Applied geologic,microbiological, and engineering constraints of in-situ BTEX bioremediation

An in-situ bioremediation project has been designed and constructed for a site in south-central Kansas just north of Wichita. A pipeline leaked an unknown quantity of refinedfuels in the 1970s. The spill was undetected until hydrocarbons were found in a nearby municipal water supply well. Of concern, from a regulatory perspective, are the alkylbenzene components found in the groundwater, including benzene, toluene, ethylbenzene, and xylene (BTEX). Initial abatement procedures, including free product removal and pumping, had become ineffective. In-situ bioremediation was selected to complete the restoration process. The project emphasizes the need for a strong understanding of the geologic and hydrogeologic conditions prevalent under the site. Site studies were conducted to determine the distribution and mass of the contaminant and the hydraulic regime. Laboratory microbial studies were used to determine the efficacy of nitrate as a primary electron acceptor. Information from site studies was used to design a treatment system tailored to the requirements of the site. The treatment system is designed to deliver the maximum amount of nutrient-enriched water to the contaminated zone while maintaining hydraulic control of the site.     

A method to compare groundwater cleanup technologies

DuPont has developed a method to compare, on a consistent economic basis, in situ remediation technologies. The methodology employs a template site with a perchloroethylene plume 1000 ft long by 400 ft wide, and incorporates various aquifer thicknesses and depths. Variables considered in the methodology include duration of the remediation; estimated engineering and flow/transport modeling costs; equipment costs; and operation, maintenance, and monitoring costs. In this article, substrate-enhanced anaerobic bioremediation, intrinsic bioremediation, in situ permeable reactive barriers, and pump-and-treat systems are evalutated. Cost metrics include present cost, cost per pound of contaminant removed, and cost per 1000 gals treated, using a discounted cash-flow analysis. Costs of the remedial alternatives increase starting from intrinsic bioremediation, to substrate-enhanced anaerobic bioremediation, to a biological substrate-enhanced anaerobic barrier, to in situ permeable reactive barriers, to pump-and-treat systems with air stripping and carbon adsorption.     

Advanced site diagnostic tool 3D‐CSIA for in situ remediation

In situ remediation is inherently considered “green remediation.” The mechanisms of destruction by in situ technologies, however, are often unseen and not well understood. Further, physical effects of amendment application affect concentration data in an identical manner as the desired reactive mechanism. These uncertainties have led to the weight‐of‐evidence approach when proving viability: multiple rounds of data collection, bench studies, pilot studies, and so on. Skipping these steps has resulted in many failed in situ applications. Traditional assessment data are often tangential to the desired information (e.g., “Is contaminant being destroyed or just being pushed around and diluted?” and “What is the mechanism of the destruction and can it be monitored directly?”). An advanced site diagnostic tool, “Three‐Dimensional Compound Specific Stable Isotope Analysis” (3D‐CSIA), can assess the viability of in situ technologies by providing definitive data on contaminant destruction that are not concentration‐related. The 3D‐CSIA tool can also locate source zones and apportion remediation cost by identifying plumes of different isotope signatures and fractionation trends. Further, use of the 3D‐CSIA tool allows remediation professionals to evaluate effectiveness of treatment and make better decisions to expedite site closure and minimize costs. This article outlines the fundamentals of advanced site diagnostic tool 3D‐CSIA in detail, and its benefit is highlighted through a series of case studies at chlorinated solvent–contaminated sites. © 2010 Wiley Periodicals, Inc.     

