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Disposal of Neutralent Wastes 1 Overview Since World War I, the United States has considered it necessary to have the capability to engage in chemical warfare. Today, however, chemical warfare materiel (CWM) accumulated over the years is considered obsolete and dangerous, and the United States and other signatories of the Chemical Weapons Convention (CWC) are committed to destroying all recovered CWM by 2007. 1 U.S. law and international treaties have divided CWM into two categories: stockpile and nonstockpile materiel. Stockpile materiel includes all chemical agents available for use on the battlefield, including chemical agents assembled into weapons and chemical agents stored in bulk (one-ton) containers. Stockpile materiel is stored at eight locations in the United States and on Johnston Island in the Pacific Ocean. Nonstockpile materiel includes all other chemical weapon-related items, such as buried CWM, recovered CWM, binary chemical weapons, former production facilities, and miscellaneous materiel. Much of the CWM was buried on military sites but is being rediscovered as the land is returned to the civilian sector. Some CWM is also buried at former test and firing ranges. According to the CWC, nonstockpile CWM items in storage at the time of treaty ratification (April 1997) must be destroyed within two, five, or ten years, depending on the type of chemical weapon and the type of agent. Nonstockpile CWM recovered after treaty ratification must be declared and destroyed “as soon as possible” (U.S. Army, 1999a). The Army's Program Manager for Chemical Demilitarization (PMCD) has overall responsibility for disposing of all CWM under PMCD's two programs: the Chemical Stockpile Disposal Program and the Non-Stockpile Chemical Materiel Program (NSCMP). Although this study is concerned with the destruction of nonstockpile materiel, a brief review of the Chemical Stockpile Disposal Program is given below for two reasons. First, this program has been in progress for a longer time than the NSCMP. Second, many of the technologies and social and political factors that have influenced the Chemical Stockpile Disposal Program are expected to influence the NSCMP. CHEMICAL STOCKPILE DISPOSAL PROGRAM Baseline Program In November 1985, Congress passed Public Law 99-145, which requires the destruction of stockpile agents and munitions. Therefore, the U.S. program to destroy stockpile chemical materiel was well under way at the time the CWC was first signed (January 1993). The Army selected incineration as the baseline method for destroying chemical agent in the stockpile materiel; two incinerators, one on Johnston Atoll in the Pacific Ocean and one at the Deseret Chemical Depot near Tooele, Utah, are currently in operation. Together these incinerators are expected to destroy about one-half of the U.S. stockpile, the remainder of which is dispersed among seven storage sites in the continental United States. Because federal law (P.L. 103-337) prohibits the inter-state shipment of chemical weapons, the Army had planned to construct similar incineration systems at the seven other sites. In fact, baseline facilities have been permitted and are under construction at three sites: Anniston, Alabama; Pine Bluff, Arkansas; and Umatilla, Oregon. 1 The Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and Their Destruction, known as the Chemical Weapons Convention, was signed by the United States on January 13, 1993, and ratified by the U.S. Congress on April 25, 1997. The CWC specifies deadlines for the destruction of CWM covered by the treaty. Countries may apply for an extension of up to five years.
