Characterization and pilot‐scale studies for chemical oxidation remediation of fractured shale

The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 Wiley Periodicals, Inc.     

Using integrated food‐web and population‐based models for environmental monitoring,remediation decisions,and long‐term planning

While ecologists have used food‐web models to understand how ecosystems function, the potential role of integrated food‐web and population‐based models in environmental monitoring and decision making has been ignored. Sound ecological principles should be integrated with state‐of‐the‐art monitoring and management practices. This article presents the ways in which population‐based models can answer basic ecological questions necessary for decision making about remediation and restoration, and for monitoring to ensure long‐term stewardship. Discussed are the uses of food‐web and population‐based models for understanding the movement of chemicals through different trophic levels. Three examples, including global warming, tributyltin, and monomethylmercury scenarios, are presented to illustrate how such models are useful. The responses of the component parts varies, depending on parameters such as birth, death, and respiration, as well as feeding rates, predator‐prey rates, and uptake and elimination rates. There are several different models available for decision making, with different levels of complexity, based on the specific hypothesis or question being asked and the amount of current information available. Therefore, it is recommended to use deterministic‐based, population‐based food‐web models for ecological risk assessment. © 2001 John Wiley & Sons, 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.     

Perils of categorical thinking: “Oxic/anoxic” conceptual model in environmental remediation

Given ambient atmospheric oxygen concentrations of about 21 percent (by volume), the lower limit for reliable quantitation of dissolved oxygen concentrations in groundwater samples is in the range of 0.1–0.5 mg/L. Frameworks for assessing in situ redox condition are often applied using a simple two‐category (oxic/anoxic) model of oxygen condition. The “oxic” category defines the environmental range in which dissolved oxygen concentrations are clearly expected to impact contaminant biodegradation, either by supporting aerobic biodegradation of electron‐donor contaminants like petroleum hydrocarbons or by inhibiting anaerobic biodegradation of electron‐acceptor contaminants like chloroethenes. The tendency to label the second category “anoxic” leads to an invalid assumption that oxygen is insignificant when, in fact, the dissolved oxygen concentration is less than detection but otherwise unknown. Expressing dissolved oxygen concentrations as numbers of molecules per volume, dissolved oxygen concentrations that fall below the 0.1 mg/L field detection limit range from 1 to 10¹⁷ molecules/L. In light of recent demonstrations of substantial oxygen‐linked biodegradation of chloroethene contaminants at dissolved oxygen concentrations well below the 0.1–0.5 mg/L field detection limit, characterizing “less than detection” oxygen concentrations as “insignificant” is invalid. © 2012 Wiley Periodicals, Inc.     

Pilot scale testing composite swellable organosilica nanoscale zero‐valent iron—Iron‐Osorb®—for in situ remediation of trichloroethylene

Iron‐Osorb^® is a solid composite material of swellable organosilica with embedded nanoscale zero‐valent iron that was formulated to extract and dechlorinate solvents in groundwater. The unique feature of the highly porous organosilica is its strong affinity for chlorinated solvents, such as trichloroethylene (TCE), while being impervious to dissolved solids. The swellable matrix is able to release ethane after dechlorination and return to the initial state. Iron‐Osorb^® was determined to be highly effective in reducing TCE concentrations in bench‐scale experiments. The material was tested in a series of three pilot scale tests for in situ remediation of TCE in conjunction with the Ohio Environmental Protection Agency at a site in central Ohio. Results of these tests indicate that TCE levels were reduced for a period of time after injection, then leveled out or bounced back, presumably due to depletion of zero‐valent iron. Use of tracer materials and soil corings indicate that Iron‐Osorb^® traveled distances of at least 20 feet from the injection point during soil augmentation. The material appears to remain in place once the injection fluid is diluted into the surrounding groundwater. Overall, the technology is promising as a remediation method to treat dilute plumes or create diffuse permeable reactive barriers. Keys to future implementation include developing injection mechanisms that optimize soil distribution of the material and making the system long‐lasting to allow for continual treatment of contaminants emanating from the soil matrix. © 2011 Wiley Periodicals, Inc.     