A Cost Comparison of Organic versus Inorganic Ion Exchange Resin for Remediation of High-Level Waste

Ion exchange (IX) can be used to aid in the remediation of underground storage tank (UST) radioactive waste at the U.S. Department of Energy's Hanford site in the state of Washington. In particular, IX can be used to concentrate the radionuclides in liquid-based waste prior to immobilization for final disposal. Concentration of the radionuclides can significantly reduce the final immobilized high-level waste volume and consequent overall remediation cost. Organic and inorganic IX resins each have unique advantages and disadvantages regarding the remediation process. This study presents a comparison of the remediation cost for UST waste at Hanford for a phenol-formaldehyde type organic resin versus crystalline silico-titanate inorganic resin. It was determined that with optimum processing conditions such as waste blending and sludge washing, remediation with the inorganic resin would be less expensive than the organic resin. Assuming baseline remediation conditions, the use of inorganic rather than organic IX resin for UST remediation at Hanford can save approximately $383 million. A limited sensitivity analysis was performed as pan of this study and is reported in the following. © 1999 John Wiley & Sons, Inc.     

Feasibility of greenhouse gas emissions offsets for natural source zone depletion of petroleum hydrocarbons

Hydrocarbon biodegradation is an important process for remediating petroleum hydrocarbons and managing large sites. However, this biodegradation results in what are essentially unavoidable CO₂ emissions to the atmosphere. A feasibility assessment was conducted to quantitatively consider reuse options for petroleum brownfields that would offset contaminant respiration emissions rates in the 2 to 10 micromoles CO₂ per meters squared per second (μmol CO₂ m^?2 s^?1) typically observed. Under a wide range of solar resource scenarios, placement of solar panels over only a fraction (no more than 35%) of the site footprint is estimated as necessary to achieve an emissions offset. Similarly, placement of one 30‐meter tall wind turbine of moderate rating (approximately 30 to 50 kW) is sufficient to provide an offset for a nominal 1,000 square meters site. For spreading of spent calcium‐rich construction materials, under even a high emissions scenario, the required footprint for the offset is less than the site footprint. While these approaches appear feasible, revegetation as forestland is estimated as sufficient only at contaminant respiration rates up to 2 μmol CO₂ m^?2 s^?1. Revegetation as rangeland and cropland, which sequesters CO₂ mainly in soil organic carbon, is estimated as requiring more than the site footprint under many contaminant respiration rates. Revegetation as a wetland fares slightly better from a carbon storage perspective, but it also has the potential for N₂O and CH₄ emissions that may largely undo the benefit from sequestration in soil organic matter. Overall, the results indicate several methods that are viable for achieving emissions offsets and a quantitation method that can be honed with site‐specific input parameters as appropriate.     

Spreadsheet‐Based Design Tool for In Situ Anaerobic Bioremediation Using Soluble Substrate

A Microsoft Excel spreadsheet‐based design tool has been developed to assist remediation professionals in the design of injection systems for distributing soluble substrate (SS) to enhance in situ anaerobic bioremediation. The user provides site data, design parameters, and unit‐cost information to generate estimates of remediation‐system cost and steady‐state contact efficiency (CE_SS) for various designs. CE_SS is estimated from a nonlinear regression equation that includes terms for the SS injection concentration (C_I), minimum substrate concentration (C_MIN), groundwater travel time between rows of injection wells (T_T), SS half‐life (T_H), substrate reinjection time interval (T_R), and pore volumes of substrate solution injected (PV). With this tool, users can quickly compare the relative costs and performance of different injection alternatives and identify the best design for their specific site conditions. The design process embodied in the tool includes: (1) entering injection‐well configuration and unit costs for well installation, injection, and substrate; (2) determining treatment‐zone dimension; (3) selecting trial injection‐well spacing, time period between substrate reinjection, and injection pore volume; and (4) estimating contact efficiency and capital and life‐cycle costs. This process is then repeated until a final design is selected. In most cases, injection costs increase with increasing CE_SS. However, the best (highest) ratio of CE_SS to injection cost typically occurs for CE_SS in the range of 70 to 80 percent. © 2013 Wiley Periodicals, Inc.     