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Disposal of Neutralent Wastes Alternative Technologies for Destroying the Stockpile Because incineration as a disposal technology has met with strong public and political opposition, the Army began a search for alternative, nonincineration technologies for destroying stockpile chemical agents in two key programs: one for chemical agents stored in bulk, one-ton containers (sulfur mustard [HD] at Aberdeen Proving Ground, Maryland, and VX [a nerve agent] at Newport, Indiana). In addition, as directed by Congress, the Army is investigating alternate disposal technologies for chemical agents in assembled chemical weapons at two other sites (Pueblo, Colorado, and Lexington Blue Grass, Kentucky) (NRC 1999b). Alternative Technologies and Approaches Program In April 1994, the Department of the Army issued the Alternative Demilitarization Technology Report to Congress (U.S. Army, 1994a). A subsequent report (U.S. Army, 1994b) outlined an aggressive research and development program to evaluate two alternatives to incineration: neutralization alone and neutralization followed by biodegradation. In 1994, the Army's Product Manager for Alternative Technologies and Approaches (ATAP), under the Office of Chemical Demilitarization, undertook a focused research program on the proposed neutralization-based processes for agent destruction. As a result, two processes have been developed. Hydrolysis of chemical agent in pure water followed by biodegradation has been developed to destroy the HD stored in bulk containers at Aberdeen, Maryland. Neutralization by aqueous sodium hydroxide, followed by supercritical water oxidation (SCWO), is being developed to destroy the VX stored in bulk containers at Newport, Indiana. The Army is in the process of designing, constructing, and testing these neutralization-based systems (NRC 1994, 1998a, 2000a). Alternative Technologies Program for Assembled Chemical Weapons Assessment In 1996, Congress also appropriated money and mandated that the Army demonstrate at least two nonincineration technologies for the destruction of assembled chemical weapons at Pueblo, Colorado, and Lexington Blue Grass, Kentucky. The Army established the Assembled Chemical Weapons Assessment (ACWA) Program (NRC, 1999b) to carry out this mandate. Seven technologies passed the initial screening. One was eliminated shortly thereafter because of technical problems. Three were selected for demonstration (Demo I): plasma-arc technology, hydrolysis followed by treatment with SCWO, and hydrolysis followed by bio-degradation (NRC, 2000a). Prototype equipment for unit operations was constructed and tested, and engineering design is under way for integrated systems. Congress subsequently mandated that ACWA also test the remaining three undemonstrated technologies: electro-chemical oxidation, gas-phase chemical reduction (GPCR), and solvated-electron technology (SET). Demonstrations for these three technologies were started in early summer 2000 and ended in September 2000 (Demo II). Results of these demonstrations were received too late for inclusion in this report. Following Demo II, the Army will determine whether alternative technologies will be used at the Pueblo, Colorado, and Lexington Blue Grass, Kentucky, stockpile sites. NON-STOCKPILE CHEMICAL MATERIEL DISPOSAL PROGRAM Prior to 1991, efforts to dispose of CWM were limited to stockpile materiel. A part of the 1991 Defense Appropriations Act (House Appropriations Report 101-822) directed the Secretary of Defense to establish an office with the responsibility of destroying nonstockpile materiel. The program manager for NSCMP was assigned this task under the newly established U.S. Army Chemical Materiel Destruction Agency (NRC, 1999a). Nonstockpile Sites In the 1993 Defense Appropriations Act (P.L. 102-484, Section 176), Congress directed the Army to (1) report the locations, types, and quantities of nonstockpile chemical materiel; (2) specify the methods to be used for its destruction; (3) provide cost and time estimates; and (4) assess transportation options. In a Survey and Analysis Report, the Army provided an overview of its task (U.S. Army, 1996). According to this report, nonstockpile CWM is located at more than 200 sites in the United States and U.S. territories. CWM at most sites includes small quantities of chemical agent but does not appear to pose immediate hazards to the public or the environment. However, chemical weapons agreements and continuing discoveries of contaminated sites have increased the impetus for locating and disposing of all nonstockpile CWM. The purpose of the NSCMP is to provide centralized management and direction for the characterization and destruction of nonstockpile CWM, develop disposal facilities, provide schedule and cost estimates, and ensure compliance with federal, state, and local regulations. Transportable Treatment Systems Because a large number of locations have only small quantities of CWM, the Army decided to develop transportable disposal systems that can be moved from site to site as needed. To treat the entire range of materiel (e.g., munitions containing a variety of chemical agents, 2 some configured 2 See Table 1-1 in Disposal of Chemical Agent Identification Sets (NRC 1999a).
