In situ chemical oxidation: Lessons learned at multiple sites

This paper compiles a detailed set of in situ chemical oxidation (ISCO) lessons learned pertaining to design, execution, and safety based on global experiences over the last 20 years. While the benefits of a “correct” application are known (e.g., cost effectiveness, speed, permanence of treatment), history also provides examples of a variety of “incorrect” applications. These provide an opportunity to highlight recurring themes that resulted in failures. ISCO is, and will continue to provide, an important remedial tool for site remediation, particularly as a component of a multifaceted approach for addressing large and complex sites. Future success, however, requires an objective understanding of both the benefits and the limitations of the technology. The ability to learn from the mistakes of the past provides an opportunity to eliminate, or at least minimize, them in the future. Over the last 25 years of ISCO application, process understanding and knowledge have improved and evolved. This paper combines a thorough discussion of lessons learned through decades of ISCO implementation throughout all aspects of ISCO projects with an analysis of changes to the ISCO remediation market. By discussing the interplay of these two themes and providing recommendations from collective lessons learned, we hope to improve the future of safe, cost‐effective, and successful applications of ISCO.     

有机污染土壤原位化学氧化药剂投加方式的综述

原位化学氧化技术是修复有机污染土壤最经济有效的技术之一。药剂的投加与分散技术是原位化学氧化修复技术的核心。药剂投加与分散方式的选择与污染场地的土壤渗透性、特征水平、污染深度、氧化剂性质、修复费用等相关。阐述了直压式注射法、注射井法、土壤置换法和高压-旋喷注射法等药剂投加与分散技术的适用性、控制参数及优缺点等,引用工程实例对药剂投加与分散技术在原位化学氧化修复过程中的应用情况进行了论证。     

The effects of in situ chemical oxidation on microbiological processes: A review

The effects of in situ chemical oxidation (ISCO) on biological processes, as reported in the literature, were researched to determine if coupling ISCO with in situ bioremediation could be achieved in field and laboratory experiments. Literature was compiled concerning the effect of ISCO on microbial communities following addition of a chemical oxidant at a range of concentrations designed to treat a variety of subsurface contaminants. The results indicate that although microbial communities may potentially be adversely affected by chemical oxidation in the short term, a rebound of microbial biomass and/or bioremediation activity can be expected. Successfully coupling ISCO with bioremediation in field applications may be a cost‐effective method of achieving risk‐based site remediation goals. © 2006 Wiley Periodicals, Inc.     

DNAPL Source Depletion: 2. Attainable Goals and Cost–Benefit Analyses

It is difficult to quantify the range in source strength reduction (MdR) that may be attainable from in situ remediation of a dense nonaqueous‐phase liquid (DNAPL) site given that available studies typically report only the median MdR without providing insights into site complexity, which is often a governing factor. An empirical study of the performance of in situ remediation at a wide range of DNAPL‐contaminated sites determined MdRs for in situ bioremediation (EISB), in situ chemical oxidation (ISCO), and thermal treatment remedies. Median MdR, geometric mean MdR, and lower/upper 95 percent confidence interval for the mean were: 49x, 105x, 20x/556x, respectively, for EISB; 9x, 21x, and 4x/110x for ISCO; and 19x, 31x, and 6x/150x for thermal treatment. Lower MdR values were determined for large, complex sites and for sites with DNAPL pool‐dominated source zones. A feasibility analysis of partial DNAPL depletion is described for a pool‐dominated source zone. Back‐diffusion from low‐hydraulic conductivity units within a pool‐dominated source zone is shown to potentially sustain a secondary source for more than 1,000 years, indicating that aggressive source treatment may not reduce the remediation timeframe. Estimated plume response demonstrates there may be no reduction in cost associated with aggressive treatment, and little difference in risk reduction associated with the various alternatives. Monitored natural attenuation (MNA) for the source zone is shown to be a reasonable alternative for the pool‐dominated source zone considered in this example. It is demonstrated that pool‐dominated source zones with a large range in initial DNAPL mass (250 to 1,500 kg) may correspond to a narrow range in source strength (20 to 30 kg/year). This demonstrates that measured source strength is nonunique with respect to DNAPL mass in the subsurface and, thus, source strength should not be used as the sole basis for predicting how much DNAPL mass remains or must be removed to achieve a target goal. If aggressive source zone treatment is to be implemented due to regulatory requirements, strategic pump‐and‐treat is shown to be most cost effective. These remedial decisions are shown to be insensitive to a range of possible DNAPL pool conditions. At sites with an existing pump‐and‐treat system, a significant increase in mass removal and source strength reduction may be achieved for a low incremental cost by strategic placement of extraction wells and pumping rate selection. © 2014 Wiley Periodicals, Inc.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