Case study of ex situ remediation and conversion to a combined in situ/ex situ bioremediation approach at an oxygenated gasoline release site

In response to an oxygenated gasoline release at a gas station site in New Hampshire, a temporary treatment system consisting of a single bedrock extraction well, a product recovery pump, an air stripper, and carbon polishing units was installed. However, this system was ineffective at removing tertiary butyl alcohol from groundwater. The subsequent remedial system design featured multiple bedrock extraction wells and an ex situ treatment system that included an air stripper, a fluidized bed bioreactor, and carbon polishing units. Treated effluent was initially discharged to surface water. Periodic evaluation of the remediation system performance led to system modifications, which included installing an additional extraction well to draw contaminated groundwater away from an on‐site water supply well, adding an iron and manganese pretreatment system, and discharge of treated effluent to an on‐site drywell. Later, the air stripper and carbon units were eliminated, and an infiltration gallery was installed to receive treated, oxygenated effluent in order to promote flushing of the smear zone and in situ bioremediation in the source area. This article discusses the design, operation, performance, and modifications to the remediation system over time, and provides recommendations for similar sites. © 2007 Wiley Periodicals, Inc.     

Rapid full‐scale bioremediation of perchlorate in soil at a large brownfields site

The former Bermite site north of Los Angeles, California, was used to manufacture various explosives and related products containing energetic compounds, including perchlorate. Remediation of perchlorate in site soil and groundwater is being conducted to meet regulatory requirements and allow planned redevelopment activities to proceed. The general approach to perchlorate remediation of shallow soil at the site includes excavation of affected soils followed by ex situ bioremediation. Glycerin was chosen for use as an electron donor because of its stability, safety, low cost, and regulatory acceptance. However, full‐scale bioremediation operation with glycerin initially resulted in inconsistent results despite consistent perchlorate biodegradation observed in treatability study microcosms. To eliminate the inconsistency and optimize the biotreatment process, additional studies were performed in the field on parallel tracks to determine crucial factor(s) that influenced inconsistent breakdown of perchlorate in site soils. Total Kjeldahl nitrogen (TKN) was determined to be a significant factor limiting perchlorate biodegradation. The addition of di‐ammonium phosphate (DAP) resulted in the consistent and complete perchlorate removal, generally within two weeks of incubation with a median destruction rate of about 200 μg/kg/day. Soil processing rates were gradually increased over the year, and, by the summer, approximately 2,000 to 2,500 tons of soil were being processed per day with a total of approximately 160,000 tons processed by the end of July. The total unit treatment cost for the process is about approximately $35/ton. The glycerin‐DAP process is playing a major role in the remediation of this 1,000‐acre former industrial site. © 2008 Wiley Periodicals, Inc.     

Remediation,land use,and risk at Hanford

U.S. Department of Energy (US DOE) remediation responsibilities include the Hanford site in Washington State. Cleanup is governed by the Tri‐Party Agreement (TPA) between the US DOE as the responsible party and the U.S. Environmental Protection Agency and Washington State Department of Ecology as joint regulators. In 2003, the US DOE desired to implement a “Risk‐Based End State” (RBES) policy at Hanford, with remediation measures driven by acceptable risk standards using exposure scenarios based on the 1999 Hanford Comprehensive Land‐Use Plan. Facing resistance from regulators and stakeholders, the US DOE solicited public input on its policy. This led to a Hanford Site End State Vision in 2005 and a commitment that the TPA would continue to control remediation. This article describes how regulator and public participation modified RBES to an end‐state vision. © 2010 Wiley Periodicals, Inc.     