Use of bio‐traps with multiple substrates and electron acceptors to optimize remediation

Bio‐Traps® were used to investigate biodegradation of benzene, methyl tertiary butyl ether (MTBE), and tertiary butyl alcohol (TBA) under different conditions at a fractured rock site to aid the selection of a bioremediation approach. The Bio‐Traps were amended with the ¹³C‐labeled constituent of interest and sampled sequentially at 15‐, 30‐, 60‐, and 90‐day intervals. The conditions tested were biodegradation during operation of an air sparge system, amendment with nitrate during the air sparge operation, anaerobic biodegradation with the system turned off, and anaerobic biodegradation with nitrate amendment. There was increased biomass with nitrate amendment whether the air sparge system was on or off for all the constituents of interest. The diversity of the microbial community, determined by phospholipid fatty acid analysis, decreased with nitrate amendment as more specialized degraders were selected. The most negative indicators of potential biodegradation performance were observed with the anaerobic control. There was less biomass overall, less incorporation of ¹³C into biomass, and decreased membrane permeability. As testing with additional amendments continues at the site, it is not yet certain which treatment might be selected for bioremediation, but the Bio‐Trap tests thus far have identified that the in situ, natural attenuation condition is least favorable for biodegradation. © 2009 Wiley Periodicals, Inc.     

Optimization and validation of enhanced biological reduction of 1,2,3‐trichloropropane in groundwater

Laboratory and field demonstration studies were conducted to assess the efficacy of enhanced biological reduction of 1,2,3‐trichloropropane (TCP) in groundwater. Laboratory studies evaluated the effects of pH and initial TCP concentrations on TCP reduction and the activity of a microbial inoculum containing Dehalogenimonas (Dhg). Laboratory results showed successful reduction at a pH of 5 to 9 with optimal reduction at 7 to 9 and at initial TCP concentrations ranging from 10 to over 10,000 micrograms per liter (μg/L). Based on findings from the laboratory study, the effects of TCP concentration, geochemical conditions, and amendment concentration on bioremediation efficacy were investigated during a field demonstration at a site with relatively low initial concentrations of TCP (< 2 μg/L). The field demonstration included injection of emulsified vegetable oil (EVO) and lactate as a carbon substrate for biostimulation, followed by bioaugmentation using the microbial inoculum containing Dhg. Post‐injection performance monitoring demonstrated reduction of TCP to below laboratory detection limits (< 0.005 μg/L) after an initial lag period of approximately six months following injections. TCP reduction was accompanied by generation of the degradation byproduct propene. A marginal increase in TCP concentrations, potentially due to an influx of upgradient aerobic groundwater containing TCP, was observed eight months after injections thereby demonstrating the sensitivity of this bioaugmentation application to changes in geochemical parameters. Despite this marginal increase, performance monitoring results indicate continued TCP biodegradation 15 months after implementation of the injection program. This demonstration suggests that enhanced biodegradation of TCP by combining biostimulation and bioaugmentation may be a promising solution to the challenges associated with remediation of TCP, even when present at low part per billion concentrations in groundwater.     