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Disposal of Neutralent Wastes TABLE 1-1 Transportable Treatment Systems for Nonstockpile Chemical Materiel System Type of Materiel Status Rapid Response System (RRS) Chemical Agent Identification Sets (CAIS). Full-scale prototype designed and assembled; testing was completed summer 2000, however, the results were not available for inclusion in this report. Munitions Management Device (MMD) a Nonstockpile chemical munitions with no explosive components; small containers of chemical agent; chemical samples. Full-scale prototype designed and assembled; testing was completed summer 2000, however, the results were not available for inclusion in this report. Explosive Destruction System (EDS) Chemical munitions with explosive components. Phase I prototype in testing; Phase II model in design. Source: U.S. Army, 1999b. a The development of a successor system, the MMD-2, designed to handle explosively configured materiel, has been suspended for cost reasons. Explosively configured materiel will probably be treated in a fixed facility to be built in Pine Bluff, Arkansas, where most of the recovered munitions are currently stored (Brankowitz, 2000). with explosives), the Army decided it would need three separate transportable systems ( Table 1-1 ). Two of the three systems—the rapid response system (RRS) and the munitions management device (MMD)—are ready for testing. The RRS is designed to treat chemical agent identification sets (CAIS). The MMD is designed to treat nonexplosively configured munitions and containers filled with sulfur mustard, HD, phosgene, satin (GB), and VX. These two systems are the focus of this study. The third system, the explosive destruction system (EDS), has been tested in England, but the neutralent waste has not yet been characterized. Both the RRS and MMD systems can be mounted on a series of trailers, and both use chemical processes to treat agents. The design of an MMD-2 system, intended to treat explosively configured munitions, has recently been postponed (Brankowitz, 2000). At the time of this writing, the RRS and MMD systems had been permitted for testing in Utah. Handling Processes Figure 1-1 is a flow chart illustrating the Army's planned disposition of nonstockpile CWM. As the figure shows, when CWM is discovered, CAIS items are separated from munitions and other containers and treated in the RRS, producing a neutralent waste stream (inside the dotted box). Munitions are then evaluated to determine the type of chemical agent fill and whether they contain energetics. Chemical agent fill is analyzed by using portable isotopic neutron spectroscopy (PINS). If the munitions do not contain energetics, they are treated in the MMD, which also produces a neutralent waste stream (inside the dotted box). Munitions containing energetics with a total explosive force of about one pound of dynamite (e.g., 75-mm projectiles, 4.2-inch mortar rounds, 8-inch live rounds) are expected to be treated in the EDS Phase 1. Munitions containing larger quantities of explosives will be treated in the EDS Phase 2, which is currently being designed and is expected to be accepted by mid-2002. The waste streams shown inside the dotted box at the bottom of Figure 1-1 are the subject of this study. Waste streams outside the box, as well as alternative treatment processes that might replace the RRS, MMD, and EDS, will be considered in another study next year. Neutralent Waste Streams In both the RRS and MMD, munitions or containers are opened, and liquid reagents are mixed with the chemical agents. According to Army test data, the agent concentration in the reaction vessel is thereby reduced to less than 50 parts per million (ppm) for mustard and lewisite and less than 50 parts per billion (ppb) for VX and GB (U.S. Army, 1999b). However, because of the treatment reagents, the liquid waste streams from both the RRS and MMD (called “neutralents ” in this study) will contain chlorinated organic chemicals (only RRS), excess reactants, and reaction products and are likely to be considered hazardous waste under Subtitle C of the Resource Conservation and Recovery Act (RCRA), which provides national standards (regulations) for the “cradle-to-grave” management of hazardous waste. Thus, RRS and MMD neutralents cannot be released directly to the environment unless they are treated further. In addition, neutralents may contain Schedule 2 precursors, 3 which also 3 Under the CWC, Schedule 2 chemicals have limited commercial utility and can be readily converted to chemical weapons. Production of these chemicals above specified limits is subject to reporting requirements and verification through on-site inspections.
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Disposal of Neutralent Wastes FIGURE 1-1 Flow chart for the disposal of nonstockpile CWM in transportable systems. Waste streams in the dotted box are the focus of this report. require further treatment. Currently, although the Army plans to incinerate neutralent derived from its mobile systems, alternative destruction technologies are also being investigated. Studies of Alternative Technologies The Army enlisted two organizations to study alternatives to incineration for the treatment of neutralents. Mitretek was asked to determine whether technologies originally proposed for the treatment of stockpile CWM under the ACWA Program might also be used to treat neutralents generated from the RRS and MMD. Using weighted evaluation criteria, Mitretek ranked the six ACWA technologies in order of their suitability for treating the neutralents. 4 4 Mitretek ranked the six technologies in the following order of preference: (1) SCWO, (2) GPCR, (3) plasma arc technology, (4) silver II, (5) SET, and (6) hydrolysis/biotreatment (Mitretek, 1999).