Evolution of predictive tools for in situ bioremediation and natural attenuation evaluations

Proving the viability of in situ bioremediation technologies and gathering data for its full‐scale implementation typically involves collecting multiple rounds of data and often completing microcosm studies. Collecting these data is cumbersome, time‐consuming, costly, and typically difficult to scale. A new method of completing microcosm studies in situ using an amendable sampling device deployed and incubated in groundwater monitoring wells provides actionable data to expedite site cleanup. The device, referred to as a Bio‐Trap® sampler, is designed to collect actively colonizing microbes and dissolved organic compounds from groundwater for analysis using conventional analytical techniques and advanced diagnostic tools that can answer very specific design and viability questions relating to bioremediation. Key data that can be provided by in situ microcosm studies using Bio‐Trap® samplers include definitively demonstrating contaminant destruction by using compound‐specific isotope analysis and providing data on the mechanism of the degradation by identifying the responsible microbes. Three case studies are presented that demonstrate the combined flexibility of Bio‐Trap® samplers and advanced site diagnostics. The applications include demonstrating natural attenuation of dissolved chlorinated solvents, demonstrating natural attenuation of dissolved petroleum compounds, and using multiple Bio‐Trap® samplers to comparatively assess the viability of bioaugmentation at a chlorinated solvent release site. At each of these sites, the in situ microcosm studies quickly and cost‐effectively answered key design and viability questions, allowing for regulatory approval and successful full‐scale implementation. © 2010 Wiley Periodicals, Inc.     

Successful full‐scale enhanced anaerobic dechlorination at a NAPL strength 1,1,1‐TCA source area

Bioremediation of 1,1,1‐trichloroethane (TCA) is more challenging than bioremediation of other chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). TCA transformation often occurs under methanogenic and sulfate‐reducing conditions and is mediated by Dehalobacter. The source area at the project site contains moderately permeable medium sand with a low hydraulic gradient and is approximately 0.5 acre. TCA contamination generally extended to 35 feet, with the highest concentrations at approximately 20 feet. The concentrations then decreased with depth; several wells contained 300 to 600 mg/L of TCA prior to bioremediation. The area of treatment also contained 2 to 30 mg/L of TCE from an upgradient source. Initial site groundwater conditions indicated minimal biotic dechlorination and the presence of up to 20 mg/L of nitrate and 90 mg/L of sulfate. Microcosm testing indicated that TCA dechlorination was inhibited by the site's relatively low pH (5 to 5.5) and high TCA concentration. After the pH was adjusted and TCA concentrations were reduced to less than 35 mg/L (by dilution with site water), dechlorination proceeded rapidly using whey (or slower with sodium lactate) as an electron donor. Throughout the remediation program, increased resistance to TCA inhibition (from 35 to 200 mg/L) was observed as the microbes adapted to the elevated TCA concentrations. The article presents the results of a full‐scale enhanced anaerobic dechlorination recirculation system and the successful efforts to eliminate TCA‐ and pH‐related inhibition. © 2012 Wiley Periodicals, Inc.     

Estimating Remediation and Contaminant Respiration Emissions for Alternatives Comparisons at Petroleum Spill Sites

Greenhouse gas emissions assessments for site cleanups typically quantify emissions associated with remediation and not those from contaminant biodegradation. Yet, at petroleum spill sites, these emissions can be significant, and some remedial actions can decrease this additional component of the environmental footprint. This article demonstrates an emissions assessment for a hypothetical site, using the following technologies as examples: excavation with disposal to a landfill, light nonaqueous‐phase liquid (LNAPL) recovery with and without recovered product recycling, passive bioventing, and monitored natural attenuation (MNA). While the emissions associated with remediation for LNAPL recovery are greater than the other considered alternatives, this technology is comparable to excavation when a credit associated with product recycling is counted. Passive bioventing, a green remedial alternative, has greater remedial emissions than MNA, but unlike MNA can decrease contaminant‐related emissions by converting subsurface methane to carbon dioxide. For the presented example, passive bioventing has the lowest total emissions of all technologies considered. This illustrates the value in estimating both remediation and contaminant respiration emissions for petroleum spill sites, so that the benefit of green remedial approaches can be quantified at the remedial alternatives selection stage rather than simply as best management practices. ©2015 Wiley Periodicals, Inc.     