Coupling surfactants/cosolvents with oxidants for enhanced DNAPL removal: A review

Surfactants and cosolvents are useful for enhancing the apparent solubility of dense nonaqueous‐phase liquid (DNAPL) compounds during surfactant‐enhanced aquifer remediation (SEAR). In situ chemical oxidation (ISCO) with permanganate, persulfate, and catalyzed hydrogen peroxide has proven to be a cost‐effective and viable remediation technology for the treatment of a wide range of organic contaminants. Coupling compatible remedial technologies either concurrently or sequentially in a treatment train is an emerging concept for more effective cleanup of DNAPL‐contaminated sites. Surfactants are effective for DNAPL mass removal but not useful for dissolved plume treatment. ISCO is effective for plume control and treatment but can be less effective in areas where large masses of DNAPL are present. Therefore, coupling SEAR with ISCO is a logical next step for source‐zone treatment. This article provides a critical review of peer‐reviewed scientific literature, nonreviewed professional journals, and conference proceedings where surfactants/cosolvents and oxidants have been utilized, either concurrently or sequentially, for DNAPL mass removal. © 2010 Wiley Periodicals, Inc.     

Spreadsheet‐based modeling of ISCO with permanganate

CDISCO, a Microsoft Excel spreadsheet–based model, can be used to assist with the design of in situ chemical oxidation (ISCO) systems using permanganate (MnO₄^?). The model inputs are the aquifer characteristics (porosity, hydraulic conductivity, effective aquifer thickness, natural oxidant demand, kinetic parameters, contaminant concentrations, etc.), injection conditions (permanganate injection concentration, flow rate, and duration), and unit costs for reagent, drilling, and labor. MnO₄^? transport in the aquifer is simulated and used to estimate the effective radius of influence (ROI) and required injection point spacing. CDISCO then provides a preliminary cost estimate for the selected design conditions. The user can perform multiple runs of CDISCO to optimize the cost of the ISCO design. Comparisons with analytical and numerical models of nonreactive and reactive transport demonstrate that CDISCO accurately simulates MnO₄^? transport and consumption. Comparison of CDISCO results with the three‐dimensional heterogeneous simulations show that aquifer volume contact efficiency and contaminant mass treatment efficiency are closely correlated with the ROI overlap factor. © 2011 Wiley Periodicals, Inc.     

Sustainable wind‐driven bioventing at a petroleum hydrocarbon–impacted site

Bioventing—the injection of air into the vadose zone to increase microbial activity—is a commonly used, proven technology for remediating volatile organic compounds present in the vadose zone. Passive systems driven by wind or solar power are both more cost‐effective and sustainable than conventional systems. Such a passive system is being applied successfully to remediate a site impacted with total petroleum hydrocarbons (TPH) and benzene, toluene, ethylbenzene, and xylenes (BTEX) in soil. Bioventing technology was approved by the regulatory agency as an interim remedial action to remove chemicals of concern (COCs) in the vadose zone. A bioventing pilot study was conducted to evaluate the effectiveness of COC removal and collect parameters for full‐scale design and implementation. To evaluate the potential to use wind‐driven bioventing technology, two mobile weather stations were installed at the site and monitored for one month for a wind speed study. Based on the pilot‐test data and wind speed research, 12‐inch diameter funnel/vane 360‐degree wind collectors were designed as passive wind‐driven air‐injection devices and connected to existing monitoring wells. The measured air velocity ranged from 20 to 110 feet per minute during the start‐up and the first three months of operation and maintenance. Monitoring indicated a 20 percent oxygen delivery and greater than 90 percent reduction in COC concentrations, demonstrating a successful sustainable remediation with no power requirement and minimal operation and maintenance. © 2012 Wiley Periodicals, Inc.     

