals are reported. © 2004 Wiley Periodicals, Inc.     

Treatment of creosote-contaminated groundwater in vegetated sorption/bio-barriers in cold climates

Permeable barriers are structures installed in situ to treat contaminated groundwater. Pollutants are removed as contaminated groundwater flows through a barrier material. A compost/sand barrier and a plant covered permeable barrier with soil/sand and peat/sand were tested in pilot-scale to treat creosote-contaminated groundwater by sorption and biological removal in situ. Outlet concentrations of the barriers were consistently low during the 29 months of operation. Although sorption sites were filled up with polycyclic aromatic hydrocarbons, they seemed to be regenerated because of biodegradation under aerobic conditions. The vegetated section was least efficient, probably because of lack of oxygen, hence it could not be determined if the plants had a positive effect. As long as biodegradation is efficient the barrier is expected to function for several more years.