National Research Council (NRC) reports have evaluated a wide range of destruction technologies developed or implemented in the United States. The obligation to destroy recovered chemical warfare materiel (RCWM) applies to many other nations. In the last few years, a number of chemical warfare materiel (CWM) destruction technologies have been developed or refined outside the United States. As discussed in Chapter 2, the United States will increasingly be faced with the need to evaluate and determine how to address buried CWM. The time, therefore, is apropos to evaluate the international CWM destruction technologies that could offer complementary capabilities or possibly even replace current equipment. The statement of task with which the committee was charged is as follows:
The NRC will establish a committee to review and evaluate international technologies for the destruction of non-stockpile chemical materiel. The committee will provide independent scientific and technical evaluations of international systems, facilities, and disposal technologies currently employed or under research and development in countries with inventories of non-stockpile materiel for their treatment and destruction. The committee will compare these technologies with those utilized by the U.S. Army Project Manager for Non-Stockpile Chemical Materiel, in an overall effort to determine and further define state-of-the-art technologies for destruction worldwide of non-stockpile chemical materiel. The committee will:
Review and evaluate systems and technologies employed or under development in countries with inventories of non-stockpile materiel for the treatment and destruction of non-stockpile munitions, materiel, and secondary waste streams. Such countries include, but are not limited to, France, Germany, Japan, Russia, and the United Kingdom.
Compare and contrast foreign disposal technologies, facilities, and/or systems and their present or future potential to be more effective for the overall disposal of specific types of non-stockpile materiel, as compared with corresponding disposal technologies, facilities, and/or systems presently in use by the U.S. Army Project Manager for Non-Stockpile Chemical Materiel. This comparison will include an assessment of technical feasibility, level of maturity, and overall degree of scientific acceptance versus the disposal technologies presently in use by the U.S. Army Project Manager for Non-Stockpile Chemical Materiel, as well as other items or areas detailed below.
As part of this analysis, the committee will:
Consider implementation and deployment issues related to cost, safety, risk, and protection of the environment of the foreign technologies and systems
At this early stage of assessment of systems and technologies, address acceptability to regulators and stakeholders to the extent that the committee judges that significant problematic issues exist or are relevant.
The NRC will deliver its report to the sponsor within 14 months of contract award.
This report primarily evaluates technologies for the complete destruction of recovered non-stockpile munitions and, to a lesser degree, technologies more suited to the destruction of recovered non-stockpile chemical agent only. Since many of the sources of information on destruction technologies were also the sources of information on technologies addressing remote detection and accessing of buried CWM, and since it was asked to do so by the U.S. Army as sponsor of the report, the committee collected the latter type of information as well. It did so to the extent that resources were not significantly diverted from the primary purpose of the study. This information is presented in Chapter 7.
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel 1 Introduction and Background PURPOSE OF THIS REPORT National Research Council (NRC) reports have evaluated a wide range of destruction technologies developed or implemented in the United States. The obligation to destroy recovered chemical warfare materiel (RCWM) applies to many other nations. In the last few years, a number of chemical warfare materiel (CWM) destruction technologies have been developed or refined outside the United States. As discussed in Chapter 2, the United States will increasingly be faced with the need to evaluate and determine how to address buried CWM. The time, therefore, is apropos to evaluate the international CWM destruction technologies that could offer complementary capabilities or possibly even replace current equipment. The statement of task with which the committee was charged is as follows: The NRC will establish a committee to review and evaluate international technologies for the destruction of non-stockpile chemical materiel. The committee will provide independent scientific and technical evaluations of international systems, facilities, and disposal technologies currently employed or under research and development in countries with inventories of non-stockpile materiel for their treatment and destruction. The committee will compare these technologies with those utilized by the U.S. Army Project Manager for Non-Stockpile Chemical Materiel, in an overall effort to determine and further define state-of-the-art technologies for destruction worldwide of non-stockpile chemical materiel. The committee will: Review and evaluate systems and technologies employed or under development in countries with inventories of non-stockpile materiel for the treatment and destruction of non-stockpile munitions, materiel, and secondary waste streams. Such countries include, but are not limited to, France, Germany, Japan, Russia, and the United Kingdom. Compare and contrast foreign disposal technologies, facilities, and/or systems and their present or future potential to be more effective for the overall disposal of specific types of non-stockpile materiel, as compared with corresponding disposal technologies, facilities, and/or systems presently in use by the U.S. Army Project Manager for Non-Stockpile Chemical Materiel. This comparison will include an assessment of technical feasibility, level of maturity, and overall degree of scientific acceptance versus the disposal technologies presently in use by the U.S. Army Project Manager for Non-Stockpile Chemical Materiel, as well as other items or areas detailed below. As part of this analysis, the committee will: Consider implementation and deployment issues related to cost, safety, risk, and protection of the environment of the foreign technologies and systems At this early stage of assessment of systems and technologies, address acceptability to regulators and stakeholders to the extent that the committee judges that significant problematic issues exist or are relevant. The NRC will deliver its report to the sponsor within 14 months of contract award. STUDY SCOPE AND STRUCTURE Scope This report primarily evaluates technologies for the complete destruction of recovered non-stockpile munitions and, to a lesser degree, technologies more suited to the destruction of recovered non-stockpile chemical agent only. Since many of the sources of information on destruction technologies were also the sources of information on technologies addressing remote detection and accessing of buried CWM, and since it was asked to do so by the U.S. Army as sponsor of the report, the committee collected the latter type of information as well. It did so to the extent that resources were not significantly diverted from the primary purpose of the study. This information is presented in Chapter 7.