Successful unsaturated zone treatment of PCE with sodium permanganate

In situ chemical oxidation (ISCO) with permanganate has been widely used for soil and groundwater treatment in the saturated zone. Due to the challenges associated with achieving effective distribution and retention in the unsaturated zone, there is a great interest in developing alternative injection technologies that increase the success of vadose‐zone treatment. The subject site is an active dry cleaner located in Topeka, Kansas. A relatively small area of residual contamination adjacent to the active facility building has been identified as the source of a large sitewide groundwater contamination plume with off‐site receptors. The Kansas Department of Health and Environment (KDHE) currently manages site remedial efforts and chose to pilot‐test ISCO with permanganate for the reduction of perchloroethene (PCE) soil concentrations within the source area. KDHE subsequently contracted Burns & McDonnell to design and implement an ISCO pilot test. A treatability study was performed by Carus Corporation to determine permanganate‐soil‐oxidant‐demand (PSOD) and the required oxidant dosing for the site. The pilot‐test design included an ISCO injection approach that consisted of injecting aqueous sodium permanganate using direct‐push technology with a sealed borehole. During the pilot test, approximately 12,500 pounds of sodium permanganate were injected at a concentration of approximately 3 percent (by weight) using the methods described above. Confirmation soil sampling conducted after the injection event indicated PCE reductions ranging from approximately 79 to more than 99 percent. A follow‐up treatment, consisting of the injection of an additional 6,200 pounds of sodium permanganate, was implemented to address residual soil impacts remaining in the soil source zone. Confirmation soil sampling conducted after the treatment indicated a PCE reduction of greater than 90 percent at the most heavily impacted sample location and additional reductions in four of the six samples collected. © 2009 Wiley Periodicals, Inc.     

Debunking myths about sustainable remediation

Sustainable remediation concepts have evolved during the decade 2007–2017. From the establishment of the first Sustainable Remediation forum (SURF) in 2007, to publication of ASTM and ISO standards by 2017. Guidance has been developed around the world to reflect local regulatory systems, and much has been learned in applying sustainability assessment to contaminated site management projects. In the best examples, significant improvements in project sustainability have been delivered, including concurrent reduction of the environmental footprint of the remediation program, improved social performance, and cost savings and/or value creation. The initial advocates for the concept of sustainable remediation were quickly supported by early adopters who saw its potential to improve the remediation industry's performance, but they also had to overcome some inertia and scepticism from other parties. During the debates and discussions that occurred at numerous international conferences and SURF workshops around the world, various opinions were formed and positions stated. Some proved to be correct, others not so. With the recent publication of ISO Standard 18504 and the benefit of a decade's‐worth of hindsight on sustainable remediation programs implementation and project delivery, this paper summarizes a number of myths and misunderstandings that have been stated regarding sustainable remediation and seeks to debunk them. Sustainable remediation assessment shows us how to manage unacceptable risks to human health and the environment in the best, that is to say the most sustainable, way. It provides the contaminated land management industry a framework to incorporate sustainable development principles into remediation projects and deliver significant value for affected parties and society more broadly. In dispelling some myths about sustainable remediation set out in this paper, it is hoped that consistent application of ISO18504/SuRF‐UK (or equivalently robust guidance) will facilitate even wider use of sustainable remediation around the world.     

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.     

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.     

