In‐Canal Stabilization/Solidification of NAPL‐Impacted Sediments

In situ solidification (ISS) has been used with increasing frequency as a remedial technology for source area treatment at upland sites impacted with a variety of organic contaminants, including coal tar, creosote, and other nonaqueous phase liquids (NAPLs). With several large, complex, urban water ways and rivers impacted with NAPLs, ISS is more recently being considered as a technology of choice to help reduce remedial costs, minimize short‐ and long‐term impacts of mobile NAPL, and lower the carbon footprint. This article presents the results of a successful pilot study of ISS at the Gowanus Canal Superfund site in Brooklyn, New York. This represents the first major sediment ISS field demonstration project in a saline environment and the first project to evaluate large‐scale implementation of ISS from a barge and through overlaying sediment. ©2016 Wiley Periodicals, Inc.     

Estimating PAH sources in harbor sediments using diagnostic ratios

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the global environment and are subsequently transported into aquatic sediments. As PAHs are formed by various processes, source identification using diagnostic ratios can provide insight to PAH emission sources to distinguish between pyrogenic and petrogenic PAH sources. PAH diagnostic ratios were applied as a forensic source apportionment technique to assess aggregate historical sediment data from 31 small craft harbors (SCHs) across Nova Scotia, Canada. Multiple diagnostic ratios suggest that PAHs present in Nova Scotia SCH sediments are pyrogenic (combustion) in origin, while consistently suggesting that coal‐related PAH sources are potential dominant specific sources. National Institute of Standards and Technology Standard Reference Materials (SRMs) were used as reference for coal tar, urban dust, and diesel exhaust particulates in ratio applications. The SRM for coal tar was most similar to Nova Scotia SCH sediments in multiple ratio applications. Diagnostic ratio results were corroborated by comparing the PAH profile of sediments to source profiles from the literature. Results indicate that Nova Scotia SCH sediments follow global trends by exhibiting a dominant pyrogenic PAH signature, and the specific coal‐related PAH signature of Nova Scotia SCH sediments may be influenced by contamination inputs related to historical industrial coal mining and combustion activities in the province.     

Investigation of NAPL transport through a model sand cap during ebullition

Nonaqueous‐phase liquid (NAPL) migration from sediments to the surface of water bodies has been reported frequently at sites with sediments contaminated with NAPLs, such as coal tar and creosote. Commonly, transport of NAPL from sediment is facilitated by gas ebullition caused by anaerobic biodegradation of organic matter in the sediment. A remedy often specified for these sites is a sand cap, and sand caps amended with sorbent materials (such as organoclays) are being pilot‐tested. This article discusses a laboratory study to assess the effectiveness of a sand layer for controlling NAPL migration. The study used a test column composed of a Plexiglas tube containing a tar source that was buried beneath a 30‐cm‐thick layer of fine sand. Water was added to the column until 5 cm of standing water covered the sand layer. To simulate ebullition, air was injected into the base of the sand column at approximately 200 mL/min. It was observed that the gas and NAPL migrated primarily through channels and fractures in the sand, and was not filtered through a network of stable pores. Tar migrated through the sand layer in 12 hours and accumulated on the water surface for several hours before losing its buoyancy and settling back down to the sand surface. After ending the tar migration experiment, the test column was frozen to preserve structures in the sand. The study showed that the tar migrated through the simulated sand cap in small (2‐mm) channels only a few sand grains thick. The results of this laboratory work call into question the effectiveness of sand caps for controlling NAPL migration from sediment in the presence of ebullition. © 2009 Wiley Periodicals, Inc.     

Contaminant mass flux and forensic assessment of polycyclic aromatic hydrocarbons: Tools to inform remediation decision making at a contaminated site in Canada