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Disposal of Neutralent Wastes The Army also requested that Stone and Webster publish a Commerce Business Daily announcement calling for proposals for technologies to treat RRS and MMD neutralents and then evaluate their applicability. Stone & Webster's analysis 5 is limited to the proposals received in response to the announcement. APPLICABILITY OF ACWA TECHNOLOGIES All six of the technologies submitted to the ACWA Program have been tested, although the results of the most recent tests (Demo II), which were completed in September 2000, have not yet been published. Much of the equipment used in the demonstration tests will continue to be used by the Army, and three of the test units would be large enough to treat the total quantities of MMD and RRS neutralents. All of the technologies selected for testing were considered acceptable alternatives to incineration by the citizen stakeholders involved in the selection process. Because the equipment used in the ACWA demonstrations may be available to treat neutralents in the near future, using the demonstration equipment may prove to be an expedient and cost-effective solution for the destruction of neutralents even though the technology (assuming it meets safety criteria) is not the one best suited to the job. Regulatory Requirements The use of the RRS and MMD mobile systems presents significant regulatory challenges. Many federal and state regulations will affect the treatment and management of neutralents. The entire process, including neutralization, storage, transportation, and ultimate disposal of the neutralent, will be regulated under Subtitle C of RCRA. The Clean Water Act may apply, if the neutralent is sent to a publicly owned treatment works (POTW). RCRA regulatory requirements are codified under federal and state rules and regulations. In some cases, state environmental regulations are even more stringent than federal regulations, making a single national approach practically impossible. Additional regulatory requirements may apply if some of the chemicals in the neutralents are defined as “lethal chemical agents” under the CWC and U.S. statutes (e.g., 50 U.S.C. § 1512 (j)(2)). ROLE OF THE NATIONAL RESEARCH COUNCIL Involvement with the Non-Stockpile Chemical Materiel Disposal Program This is the second of three reports the National Research Council was asked to produce for the Army. In the first report, delivered in 1999, the committee reviewed disposal options for CAIS (NRC, 1999a). In this second report, the committee evaluates nonincineration technologies for the treatment and/or destruction of neutralents. However, due to a recent change in the strategic direction of the NSCMP, the National Research Council was asked to produce two additional reports (in place of the third report) over the ensuing 18 months. The first, scheduled to be delivered in late 2001, will make recommendations for disposing of EDS waste streams; the second, to be delivered in early 2002, will evaluate alternative (nonincineration) strategies for the comprehensive treatment of nonstockpile CWM, including agents, energetics, and munitions/containers. Statement of Task for This Study The committee was given the following Statement of Task for this study: 6 Evaluate the near-term (1999–2005) application of advanced (non-incineration) technologies, such as from Army's Assembled Chemical Weapons Assessment (ACWA) program and the Alternative Technologies and Approaches Project (ATAP), in a semi-fixed, skid-mounted mode to process Rapid Response System (RRS), Munitions Management Device (MMD), and Explosive Destruction System (EDS) liquid neutralization wastes. SCOPE OF THIS STUDY This report focuses on nonincineration, alternative technologies for the treatment of liquid neutralents from the RRS and MMD; the method by which the agent is accessed and separated from the munition or container is not considered. Solid waste streams from the RRS and MMD (e.g., carbon filters, metal parts, dunnage) are not considered. The treatment of liquid waste streams from the EDS, which have not been well characterized but will most likely contain both unexploded energetics and by-products from the explosives used to access the munitions, will be considered in a separate report. The nonincineration technologies considered in this study are based on the following sources: 5 Stone & Webster's technology evaluation panel recommended the following six technologies: (1) catalytic hydrothermal conversion technology; (2) catalytic transfer hydrogenation technology; (3) gas-phase chemical reduction; (4) MGC PLASMOX® process; (5) solvated-electron/persulfate oxidation technology; and (6) supercritical water oxidation (Stone & Webster, 2000). 6 The original contractual language was updated and modified in discussions with the Army, resulting in the Statement of Task that follows.