Nanotechnology for site remediation

As a remediation tool, nanotechnology holds promise for cleaning up hazardous waste sites cost‐effectively and addressing challenging site conditions, such as the presence of dense nonaqueous phase liquids (DNAPLs). Some nanoparticles, such as nanoscale zero‐valent iron (nZVI) are already in use in full‐scale projects with encouraging success. Ongoing research at the bench and pilot scale is investigating particles such as self‐assembled monolayers on mesoporous supports (SAMMS™), dendrimers, carbon nanotubes, and metalloporphyrinogens to determine how to apply their unique chemical and physical properties for full‐scale remediation. There are many unanswered questions regarding nanotechnology. Further research is needed to understand the fate and transport of free nanoparticles in the environment, whether they are persistent, and whether they have toxicological effects on biological systems. In October 2008, the U.S. Environmental Protection Agency's Office of Superfund Remediation and Technology Innovation (OSRTI) prepared a fact sheet entitled “Nanotechnology for Site Remediation,” and an accompanying list of contaminated sites where nanotechnology has been tested. The fact sheet contains information that may assist site project managers in understanding the potential applications of this group of technologies. This article provides a synopsis of the US EPA fact sheet, available at http://clu‐in.org/542F08009 , and includes background information on nanotechnology; its use in site remediation; issues related to fate, transport, and toxicity; and a discussion of performance and cost data for field tests. The site list is available at http://clu‐in.org/products/nanozvi . © 2008 Wiley Periodicals, Inc.     

Injecting remediation compounds—How you inject is equally as important as what you inject

The injection of remediation compounds has rapidly become a widely accepted approach for addressing contaminated sites. One of the most fundamental questions surrounding the use of in situ remediation has been “What compound are you injecting at your site?” With the advances in the industry's understanding and acceptance of the in situ remediation process remediation professionals are now asking a follow‐up question that has become equally important to the success of a project: “How are you injecting a compound at your site?” This article discusses advances in field applications for in situ remediation and injecting remediation compounds. © 2003 Wiley Periodicals, Inc.     

Use of a low‐cost substrate in a continuous recirculation process to stimulate plumewide anaerobic dechlorination of chlorinated solvents

Over the past 20 years, significant time and money have been spent on better understanding and successfully applying bioremediation in the field. The results of these efforts provide a deeper un‐derstanding of aerobic and anaerobic microbial processes, the microbial species and environ‐mental conditions that are desirable for specific degradation pathways, and the limitations that may prevent full‐scale bioremediation from being successfully applied in heterogeneous subsur‐face environments. Numerous substrates have been identified as effective electron donors to stimulate anaerobic dechlorination of chlorinated ethenes, but methods of delivering these sub‐strates for in situ bioremediation (direct‐push injections, slug injections, high‐pressure injections, fracture wells, etc.) have yet to overcome the main limitation of achieving contact between these substrates and the contaminants. Therefore, although it is important (from a full‐scale remedia‐tion standpoint) to select an appropriate, low‐cost substrate that can be supplied in sufficient quantity to promote remediation of a large source area and its associated plume, it is equally im‐portant to ensure that the substrate can be delivered throughout the impacted plume zone. Failure to achieve substrate delivery and contact within the chlorinated solvent plume usually re‐sults in wasted money and limited remediation benefit. Bioremediation is a contact technology that cannot be effectively implemented on a large scale unless a method for rapidly delivering the low‐cost substrate across the entire source and plume areas is utilized. Unfortunately, many cur‐rent substrate delivery methods are not achieving sitewide distribution or treatment of the sorbed contaminant mass that exists in the organic fraction of a soil matrix. The following discussion sum‐marizes substrate delivery using an aggressive groundwater recirculation approach that can achieve plumewide contact between the contaminants and substrate, thus accelerating dechlori‐nation rates and shortening the overall remediation time frame. © 2006 Wiley Periodicals, Inc.     