Polycyclic aromatic hydrocarbons (PAHs) and metal(loid) mass flux estimates and forensic assessment using PAH diagnostic ratios were used to inform remediation decision making at the Sydney Tar Ponds (STPs) and Coke Ovens cleanup project in eastern Canada. Environmental effects monitoring of surface marine sediments in Sydney Harbor indicated significantly higher PAH concentrations during the first year of remediation monitoring compared to baseline. This was equivalent to PAH loadings of ～2,000 kg over a 15‐month period. Increases in sediment PAH concentrations raised serious concerns for regulators, who requested cessation of remediation activities early in the $400 M (CAD) project. Historically, the STPs were reported as the primary source of PAH contamination in Sydney Harbor with estimated discharges of 300 to 800 kg/year between 1989 and 2001. Mass flux estimates of PAHs and metal(loid)s and PAH diagnostic ratios were used to evaluate if increases in PAH concentrations in marine sediments were the result of the STPs remediation activities. PAH mass flux estimates approximated that 17 to 97 kg/year were discharged from the STPs during three years of remediation and were corroborated by an independent PAH flux estimate of 119 kg in year 1. PAH fluxes to the Sydney Harbor were mostly surface water derived, with groundwater contributing negligible quantities (0.002–0.005 kg/year). Fluxes of metal(loid)s to harbor sediments were stable or declining across all years and were mirrored in sediment metal(loid) concentrations, which lacked temporal variation, unlike total PAH concentrations. Flux results were also corroborated using PAH diagnostic ratios, which found a common source of PAHs. Coal combustion was likely the principal source of PAHs and not migration from the STPs during remediation. Although short‐term residual sediment PAH increases during onset of remediation raised concerns for regulators, calls for premature cessation of remediation early in the project were unwarranted based on only one year of monitoring data. Mass flux estimates and forensic assessments using PAH diagnostic ratios proved useful tools to inform remediation decision making that helped environmental protection and reduced costs associated with lost cleanup time.     

Contributions of common sources of polycyclic aromatic hydrocarbons to soil contamination

Asphalt products, particularly sealants, are prepared using petroleum products that contain a com‐plex mixture of aliphatic and aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs). Clearly, these products are ubiquitous in urban environments, which raises an issue regard‐ing the potential for PAHs to be transported from parking lots to underlying or adjacent soil, surface‐water bodies, or groundwater. Based on a literature review, there are limited studies focus‐ing on this issue; however, the studies that have been published have fascinating conclusions. The literature shows, as expected, that asphalt‐based products contain PAHs. The highest PAH concen‐trations are present in asphalt sealants, particularly those manufactured using coal tar. Furthermore, due to the low solubility and high partition coefficients of PAHs, the potential for PAHs to leach from asphalt surfaces is negligible, which has been confirmed by leachability studies. Thus, there is little risk that PAHs will be present in stormwater runoff or leach into groundwater from asphalt‐paved areas in a dissolved form. However, asphalt pavement and sealants produce particulate matter that can contain concentrations of PAHs in the sub‐percent range (100s to 1,000s mg/kg total PAHs) that is transported in stormwater runoff. Some studies show that this can cause soil and sediment con‐tamination with total PAH concentrations in the range of 1 to 10 mg/kg. From a remediation per‐spective, many site cleanups are conducted to remediate the presence of PAHs to cleanup goals below 1 mg/kg or, in some cases, 0.1 mg/kg or lower. From a total risk perspective, remediating sites to low PAH cleanup goals may be unwarranted in light of the risk of transportable PAHs produced from paved parking surfaces. In other words, is it reasonable to conduct a cleanup to remediate low PAH concentrations and then redevelop the area with asphalt pavement and sealant, which may pose a greater PAH‐related risk? © 2006 Wiley Periodicals, Inc.     

Simulation of flow and mercury transport in Upper East Fork Poplar Creek,Oak Ridge,Tennessee

As a result of nuclear processing activities started back in the 1950s, the environment in the vicinity of the Y‐12 National Security Complex (Y‐12 NSC) in Oak Ridge, Tennessee, and surrounding watersheds has been contaminated by nearly 1,000 tons of elementary mercury. To comply with the state and federal surface water quality standards, a significant reduction in mercury concentration to parts‐per‐trillion levels has been proposed. In order to analyze the mercury cycle in the environment and provide forecasting capabilities for the flow and transport of mercury within the Upper East Fork Poplar Creek (UEFPC) watershed, an integrated surface and subsurface flow and transport model has been developed using the hydrodynamic and transport numerical package, MIKE, developed by the Danish Hydraulic Institute. The model has been constructed and calibrated using an extensive collection of historical records (i.e., hydrological data, and mercury concentration measurements in groundwater, soil, and sediment) obtained from the Oak Ridge Environmental Information System database. Daily fluctuations in stream flow, as a result of scattered rainfall, flooding, and flow augmentation, resuspend the contaminated streambed sediments and/or erode the polluted streambank soil and provide a secondary source of mercury to the creek. In order to investigate the significance of sediment‐mercury interactions on the fate and transport of mercury within the UEFPC study domain, simulations were performed for two different cases (i.e., with and without consideration of sediment‐mercury interactions). Computed total suspended solids and mercury concentrations at the integration point of the creek are compared with the corresponding historical records in both cases. As confirmed by the numerical simulations, a substantial portion of the mercury detected in the river is likely in the form of sediment particle–bound mercury (i.e., mercury particulates). © 2012 Wiley Periodicals, Inc.     