Sodium Persulfate Oxidation for the Remediation of Chlorinated Solvents (USEPA Superfund Innovative Technology Evaluation Program)

This study has been conducted at the University of Connecticut (UCONN) in connection with the USEPA Superfund Innovative Technology Evaluation (SITE) program to evaluate a chemical oxidation technology (sodium persulfate) developed at UCONN. A protocol to assess the efficacy of oxidation technologies has been used. This protocol, which consists of obtaining data from a treatability study, tested two in-situ chemical oxidation technologies that can be used on soil and groundwater at a site in Vernon, Connecticut. Based on the treatability report results and additional field data collected at the site, the design for the field implementation of the chemical oxidation remediation was completed. The results indicate that both sodium persulfate and potassium permanganate were able to effectively degrade the target VOCs (i.e., PCE, TCE and cis-DCE) in groundwater and soil-groundwater matrices. In the sodium persulfate tests (120 hrs), the extent of destruction of target VOCs was 74% for PCE, 86% for TCE and 84% for cis-DCE by Na₂S₂O₈ alone and 68% for PCE, 76% for TCE, and 69% for cis-DCE by Fe(II)-catalyzed Na₂S₂O₈. The results demonstrate the sodium persulfate's ability to degrade PCE, TCE and cis-DCE. It is expected that given sufficient dose and treatment time, a higher destruction rate of the dissolved phase contamination can be achieved. The data also indicates that the catalytic effect of the iron chelate on persulfate chemistry was much less pronounced in the soil-groundwater matrix. This indicates an interaction between the iron chelate solution and the soil, which may have resulted in a lower availability of the chelated iron for catalysis. The study showed that the remediation of the VOCs-contaminated soil and groundwater by in-situ chemical oxidation using sodium persulfate is feasible at the Roosevelt Mills site. As a result, the USEPA SITE program will evaluate this technology at this site.     

Vegetative remediation process offers advantages over traditional pump-and-treat technologies

The use of bioremediation technologies to clean up contaminated soil and groundwater is increasingly winning favor over more costly and often ineffective mechanical approaches. One new type of bioremediation process, known as TreeMediation^TM, uses trees and other vegetation to remediate soil by acting as a natural pump to extract and remediate contaminated groundwater in aquifers less than 30 feet deep. This article describes this innovative treatment method, shows its advantages over traditional pump and-treat techniques, and explains how TreeMediation is being used to extract nitrate and ammonium contamination from an aquifer in New Jersey.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

A conceptual study on the bio-wall technology: Feasibility and process design

In-situ bioremediation is a process by which contaminants in subsurface environments are biologically eliminated or mineralized; however, it is often difficult to implement. Microbes sparsely distributed in deep soils are incapable of degrading a chemical rapidly; furthermore, fine-pore structures of soils tend to retard the penetration and propagation of these microbes and hinder oxygen transfer. The latter is particularly detrimental to the aerobic growth of microbes, which is often essential for bioremediation. Measures intended to promote bioremediation, such as the addition of surfactants for enhancing dissolution and the application of genetically engineered microbes for accelerating the biodegradation of contaminants, are almost impossible to adopt. This is attributable to the fact that various facets of the bioremediation process (e.g., the distribution of dissolved contaminants, nutrients, and oxygen, and the concentration of microbes) cannot be readily manipulated. This article proposes a novel technology, namely, bio-wall. This technology resorts to an in-situ constructed medium with porosity and organic content greater than those of the original soil for promoting the adsorption and retention of microbes and the biodegradation of contaminants. Moreover, oxygen and nutrients are supplied to the bio-wall to facilitate microbialgrowth. The results of conceptual design study and simulation have revealed that the technology is indeed feasible and, under certain environmental conditions, cost-effective. Particularly noteworthy is the fact that bio-wall can prevent contaminant migration through the enhancement of the biodegradation rate and reduction of the plume-distance, both by several orders of magnitude.     