Life‐cycle assessment of in situ thermal remediation

A detailed cradle‐to‐grave life‐cycle assessment (LCA) of an in situ thermal treatment remedy for a chlorinated‐solvent‐contaminated site was performed using process LCA. The major materials and activities necessary to install, operate, monitor, and deconstruct the remedy were included in the analysis. The analysis was based on an actual site remedy design and implementation to determine the potential environmental impacts, pinpoint major contributors to impacts, and identify opportunities for improvements during future implementation. The Electro‐Thermal Dynamic Stripping Process (ET‐DSP?) in situ thermal technology coupled with a dual‐phase extraction and treatment system was evaluated for the remediation of 4,400 yd³ of tetrachloroethene‐ and trichloroethene‐impacted soil, groundwater, and bedrock. The analysis was based on an actual site with an estimated source mass of 2,200 lbs of chlorinated solvents. The remedy was separated into four stages: remedy installation, remedy operation, monitoring, and remedy deconstruction. Environmental impacts were assessed using Sima Pro software, the ecoinvent database, and the ReCiPe midpoint and endpoint methods. The operation stage of the remedy dominated the environmental impacts across all categories due to the large amount of electricity required by the thermal treatment technology. Alternate sources of electricity could significantly reduce the environmental impacts of the remedy across all impact categories. Other large impacts were observed in the installation stage resulting from the large amount of diesel fuel, steel, activated carbon, and asphalt materials required to implement the technology. These impacts suggest where opportunities for footprint reductions can be found through best management practices such as increased materials reuse, increased recycled‐content materials use, and clean fuels and emission control technologies. Smaller impacts were observed in the monitoring and deconstruction stages. Normalized results show the largest environmental burdens to fossil depletion, human toxicity, particulate matter formation, and climate‐change categories resulting from activities associated with mining of fossil fuels for use in electricity production. In situ thermal treatment can reliably remediate contaminated source areas with contaminants located in low‐permeability zones, providing complete destruction of contaminants in a short amount of time, quick return of the site to productive use, and minimized quantities of hazardous materials stored in landfills for future generations to remediate. However, this remediation strategy can also result in significant emissions over a short period of time. It is difficult to quantify the overall value of short‐term cleanups with intense treatment emissions against longer‐term cleanups with lower treatment emissions because of the environmental, social, and economic trade‐offs that need to be considered and understood. LCA is a robust, quantitative tool to help inform stakeholder discussions related to the remedy selection process, trade‐off considerations, and environmental footprint‐reduction opportunities, and to complement a broader toolbox for the evaluation of sustainable remediation strategies. © 2012 Wiley Periodicals, Inc.     

Increase in remediation processes of oil‐contaminated soils

A study was conducted in the region of the Lena River, in northeast Russia, where oil‐contaminated soil remediation is compromised due to the reduced natural attenuation mechanisms in northern eco‐systems. The goal of the study was to analyze the effectiveness of different biological methods for remediating the permafrost soil cover contaminated with high concentrations of oil. For the remediation of the areas with approximately similar levels of contamination (in the range of 10 to 14 grams per kilogram [g/kg] of soil) different biological remediation schemes were applied: site 1: sowing plant seeds of meadow clover grass; site 2: introducing a consortium of hydrocarbon oxidizing microorganisms (HOM); and, site 3: introducing the same consortium of HOM with simultaneously sowing grass mixture. The third scheme, applied for the first time, led to the most favorable results, which might be explained by the synergistic effect based on the principle of positive inverse development.     

Microbial responses to in situ chemical oxidation,six‐phase heating,and steam injection remediation technologies in groundwater

The evaluation of microbial responses to three in situ source removal remedial technologies—permanganate‐based in situ chemical oxidation (ISCO), six‐phase heating (SPH), and steam injection (SI)—was performed at Cape Canaveral Air Station in Florida. The investigation stemmed from concerns that treatment processes could have a variety of effects on the indigenous biological activity, including reduced biodegradation rates and a long‐term disruption of community structure with respect to the stimulation of TCE (trichloroethylene) degraders. The investigation focused on the quantity of phospholipid fatty acids (PLFAs) and its distribution to determine the immediate effect of each remedial technology on microbial abundance and community structure, and to establish how rapidly the microbial communities recovered. Comprehensive spatial and temporal PLFA screening data suggested that the technology applications did not significantly alter the site's microbial community structure. The ISCO was the only technology found to stimulate microbial abundance; however, the biomass returned to predemonstration values shortly after treatment ended. In general, no significant change in the microbial community composition was observed in the SPH or SI treatment areas, and even small changes returned to near initial conditions after the demonstrations. © 2004 Wiley Periodicals, Inc.     