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel The committee reviewed the scientific literature and publicly available reports prepared for governmental entities of the United States and other countries and interviewed, among others, government scientists and engineers in Belgium, Germany, Japan, Switzerland, the United Kingdom, and the United States; staff in the Organisation for the Prohibition of Chemical Weapons; and representatives of vendors of international treatment technologies for the destruction of CWM. These communications included face-to-face meetings, site visits, telephone calls, and exchanges of e-mails. Where data were available, they were evaluated; however, of necessity, comparative evaluations of technologies rely on the professional judgment and experience of the committee members. It must be acknowledged that, in some cases, it was more difficult (or even impossible) to obtain reliable, detailed technical information from foreign government organizations and technology developers than from the U.S. Army and its contractors. Structure and Tiering of Technologies The committee determined that it would be beneficial to organize its evaluation activities in a manner that would enable it to concentrate its efforts on international technologies that appeared to be the most promising for use in non-stockpile operations. This was accomplished by separating the technologies into two groups: (1) those applicable for destroying an entire non-stockpile recovered munition, including agent, energetics, and other materials, such as the munition casing, and (2) those for destroying agent only. The technologies were further categorized in a tiered matrix. The most promising (Tier 1) technologies for munitions processing and agent-only processing are evaluated in Chapters 4 and 5, respectively. Other (Tier 2) technologies for both munitions processing and agent-only processing are described in Chapter 6. Technologies assigned to Tier 1 were those that appeared to have a good level of maturity and to possess capabilities required by the U.S. Army’s Non-Stockpile Chemical Materiel Project (NSCMP), as determined by the committee after discussions between the committee and NSCMP staff. Tier 2 technologies are of two basic types. The first type are those technologies with potential applicability to NSCMP projects but that are still at an early stage of development for such applications. The second type of Tier 2 technologies are those that have been tried out in operations for destroying recovered chemical weapons materiel but that have not, for various reasons, proven to be satisfactory. The evaluation factors analysis described in Chapter 3 was applied only to the Tier 1 technologies. The international Chemical Weapons Convention (CWC) treaty deadline for destroying CWM that have already been recovered is April 29, 2007. This date is near, so the committee focused on evaluating international destruction technologies that could satisfy operational requirements for destroying non-stockpile CWM that has yet to be recovered. In particular, the committee was interested in examining technologies that could be effectively implemented at sites where large quantities of buried materiel could be expected and where, consequently, higher throughputs for destruction operations might be achieved than with current NSCMP equipment. The committee considered the applicability of international technologies for sites where only single or a few items might be recovered. With the exception of offgas treatment technologies, the report does not specifically address separate technologies for treating secondary waste. Report Organization Chapter 1 provides background information on the NSCMP and describes the purpose and approach of the report. Chapter 2 summarizes the factual, regulatory, and other characteristics of buried CWM sites to set the stage for evaluating the international technologies examined in this report. Chapter 3 explains the criteria used to evaluate the international technologies. Chapter 4 applies these criteria to the Tier 1 treatment technologies for complete destruction of recovered CWM munitions, and Chapter 5 applies the criteria to Tier 1 technologies for treatment of recovered chemical agent. Chapter 6 describes and comments on technologies the committee assigned to Tier 2 status. Chapter 7 reports on technologies relating to the remote detection and accessing of buried CWM. That information was gathered by the committee in the course of its research on the primary treatment technologies. U.S. NON-STOCKPILE PROGRAM Chemical Demilitarization Overview The elimination of the extensive inventory of weapons containing chemical agents and of chemical agent in bulk that has been maintained by the United States has been in progress since the early 1990s. This inventory, known as the chemical weapons stockpile, or simply “stockpile,” was developed during World War II and in the following decades. Since then, it was or continues to be maintained at eight storage sites in the continental United States and on Johnston Atoll in the Pacific Ocean, southwest of Hawaii. Destruction operations on Johnston Atoll using the U.S. Army’s baseline incineration system were completed in 2000. Destruction operations using this technology at four of the continental U.S. storage sites are currently in progress. At the other four storage sites, technology based on the use of hydrolysis for destruction of agent (and, where applicable, energetic material) has been employed or is planned. At one of the latter sites (Aberdeen, Maryland), where mustard agent HD was stored in bulk, destruction operations have already been completed. Destruction of the
