The overall goal of this project was to develop reactive membrane barriers--a new and flexible technique to contain and stabilize subsurface contaminants. Polymer membranes will leak once a contaminant is able to diffuse through the membrane. By incorporating a reactive material in the polymer, however, the contaminant is degraded or immobilized within the membrane. These processes increase the time for contaminants to breakthrough the barrier (i.e. the lag time) and can dramatically extend barrier lifetimes. In this work, reactive barrier membranes containing zero-valent iron (Fe°) or crystalline silicotitanate (CST) were developed to prevent the migration of chlorinated solvents and cesium-137, respectively. These studies were complemented by the development of models quantifying the leakage/kill time of reactive membranes and describing the behavior of products produced via the reactions within the membranes. First, poly(vinyl alcohol) (PVA) membranes containing Fe° and CST were prepared and tested. Although PVA is not useful in practical applications, it allows experiments to be performed rapidly and the results to be compared to theory. For copper ions (Cu{sup 2+}) and carbon tetrachloride, the barrier was effective, increasing the time to breakthrough over 300 times. Even better performance was expected, and the percentage of the iron used in the reaction with the contaminants was determined. For cesium, the CST laden membranes increased lag times more than 30 times, and performed better than theoretical predictions. A modified theory was developed for ion exchangers in reactive membranes to explain this result. With the PVA membranes, the effect of a groundwater matrix on barrier performance was tested. Using Hanford groundwater, the performance of Fe° barriers decreased compared to solutions containing a pH buffer and high levels of chloride (both of which promote iron reactivity). For the CST bearing membrane, performance improved by a factor of three when groundwater was used in place of deionized water. The performance of high density polyethylene (HDPE) membranes containing Fe° was then evaluating using carbon tetrachloride as the target contaminant. Only with a hydrophilic additive (glycerol), was the iron able to extend lag times. Lag times were increased by a factor of 15, but only 2-3% of the iron was used, likely due to formation of oxide precipitates on the iron surface, which slowed the reaction. With thicker membranes and lower carbon tetrachloride concentrations, it is expected that performance will improve. Previous models for reactive membranes were also extended. The lag time is a measurement of when the barrier is breached, but contaminants do slowly leak through prior to the lag time. Thus, two parameters, the leakage and the kill time, were developed to determine when a certain amount of pollutant has escaped (the kill time) or when a given exposure (concentration x time) occurs (the leakage). Finally, a model was developed to explain the behavior of mobile reaction products in reactive barrier membranes. Although the goal of the technology is to avoid such products, it is important to be able to predict how these products will behave. Interestingly, calculations show that for any mobile reaction products, one half of the mass will diffuse into the containment area and one half will escape, assuming that the volumes of the containment area and the surrounding environment are much larger than the barrier membrane. These parameters/models will aid in the effective design of barrier membranes.

This report focuses on progress made in the last 12 months, with prior results briefly summarized. We emphasize that the key to our work is an increase in barrier properties. Thus, much of our work has focused on poor, thin barriers composed of PVA. WE have done so because experiments are then able to be conducted over reasonable times. At the same time, we have developed and experimentally verified theories showing how our short experiments can be extrapolated to real situations.

Containment and permeable reactive barriers have come full circle as an acceptable environmental control technology during the past 30 years. As interest shifted back toward containment in the 1990s, the industry found itself relying largely on pre-1980s technology. Fortunately, in the past 10 years important advances have occurred in several areas

Containment barrier systems are among the most widely used technologies for remediating contaminated sites. Various structures have been engineered to address site-specific needs, while barrier selection depends largely on whether regulatory requirements are prescriptive, or performance based. This publication provides an introduction to the design and construction of different containment barriers for low-level radioactive waste generated from remediation activities: basal (bottom) liners, final covers, in situ vertical barriers and in situ permeable reactive barriers. Practical aspects of each structure are discussed in theoretical case studies, which allow remediation project designers, implementers and regulators to make more informed decisions about the use of these barriers.

Remediation of groundwater is complex and often challenging. But the cost of pump and treat technology, coupled with the dismal results achieved, has paved the way for newer, better technologies to be developed. Among these techniques is permeable reactive barrier (PRB) technology, which allows groundwater to pass through a buried porous barrier that either captures the contaminants or breaks them down. And although this approach is gaining popularity, there are few references available on the subject. Until now. Permeable Reactive Barrier: Sustainable Groundwater Remediation brings together the information required to plan, design/model, and apply a successful, cost-effective, and sustainable PRB technology. With contributions from pioneers in this area, the book covers state-of-the-art information on PRB technology. It details design criteria, predictive modeling, and application to contaminants beyond petroleum hydrocarbons, including inorganics and radionuclides. The text also examines implementation stages such as the initial feasibility assessment, laboratory treatability studies (including column studies), estimation of PRB design parameters, and development of a long-term monitoring network for the performance evaluation of the barrier. It also outlines the predictive tools required for life cycle analysis and cost/performance assessment. A review of current PRB technology and its applications, this book includes case studies that exemplify the concepts discussed. It helps you determine when to recommend PRB, what information is needed from the site investigation to design it, and what regulatory validation is required.

President Carter's 1980 declaration of a state of emergency at Love Canal, New York, recognized that residents' health had been affected by nearby chemical waste sites. The Resource Conservation and Recovery Act, enacted in 1976, ushered in a new era of waste management disposal designed to protect the public from harm. It required that modern waste containment systems use "engineered" barriers designed to isolate hazardous and toxic wastes and prevent them from seeping into the environment. These containment systems are now employed at thousands of waste sites around the United States, and their effectiveness must be continually monitored. Assessment of the Performance of Engineered Waste Containment Barriers assesses the performance of waste containment barriers to date. Existing data suggest that waste containment systems with liners and covers, when constructed and maintained in accordance with current regulations, are performing well thus far. However, they have not been in existence long enough to assess long-term (postclosure) performance, which may extend for hundreds of years. The book makes recommendations on how to improve future assessments and increase confidence in predictions of barrier system performance which will be of interest to policy makers, environmental interest groups, industrial waste producers, and industrial waste management industry.

Containment and permeable reactive barriers have come full circle as an acceptable environmental control technology during the past 30 years. As interest shifted back toward containment in the 1990s, the industry found itself relying largely on pre-1980s technology. Fortunately, in the past 10 years important advances have occurred in several areas of containment, most notably in the area of permeable barriers. A balanced presentation of what is known and not known, Barrier Systems for Contaminant Containment and Environmental Treatment provides a comprehensive report on the current state of the science and technology of waste containment. Comprehensive and easily read, this book is rich with discussions and references to literature. Setting the stage for how contaminants can get into the subsurface, the authors describe pathways and introduce the essential concepts of risk. They provide details on the current state of the art for performance prediction and clearly delineate the limitations in modeling specific situations. The book addresses the materials used in barriers, defines their properties, and explores how they perform in the field. It describes available technologies and addresses their applications to various types of barriers. Tackling perhaps the most challenging aspect of waste containment technology, the book includes two case studies that demonstrate the value of validating field performance. Subsurface containment and treatment barriers will continue to be a widely used environmental control technology in the years ahead. Representing the collective knowledge and efforts of leading experts from research, industry, and regulatory agencies, this book provides a valuable reference that helps to chart the way to successfully managing many contaminated sites.