TCE plume remediation via ISCR‐enhanced bioremediation utilizing EHC® and KB‐1®

Groundwater below an operating manufacturing facility in Portland, Oregon, was impacted by chlorinated volatile organic compounds (CVOCs), with concentrations indicative of a dense, nonaqueous‐phase liquid (DNAPL) release. The downgradient plume stretched under the adjacent Willamette River, intersecting zones of legacy impacts from a former manufactured gas plant (MGP). An evaluation of source‐area and downgradient plume treatment remedies identified in situ bioremediation as most likely to be effective for the CVOC plume, while leaving the legacy impacts for other responsible parties. With multiple commercially available products to choose from, the team developed and implemented a bench test to identify the most appropriate technology, which was further evaluated in a field pilot study. The results of the testing demonstrated conclusively that bioremediation enhanced by in situ chemical reduction (ISCR) using EHC® and KB‐1® was most appropriate for this site, providing outstanding results. The following describes the implementation and results of the tests. © 2008 Wiley Periodicals, Inc.     

Sustainable soil remediation by refrigerated condensation at sites with “high‐concentration” recalcitrant compounds and NAPL: Two case studies

Remediation of recalcitrant compounds at sites with high concentrations of volatile organic compounds (VOCs) or nonaqueous‐phase liquids (NAPLs) can present significant technical and financial (long‐term) risk for stakeholders. Until recently, however, sustainability has not been included as a significant factor to be considered in the feasibility and risk evaluation for remediation technologies. The authors present a framework for which sustainability can be incorporated into the remediation selection criteria focusing specifically on off‐gas treatment selection for soil vapor extraction (SVE) remediation technology. SVE is generally considered an old and standard approach to in situ remediation of soils at a contaminated site. The focus on off‐gas treatment technology selection in this article allows for more in‐depth analysis of the feasibility evaluation process and how sustainable practices might influence the process. SVE is more commonly employed for recovery of VOCs from soils than other technologies and generally employs granular activated carbon (GAC), catalytic, or thermal oxidation, or an emerging alternative technology known as cryogenic‐compression and condensation combined with regenerative adsorption (C3–Technology). Of particular challenge to the off‐gas treatment selection process is the potential variety of chemical constituents and concentrations changing over time. Guidance is available regarding selection of off‐gas treatment technology (Air Force Center for Environmental Excellence, 1996; U.S. Environmental Protection Agency, 2006). However, there are common shortcomings of off‐gas treatment technology guidance and applications; practitioners have rarely considered sustainability and environmental impact of off‐gas treatment technology selection. This evaluation includes consideration of environmental sustainability in the selection of off‐gas treatment technologies and a region‐specific (Los Angeles, California) cost per pound and time of remediation comparisons between GAC, thermal oxidation, and C3–Technology. © 2008 Wiley Periodicals, Inc.     

Evaluation of white‐rot fungi for the remediation of creosote‐contaminated soil

Application of fungal‐based bioaugmentation was evaluated for the remediation of creosote‐contaminated soil at a wood‐preserving site in West Virginia. Soil at the site contained creosote‐range polycyclic aromatic hydrocarbons (PAHs) at concentrations in some areas that exceed industrial risk‐based levels. Two white‐rot fungi (Pleurotus ostreatus and Irpex lacteus) were evaluated for remediation effectiveness in a two‐month bench‐scale treatability test. Both fungi produced similar results, with up to 67.3 percent degradation of total PAHs in 56 days. Pilot‐scale testing was performed at the site using Pleurotus ostreatus grown on two local substrate mixtures. During the 276‐day field trial, total PAHs were degraded by up to 93.2 percent, with all individual PAHs except one achieving industrial risk‐based concentrations. It was recommended that fungal‐based remediation be applied to all contaminated soil at the site. © 2002 Wiley Periodicals, Inc.     

Breakthrough in 2D‐CSIA Technology for 1,4‐Dioxane

A dual isotope technology based on compound‐specific stable isotope analysis of carbon and hydrogen (2D‐CSIA) was recently developed to help identify sources and monitor in situ degradation of the contaminant 1,4‐dioxane (1,4‐D) in groundwater. Site investigation and optimized remediation have been the focus of thousands of CSIA applications completed for volatile organic contaminants (VOCs) worldwide. CSIA for the water miscible 1,4‐D, however, has been technically challenging. The most commercially available sample preparation settings “Purge and Trap” for VOC could not efficiently extract 1,4‐D out of water for a reliable CSIA measurement, especially when the concentration is below 100 μg/L. Such a high reporting limit has prevented CSIA from being used for effective site investigation and remediation monitoring at most 1,4‐D contaminated sites, where 1,4‐D is often present at very low ppb levels. This article outlines the recent breakthrough in 2D‐CSIA technology for 1,4‐D in water, reported down to ～1 μg/L for carbon, and ～10 μg/L to 20 μg/L for hydrogen using solid‐phase extraction based on EPA Method 522, and its benefit is highlighted through a case study at a 1,4‐D contaminated site. ©2016 Wiley Periodicals, Inc.     