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Disposal of Neutralent Wastes ACWA Program demonstrations ATAP demonstrations proposals received by Stone and Webster (or the Army) in response to the Commerce Business Daily announcement previous reviews by the North Atlantic Treaty Organization (NATO) knowledge and personal experience of committee members Technologies are discussed generically without reference to particular vendors, although the committee obtained information from some specific technology providers to complete its evaluation. In these cases, every effort was made to treat the technology as generically as possible. Each technology was evaluated for its capability to meet the following goals: Solids wastes can be sent to a RCRA Subtitle C or D landfill. 7 Any residual agents, Schedule 2 compounds, or other materials in the neutralents are at low levels that do not preclude discharge directly to a POTW or federally owned treatment works (FOTW). Air discharges contain only CO2, water vapor, oxygen, and nitrogen. (Note that the degree of containment, capture, and processing required to achieve those conditions could vary greatly.) Technologies that could meet these goals would require no further treatment except for the normal biodegradation that takes place at a POTW. Whether or not a POTW will, in fact, accept nonhazardous wastewater derived from the treatment of chemical agents has not been determined. During the course of the study, the committee was informed by the Army that treatment, storage, and disposal facilities (TSDFs) had been surveyed as potential disposal sites. Only TSDFs whose primary technology was incineration responded. However, in wet-air/O2 oxidation (WAO), one of the most promising technologies for the destruction of neutralent, the committee suggests that the Army also investigate TSDFs that use this technology. Because no information was available on actual tests of the destruction of real or simulated nonstockpile neutralent, or even any paper studies, the committee had to rely on the expert judgment of committee members to predict the most likely outcomes for each technology and identify the most promising technologies for development. Because the RRS and MMD neutralents are chemically very different from each other, the committee assessed the appropriateness of technologies for each waste stream separately. If a given technology could effectively destroy both types of neutralents, this was considered an advantage, but no technology was rejected if it would be effective for only one neutralent stream. The committee also attempted to include the views of the interested public in its deliberations. The committee met with federal regulators from the Environmental Protection Agency's (EPA) Office of Waste Management and with members of public interest groups who have been active in the policy debate. The latter were invited to present and discuss their views with the committee and to participate in site visits to observe two of the technologies being evaluated. In addition, members of the committee observed meetings of a stakeholder group convened by NSCMP (called the CORE Group) that included both regulators and members of the public. Committee Approach The committee adopted a dual approach to evaluating and selecting the technologies with the greatest potential for treating RRS and MMD neutralents in a timely, cost-effective manner consistent with the protection of human health and the environment. The first approach was opportunistic. The committee reasoned that, if the neutralents could be effectively destroyed by “piggybacking” on existing stockpile or other hazardous waste destruction campaigns, this might provide a relatively inexpensive, time-efficient, and convenient solution, even if the technology was not rated highly for destroying the neutralents according to the committee's criteria. The second approach was based on best practices in the chemical industry, which are documented in public records. The committee ranked the selected technologies qualitatively according to these criteria. Unlike the Mitretek and Stone and Webster studies mentioned above, the committee made no attempt to weight the criteria quantitatively. STRUCTURE OF THIS REPORT The neutralents generated from the RRS and MMD mobile treatment systems, which are the “input” to the disposal technologies considered in this study, are characterized in some detail in Chapter 2 . Chapter 3 describes the derivation of the criteria the committee used to evaluate the technologies. Chapter 4 presents brief descriptions of the selected alternative technologies, along with the committee's evaluations and rankings. Chapter 5 discusses issues related to public involvement in the technology selection process. Chapter 6 presents the committee's findings and recommendations. 7 A RCRA Subtitle C landfill accepts hazardous wastes; a RCRA Subtitle D landfill accepts municipal solid wastes. The committee believes that residual solids from the processes discussed in this report can be stabilized and pass regulatory requirements for disposal. However, treatability studies will be necessary to demonstrate this.
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