Demonstrating Contaminant Degradation at an MGP Site With Metabolic Gas Flux and Radio Carbon Dating

Obtaining lines of evidence indicating that contamination in sediment environments is degrading and being transformed to less toxic forms is an important component of building support for a monitored natural recovery remedy for contaminated sediments. This project was a field demonstration of manufactured gas plant contaminant degradation in river sediments using metabolic gas flux and was performed in an urban area section of a river in northeastern Indiana. CO₂ sorbent traps were deployed to measure CO₂ flux from the river sediments. Sediment samples were collected and analyzed for polycyclic aromatic hydrocarbon (PAH) concentrations and for microbial community composition using molecular techniques. The results showed that the deployment was successful, measuring CO₂ flux at all sediment locations and demonstrating that microbial contaminant degrading activity was occurring in the sediments. Radio carbon dating showed a significant portion of the CO₂ being generated (approximately 19–27 percent) was the result of fossil fuel degradation. Molecular results showed that the microbial community consisted of phylotypes known to be associated with monocyclic aromatic and PAH degradation. ©2017 Wiley Periodicals, Inc.     

Cost‐Effective Sediment Dredge Disposal Options for Small Craft Harbors in Canada

Sediment dredge disposal options were reviewed to improve cost‐effectiveness and environmental safety for dredging of coastal sediments at the Department of Fisheries and Oceans Small Craft Harbours (DFO‐SCH) program in Canada. Historically, contaminated dredge sediments exceeding federal guidelines were disposed of in nearby landfills. Recent federal regulatory changes in sediment quality guidelines adopted by provincial regulators in Canada has resulted in updates to guidelines for disposal of contaminated solids in landfills. Updates now require specific and general disposal options for contaminated dredge material destined for land‐based disposal, resulting in more expensive disposal in containment cells (if contaminated sediments exceed federal guidelines). However, as part of this study, a leachate testing method was applied to contaminated sediments to simulate migration of potential contaminants in groundwater. Using this approach, leachate quality was compared to federal freshwater criteria and drinking water quality guidelines for compliance with new regulations. Leachate testing performed on the highest sediment contaminant concentrations triggered less than 2 percent potable water exceedances, meaning that most dredge spoils could be disposed of in privately owned or provincially operated landfill sites, providing less expensive disposal options compared to containment cell disposal. Current dredge disposal practices were reviewed at 35 harbor sites across Nova Scotia and their limitations identified in a gap analysis. Improved site management was developed following this review and consultation with interested marine stakeholders. New disposal options and chemical analyses were proposed, along with improvements to cost efficiencies for management of dredged marine sediments in Atlantic Canada. © 2013 Wiley Periodicals, Inc.     

Unreliability of co‐occurrence‐based sediment quality guidelines for contaminated sediment evaluations at Superfund/hazardous chemical sites

Many Superfund/hazardous chemical sites include waterbodies whose sediments contain hazardous chemicals. With the need to assess, rank, and remediate contaminated sediments at such sites, as well as in other waterways, regulators seek a simple, quantitative assessment approach that feeds easily into a decision‐making scheme. Numeric, co‐occurrence‐based “sediment quality guidelines” have emerged with the appearance of administrative simplicity. However, the very foundation of the co‐occurrence approach, based on the total concentrations of a chemical(s) in sediment, is technically invalid; its application relies on additional technically invalid presumptions. Use of technically invalid evaluation approaches renders any assessment of the significance of sediment contamination unreliable. This article reviews the technical roots and assumptions of the co‐occurrence‐based SQGs, the fundamental flaws in the rationale behind their development and application, and their misapplication for sediment quality evaluation. It also reviews concepts and approaches for the more reliable evaluation, ranking, and cleanup assessment of contaminated sediments at Superfund sites and elsewhere. © 2005 Wiley Periodicals, Inc.     

Evaluation of the physical stability,groundwater seepage control,and faunal changes associated with an AquaBlok® sediment cap

Active sediment caps are being considered for addressing contaminated sediment areas in surface‐water bodies. A demonstration of an active cap designed to reduce advective transport of contaminants using AquaBlok® (active cap material) was initiated in a small study area of the Anacostia River in Washington, D.C. The cap remained physically stable, demonstrated the ability to divert groundwater flow, and was recolonized with native organisms after 30 months of monitoring following cap placement. However, the long‐term performance of active caps associated with harsh environmental conditions, hydrogeological settings, and subsurface gas production needs to be further evaluated. © 2008 Wiley Periodicals, Inc.     