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel entire U.S. stockpile was slated to be complete by April 29, 2012. This date represents the 5-year extension allowable under the terms of the CWC treaty, which was adopted on April 29, 1997, and called for all declared chemical weapons to be destroyed in 10 years (2007), with the possibility of a 5-year extension. However, current estimates are that only about two-thirds of the 31,500-ton original stockpile will be destroyed by 2012. In addition to the stockpile, U.S. law and international treaties recognize another category of CWM, which in the United States is designated as non-stockpile materiel. This category includes materiel that was buried on current and former military sites, some of which is now being recovered as the land is remediated. Non-stockpile munitions have been found in a variety of conditions owing to their exposure to uncontrolled environments and are generally not amenable to processing by the reverse assembly (disassembly) process used in the baseline stockpile incineration program. Non-stockpile materiel that had been recovered and was in storage prior to the ratification of the CWC is required to be destroyed by April 29, 2007. Within the U.S. Army, the NSCMP has been charged with a number of mission tasks to accomplish this under the direction of the Chemical Materials Agency, which is charged with the overall management of U.S. chemical demilitarization activities. These tasks, which include the demolition of former production facilities (such as those at Aberdeen Proving GroundEdgewood Area, Maryland, and Newport Chemical Depot, Newport, Indiana) and the destruction of recovered non-stockpile materiel that has been in storage at stockpile locations (such as at Pine Bluff Arsenal, Arkansas), are well under way and are expected to be completed by the treaty deadline. However, a large quantity of non-stockpile materiel has not yet been recovered; it is discussed later in this chapter and in Chapter 2. This materiel is not subject to CWC requirements until it is recovered. Once the recovery of such materiel is declared, however, the CWC calls for it to be destroyed “as soon as possible.” This report explores the technology options available in other countries that the U.S. Army might wish to consider using for these future operations. Chemical Weapons Convention The United States ratified the CWC in 1997.1 The CWC prohibits the use of chemical weapons and mandates the elimination of existing declared stockpiles by April 29, 2007, but allows the deadline to be extended to 2012, a provision that has been or is likely to be invoked, at least for stockpiled chemical weapons, by some of the parties to the CWC. In the CWC framework, “old chemical weapons” are chemical weapons that (1) were produced before 1925 or (2) were produced in the period between 1925 and 1946 and have deteriorated to such extent that they can no longer be used as chemical weapons. “Abandoned chemical weapons” are chemical weapons, including old chemical weapons, abandoned by a state after January 1, 1925, on the territory of another state without the consent of the latter. Each party to the CWC must declare whether chemical weapons have been abandoned on its territory, and the party that abandoned such weapons must also declare that it did so. The party that abandoned the chemical weapons is obligated to destroy them. Although there are a significant number of abandoned chemical weapons, the exact location of most of the abandoned weapons is not public information. These two categories do not impact the obligation to destroy such weapons, since the CWC requires both old chemical weapons and abandoned chemical weapons to be declared (whether on a member nation’s own territory or the territory of another) and destroyed within the CWC treaty deadline if they are unearthed prior to the deadline (Pearson and Magee, 2002). However, because old and abandoned CWM might also be found after the CWC deadline, their disposal will likely continue after 2007. The CWC requires abandoned weapons to be destroyed as toxic waste in accordance with the national regulations of the country in which the weapons reside. More generally, the term “buried chemical warfare materiel” refers to any CWM buried prior to January 1, 1977, or dumped at sea prior to January 1, 1985. Any CWM discovered and recovered after the initial declaration that was required by the CWC treaty must be destroyed (including formerly buried CWM). However, the CWC allows a member nation to exclude CWM buried on its territory before January 1, 1977, or disposed of at sea before January 1, 1985, as long as the materiel remains buried (U.S. Army, 1996). Thus, the CWC does not require buried CWM to be declared or destroyed as long as the materiel remains buried. At the time this report was prepared, CWM dumped at sea did not fall under the authority of the PMNSCM and were therefore not directly addressed by the committee. In the United States, when buried CWM are removed from their burial site (i.e., when they become RCWM), they must be identified, classified, declared, and disposed of in accordance with CWC, Environmental Protection Agency (EPA), and state environmental regulations (U.S. Army, 1996, 2001a, 2004). The CWC allows some negotiation of the timetable for the disposal of CWM declared after the treaty’s entry into force, although generally it should be “destroyed as soon as possible.”2 1 The Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on their Destruction can be found at <http://www.opcw.org/>; it is the basis for this section of the report. 2 Information derived from a meeting between representatives of the Organisation for the Prohibition of Chemical Weapons and the members of the committee, The Hague, The Netherlands, January 18, 2006.