Nitrate enhancement of in-situ bioremediation of monoaromatic compounds in groundwater

Removal of benzene, toluene, and the isomers of xylene (BTX) from gasoline-contaminated groundwater under denitrifying conditions was investigated. In laboratory microcosms, benzene removal was found to be significantly stimulated by phosphorus addition. For total xylenes, removal followed a similar response, but toluene disappearance was unaffected by phosphorus enrichment. An in-situ bioremediation project was conducted to extend this laboratory work to an actual field-scale cleanup of gasoline-contaminated groundwater. The flow of groundwater from two extraction wells to an infiltration gallery created a mostly closed loop to recycle the groundwater enriched with added nutrients and the electron acceptor (nitrate). The coincident occurrence of BTX loss (greater than 90 percent) in situ, nitrate (as well as phosphorus and ammonia) appearance, and increased levels of denitrifying bacteria at a downgradient well all suggested that denitrification may play a significant role in BTX remediation at this site.     

Particle Surface Hydrophobicity and the Dechlorination of Chloro-Compounds by Iron Sulfides

Halogenated aliphatic compounds (HACs) can be reduced by iron sulfides in aqueous systems. Generally, the thermodynamics and kinetics of dehalogenation reactions are controlled by the mineralogical and particle surface characteristics of the iron sulfide, the composition of the HAC and reaction conditions such as component concentrations, pH and Eh. In this theoretical and experimental investigation of CCl₄ and C₂Cl₆ reduction by FeS and FeS₂, the roles of hydrophobic and hydrophilic sites on the iron sulfides were analyzed. Experimental data obtained through zeta potential measurements, were used along with the Gouy-Chapman model and the simple two-layer surface complexation model to relate iron sulfide surface hydroxyl densities to the degree of HAC dehalogenation. The surface hydroxyl site densities of FeS and FeS₂ were found to be 0.11 sites/nm² and 0.21 sites/nm², respectively. During the dehalogenation reaction process, CCl₄ was found to decrease to its first intermediate product CHCl₃ within the first 20 hours followed by a slower process of conversion to CH₂Cl₂. The results also show that FeS is less hydrated (more hydrophobic) than FeS₂. For CCl₄ and C₂Cl₆, FeS is a better dehalogenator than FeS₂. These results imply that particle surface hydrophobicity is a critical factor in surface-mediated dehalogenation of chlorinated compounds.     

Insufficient source area remediation results in the rebound of TCE breakdown products in groundwater

In the early 1990s, a soil removal action was completed at a former disposal pit site located in southern Michigan. This action removed waste oil, cutting oil, and chlorinated solvents from the unsaturated zone. To contain groundwater contaminant migration at the site, a groundwater pump‐and‐treat system comprised of two extraction wells operating at a combined flow of 50 gallons per minute, carbon treatment, and a permitted effluent discharge was designed, installed, and operated for over 10 years. Groundwater monitoring for natural attenuation parameters and contaminant attenuation modeling demonstrated natural attenuation of the contaminant plume was adequate to attain site closure. As a result of incomplete contaminant source removal, a rebound of contaminants above the levels established in the remedial action plan (RAP) has occurred in the years following system shutdown and site closure. Groundwater concentrations have raised concerns regarding potential indoor air quality at adjacent residential properties constructed in the past 9 to 10 years. The only remedial option available in the original RAP is to resume groundwater pump‐and‐treat. To remediate the source area, an alternate remediation strategy using an ozone sparge system was developed. The ozone sparge remediation strategy addresses the residual saturated zone contaminants beneath the former disposal pit and reestablishes site closure requirements without resumption of the pump‐and‐treat system. A pilot study was completed successfully; and the final system design was subsequently approved by the Michigan Department of Environmental Quality. The system was installed and began operations in July 2010. As of the January 2011 monitoring event, the system has shown dramatic improvement in site contaminant concentrations. The system will continue to operate until monitoring results indicate that complete treatment has been obtained. The site will have achieved the RAP objectives when the system has been shut down and meets groundwater residential criteria for four consecutive quarters. © 2011 Wiley Periodicals, Inc.