Active capping demonstration in the Anacostia river,Washington, D.C.

An active capping demonstration project in Washington, D.C., is testing the ability to place sequestering agents on contaminated sediments using conventional equipment and evaluating their subsequent effectiveness relative to conventional passive sand sediment caps. Selected active capping materials include: (1) AquaBlokTM, a clay material for permeability control; (2) apatite, a phosphate mineral for metals control; (3) coke, an organic sequestration agent; and (4) sand material for a control cap. All of the materials, except coke, were placed in 8,000‐ft test plots by a conventional clamshell method during March and April 2004. Coke was placed as a 1.25‐cm layer in a laminated mat due to concerns related to settling of the material. Postcap sampling and analysis were conducted during the first, sixth, and eighteenth months after placement. Although postcap sampling is expected to continue for at least an additional 24 months, this article summarizes the results of the demonstration project and postcap sampling efforts up to 18 months. Conventional clamshell placement was found to be effective for placing relatively thin (six‐inch) layers of active material. The viability of placing high‐value or difficult‐to‐place material in a controlled manner was successfully demonstrated with the laminated mat. Postcap monitoring indicates that all cap materials effectively isolated contaminants, but it is not yet possible to differentiate between conventional sand and active cap layer performance. Monitoring of the permeability control layer indicated effective reductions in groundwater seepage rates through the cap, but also showed the potential for gas accumulation and irregular release. All of the cap materials show deposition of new contaminated sediment onto the surface of the caps, illustrating the importance of source control in maintaining sediment quality. © 2006 Wiley Periodicals, Inc.     

Removal,Handling, and Thermal Desorption Treatment Techniques for Manufactured Gas Plant Wastes

Due to the nature of contamination typically found at former MGP (manufactured gas plant) sites, excavation and thermal desorption of MGP wastes has proven to be an effective method for the remediation of MGP‐contaminated soil. The use of on‐site thermal desorption enables MGP sites to be quickly remediated at a low cost. Tar pits, holders, and other underground storage structures typically contain coal tar residuals and waste from former operations, and the areas around these structures are often significantly contaminated. Thus, excavation techniques, odor and vapor management, and material preparation for the treatment method are important factors to consider when developing a site remediation strategy. This article reviews typical excavation and handling methods associated with the remediation of former MGP sites and discusses the treatment of MGP wastes using on‐site thermal desorption technology. © 2001 John Wiley & Sons, Inc.     

Ambient levels of PFOS and PFOA in multiple environmental media

Making remediation and risk management decisions for widely‐distributed chemicals is a challenging aspect of contaminated site management. The objective of this study is to present an initial evaluation of the ubiquitous, ambient environmental distribution of poly‐ and perfluoroalkyl substances (PFAS) within the context of environmental decision‐making at contaminated sites. PFAS are anthropogenic contaminants of emerging concern with a wide variety of consumer and industrial sources and uses that result in multiple exposure routes for humans. The combination of widespread prevalence and low screening levels introduces considerable uncertainty and potential costs in the environmental management of PFAS. PFAS are not naturally‐occurring, but are frequently detected in environmental media independent of site‐specific (i.e., point source) contamination. Information was collected on background and ambient levels of two predominant PFAS, perfluorooctane sulfonate and perfluorooctanoate, in North America in both abiotic media (soil, sediment, surface water, and public drinking water supplies) and selected biotic media (human tissues, fish, and shellfish). The background or ambient information was compiled from multiple published sources, organized by medium and concentration ranges, and evaluated for geographical trends and, when available, also compared to health‐based screening levels. Data coverage and quality varied from wide‐ranging and well‐documented for soil, surface water, and serum data to more localized and less well‐documented for sediment and fish and shellfish tissues and some uncertainties in the data were noted. Widespread ambient soil and sediment concentrations were noted but were well below human health‐protective thresholds for direct contact exposures. Surface water, drinking water supply waters (representing a combination of groundwater and surface water), fish and shellfish tissue, and human serum levels ranged from less than to greater than available health‐based threshold values. This evaluation highlights the need for incorporating literature‐based or site‐specific background into PFAS site evaluation and decision‐making, so that source identification, risk management, and remediation goals are properly focused and to also inform general policy development for PFAS management.     