Developing Life‐Cycle Environmental Response Costs for Leaking Underground Storage Systems at Service Station Sites

Leaking underground storage tank systems at service stations have resulted in tens of thousands of petroleum releases and associated groundwater chemical plumes often extending hundreds of feet off‐site. Technical and engineering approaches to assess and clean up releases from underground tanks, product lines, and dispensers using technologies such as soil vapor extraction, air sparging, biostimulation, and monitored natural attenuation are well understood and widely published throughout the literature. This article summarizes life‐cycle environmental response costs typically encountered using site‐specific cost estimation or metric‐based cost categories considering the overall complexity of site conditions: (1) simple sites where response actions require smaller scale assessments and/or remediation and have limited or no off‐site impacts; (2) average sites where response actions require larger scale assessments and/or remediation typical of petroleum releases; (3) complex sites where response actions require greater on‐site and/or off‐site remediation efforts; and (4) mega sites where petroleum plumes have impacted public or private water supplies or where petroleum vapors have migrated into occupied buildings. Associated cleanup cost estimates rely upon appropriate combinations of individual work elements and the duration of operation, maintenance, and monitoring activities. These cost estimates can be offset by state reimbursement funds, coverage in purchase agreements, and insurance policies. A case study involving a large service station site portfolio illustrates the range of site complexity and life‐cycle environmental response costs. © 2014 Wiley Periodicals, Inc.     

Economic Project Risk Assessment in Remediation Projects Prior to Construction: Methodology Development and Case Study Application

Probabilistic economic analysis, including uncertainty of probabilities and consequences of project risks, is not widely used in remediation projects. This article presents a project risk assessment (PRA) method to identify, quantify, and analyze risks in remediation projects. The suggested method is probabilistic and includes uncertainty analysis of input variables based on expert judgment. It was originally developed as a part of a sustainability assessment tool, but is viable as a stand‐alone tool for remediation projects. The method is applied to a case study: a former paint factory that is being redeveloped into a residential area. The PRA method is used for analyzing and comparing the project risks associated with four remediation options, all including excavation but with different degrees of onsite treatment. The result of the case study application shows which alternative has the lowest mean risk cost, the highest probability to have the lowest risk cost, and how the risk costs are distributed, but also, importantly, helps the user to prioritize between risk‐reduction measures. ©2015 Wiley Periodicals     

Full‐scale in‐situ biobarrier demonstration for containment and treatment of MTBE

The Naval Facilities Engineering Service Center (NFESC), Arizona State University, and Equilon Enterprises LLC are partners in an innovative Environmental Security Technology Certification Program cleanup technology demonstration designed to contain dissolved MTBE groundwater plumes. This full‐scale demonstration is being performed to test the use of an oxygenated biobarrier at Naval Base Ventura County, in Port Hueneme, California. Surprisingly, few cost‐effective in‐situ remedies are known for the cleanup of MTBE‐impacted aquifers, and remediation by engineered in‐situ biodegradation was thought to be an unlikely candidate just a few years ago. This project demonstrates that MTBE‐impacted groundwater can be remediated in‐situ through engineered aerobic biodegradation under natural‐flow conditions. With respect to economics, the installation and operation costs associated with this innovative biobarrier system are at least 50 percent lower than those of a conventional pump and treat system. Furthermore, although it has been suggested that aerobic MTBE biodegradation will not occur in mixed MTBE‐BTEX dissolved plumes, this project demonstrates otherwise. The biobarrier system discussed in this article is the largest of its kind ever implemented, spanning a dissolved MTBE plume that is over 500 feet wide. This biobarrier system has achieved an in‐situ treatment efficiency of greater than 99.9 percent for dissolved MTBE and BTEX concentrations. Perhaps of greater importance is the fact that extensive performance data has been collected, which is being used to generate best‐practice design and cost information for this biobarrier technology. © 2001 John Wiley & Sons, Inc.     

The in situ treatment of BTEX,MTBE, and TBA in saline groundwater

A pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na₂S₂O₈) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (³⁴S and ¹⁸O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (¹³C and ²H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.