Editor's perspective‐‐‐Shale gas development: Environmental issues and opportunities

Many professionals in the environmental industry have questioned whether the rapid expansion in shale gas development, particularly in the Marcellus Shale Play, is providing business opportunities. While gas production is a routine practice, the development of shale gas requires a process (fracturing, or, more commonly, “fracing'') that uses chemicals and is far more intrusive to the subsurface environment than traditional gas production. In this Editor's Perspective, we evaluate the environmental issues surrounding shale gas development, with a specific focus on the Marcellus Shale Play because it is currently the most active play in the United States, from both the drilling and political perspectives. In addition, we examine where the business opportunities are likely to be for environmental professionals relative to shale gas development. © 2011 Wiley Periodicals, Inc.     

Case study of testing heavy‐particle concentrator‐aided remediation of lead‐contaminated rifle shooting range soil

Trials were conducted to optimize the parameters of a heavy‐particle concentrator (HPC) for the remediation of soil stockpiles contaminated by metallic lead at the Mount Stuart training area in Townsville, Queensland, Australia. A range of treatment methods, including orbital screen, HPC, and a combination of orbital screen and HPC were evaluated. The treatment efficiency, as well as reductions in Pb and Australian Standard Teaching Procedure values, was ranked: Orbital screen + HPC < HPC < 2nd run through HPC. The combination of orbital screening, HPC, and phosphate‐aided immobilization completely remediated the stockpiled material by reducing total lead to below the Australian National Environmental Protection Measure Health Investigation Level for Soil Contaminant (Recreational; < 600 milligrams lead per kilogram). The optimized parameters of HPC at 4 tonnes per hour of the < 40 millimeter (mm) orbital screen feed fraction were: inclination angle 4°, trommel speed 1,860 revolutions per minute (rpm), HPC belt speed 3.5 rpm, material distribution chute extension 100 mm and water flow 480 liters per minute.     

Preliminary studies on potential remediation of acid mine drainage‐impacted soils by amendment with drinking‐water treatment residuals

Mining operations result in a wide range of environmental impacts: acid mine drainage (AMD) and acid sulfate soils being among the most common. Due to their acidic pH and high soluble metal concentrations, both AMD and acid sulfate soils can severely damage the local ecosystems. Proper post‐mining management practices are necessary to control AMD‐related environmental issues. Current AMD‐impacted soil treatment technologies are rather expensive and typically not environmentally sustainable. We conducted a 60‐day bench‐scale study to evaluate the potential of a cost‐effective and environment‐friendly technology in treating AMD‐impacted soils. The metal binding and acid‐neutralizing capacity of an industrial by‐product, drinking water treatment residuals (WTRs) were used for AMD remediation. Two types of locally generated WTRs, an aluminum‐based WTR (Al‐WTR) and a lime‐based WTR (Ca‐WTR) were used. Highly acidic AMD‐impacted soil containing very high concentrations of metals and metalloids, such as iron, nickel, and arsenic, was collected from the Tab‐Simco coal mine in Carbondale, Illinois. Soil amendment using a 1:1 Al‐ and Ca‐WTR mix, applied at 5 and 10 percent rates significantly lowered the soluble and exchangeable fractions of metals in the AMD‐impacted soil, thus lowering potential metal toxicity. Soil pH increased from an extremely acidic 2.69 to a near‐neutral 6.86 standard units over the 60‐day study period. Results from this preliminary study suggest the possibility of a successful scale‐up of this innovative, cost‐effective, and environmentally sustainable technology for remediating AMD‐impacted acid sulfate soils.