The Hidden Potential of Mass‐based Treatment: A Method for Preventing Rebound

A major challenge for in situ treatment is rebound. Rebound is the return of contaminant concentrations to near original levels following treatment, and frequently occurs because much of the residual nonaqueous phase liquid (NAPL) trapped within the soil capillaries or rock fractures remains unreachable by conventional in situ treatment. Fine‐textured strata have an especially strong capacity to absorb and retain contaminants. Through matrix diffusion, the contaminants dissolve back into groundwater and return with concentrations that can approach pretreatment levels. The residual NAPL then serves as a continuing source of contamination that may persist for decades or longer. A 0.73‐acre (0.3‐hectare) site in New York City housed a manufacturer of roofing materials for approximately 60 years. Coal tar served as waterproofing material in the manufacturing process and releases left behind residual NAPL in soils. An estimated 47,000 pounds (21,360 kg) of residual coal tar NAPL contaminated soils and groundwater. The soils contained strata composed of sands, silty sands, and silty clay. A single treatment using the RemMetrik^® process and Pressure Pulse Technology^® (PPT) targeted the contaminant mass and delivered alkaline‐activated sodium persulfate to the NAPL at the pore‐scale level via in situ treatment. Posttreatment soil sampling demonstrated contaminant mass reductions over 90 percent. Reductions in posttreatment median groundwater concentrations ranged from 49 percent for toluene to 92 percent for xylenes. Benzene decreased by 87 percent, ethylbenzene by 90 percent, naphthalene by 80 percent, and total BTEX by 91 percent. Mass flux analysis three years following treatment shows sustained reductions in BTEX and naphthalene, and no rebound. ©2015 Wiley Periodicals, Inc.     

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.     

Designing and implementing an urban river remediation

In 2017, Consumers Energy completed a sediment response action in the Flint River to address manufactured gas plant‐related impacts in sediments and at the groundwater‐surface water interface. The project site is located in an urban, channelized, developed reach of the river. Multiple property owners and site constraints presented unique challenges for the remedial design, including the presence of Hamilton Dam at the downstream edge of the site which was considered a high‐hazard dam in “very poor condition.” An additional consideration was the City of Flint water crisis which was initially exposed in 2014. The sediment response action was not related to the water crisis because the site is located approximately two miles downstream of the City's water intake, but design, permitting, and construction began after 2014, so the timing added a heightened sense of awareness from the public stakeholders. The successful completion of the sediment response action was the result of deliberate planning, iterative engineering, and open communication with stakeholders that enabled a careful balancing of objectives with sometimes competing interests.     

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.

     

Migration of VOC Plume in the Subsurface Domain at the Y‐12 National Security Site

During the production of thermonuclear fusion weapons at the Y‐12 National Security Complex (Y‐12 NSC) in Oak Ridge, Tennessee, between 1950 and 1963, the regional environment was extensively contaminated by volatile organic compounds (VOCs). Old Salvage Yard (OSY) on the western side of the site has been characterized as the major source of VOCs. In order to analyze the long‐term fate and transport of chlorinated VOC sources, an integrated surface and subsurface flow and transport model was developed for the Y‐12 NSC using the hydrodynamic and transport numerical package MIKE‐SHE. The model was developed considering the recent hydrogeological investigations on preferential flow and transport pathways at the site. The model was calibrated using the recorded groundwater flow and water‐quality data. The modeling simulated migration of the VOC plume for the next 100 years. Considering a range of hydrogeological and transport parameters, uncertainty of the results is discussed. The modeling predicted that tetrachloroethene, trichloroethene, and 1,2‐dichloroethene may exceed human health–related risk levels for the next 10 to 20 years. However, the contamination is unlikely to migrate to surface water under the current hydrogeological conditions and will decay below acceptable risk levels within approximately 20 years. © 2013 Wiley Periodicals, Inc.     

Multiphase extraction radius of influence: Evaluation of design and operational parameters

A common remedial technology for properties with subsurface soil and groundwater contamination is multiphase extraction (MPE). MPE involves the extraction of contaminated groundwater, free‐floating product, and contaminated soil vapor from the subsurface. A network of recovery wells conveys fluids to a vacuum pump and to the treatment system for the contaminated groundwater and soil vapor. This article describes a study of MPE operational data from nine similar remediation projects to determine the most important design parameters. Design equations from guidance manuals were used to estimate the expected radius of influence (ROI) based on measured field data. ROIs were calculated for the vapor flow rate through the subsurface and for the groundwater drawdown caused by the MPE remediation activities. The calculated ROIs were compared to the measured ROIs to corroborate the assumptions made in the calculations. Once it was established that the calculated and field‐measured ROIs were comparable, a sensitivity analysis determined ranges of different design and operational parameters that most affected the ROIs. © 2012 Wiley Periodicals, Inc.