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel Types of Non-Stockpile Items Non-stockpile chemical warfare materiel (NSCWM) is far more diverse than stockpile CWM: For example, it contains U.S. unitary munitions and accessories dating back to World War I, binary munitions, and foreign munitions brought back to the United States after World War II. There is a greater variety of chemical agents in NSCWM than in stockpile materiel (including blister agents, nerve agents, blood agents, and choking agents, as well as militarized industrial chemicals). Energetics found in chemical munitions include aromatic nitro compounds such as trinitrotoluene (TNT), aromatic nitramines such as tetryl, heterocyclic nitramines such as cyclotrimethylenetrinitramine (RDX), high-melting explosive cyclotetramethylene-tetranitramine (HMX), and nitrate esters used in propellants (e.g., nitrocellulose and nitroglycerine). The most commonly encountered energetics are tetryl, TNT, and composition B (60 percent RDX, 39 percent TNT, 1 percent wax).3 The condition of the NSCWM is also much more variable than that of the stockpile, especially for items that have severely deteriorated after being buried for decades (NRC, 2002). Chemical agent identification sets (CAIS), which were also disposed of by burial and are frequently found, are also NSCWM.4 CAIS are kits consisting of small vials or ampules of diluted or full-strength chemical agents that were used by the U.S. Army for training troops to recognize the odor and the effects of CWM. Appendix A shows the inventory of recovered non-stockpile items that have been stored at various locations awaiting treatment and disposal, which is scheduled to be completed prior to the 2007 CWC treaty deadline using currently available NSCMP equipment. Except for the listed binary agent precursors (which postdate the period when the Army practiced burial of non-stockpile chemical warfare materiel), the tables in Appendix A exemplify the great variety of items that could be encountered during future recovery operations. Scope of Buried Non-Stockpile Chemical Weapons Materiel As of 1996, the U.S. Army had located 168 potential CWM burial sites at 63 locations (primarily current or former military facilities) in 31 states, the U.S. Virgin Islands, and the District of Columbia (U.S. Army, 1996).5 They include sites with CAIS only, sites with small quantities of materiel with and without associated explosives, and sites with large quantities of materiel with and without explosives. The majority of the sites involve small quantities of materiel (NRC, 2002). Based on its 1996 survey, DOD estimated the cost of disposing of buried CWM at more than $11 billion (DOD, 2003). However, the committee has not reviewed these estimates and expects that the actual cost will depend on, among other factors, the number of large burial sites, the degree to which active removal and destruction (as opposed to containment in place) is chosen as the remedy, and the number of buried CWM found in residential areas. The universe of buried CWM includes several sites where it is known that large numbers (in the thousands) of buried CWM are located—Redstone Arsenal, Alabama, which reportedly contains a mustard agent site and disposal trenches; Rocky Mountain Arsenal, Colorado, which has large numbers of buried CWM in Basin A; Aberdeen Proving Ground, Maryland, where there are large quantities in at least the Old and New “O” Field landfills; and Deseret Chemical Depot, Utah (formerly Tooele Army Depot South Area), particularly in solid waste management units 1 and 25 (U.S. Army, 1996).6 There also may be medium to large numbers of buried CWM at Pueblo, Colorado; Black Hills, South Dakota; Newport, Indiana; and Schofield Barracks, Hawaii.7 (See Table 1-1.) The characterization of a site as having large, medium, or small numbers of buried CWM in this report is qualitative. The prioritization model described in Chapter 2 is intended to more explicitly quantify the amount of CWM and should increase the priority of sites with large numbers of buried CWM that could one day pose a significant risk. An update of the 1996 survey is undergoing internal DOD review and was not available in time to inform this report. Furthermore, since new information periodically becomes available, more significant buried CWM sites could be uncovered in the United States or abroad.8 Ultimately, the cost of cleanup of buried CWM is not known or knowable precisely because the number of buried CWMs, the future use of the land in which they are buried, and the remedy that will be selected are not yet known. EXISTING NON-STOCKPILE DESTRUCTION TECHNOLOGIES This section provides basic descriptions of NSCMP equipment currently used to destroy RCWM. A number of NRC committees have reviewed and evaluated these technologies in depth in previous reports (NRC, 2001, 2002, 2004). In addition to the descriptions presented here, technical information on these NSCMP systems will appear throughout 3 Stone & Webster information paper briefed to an NRC committee on October 14, 1999. 4 See NRC (1999) for additional details on CAIS. 5 The 1996 report was a second, updated version of the 1993 survey that was required by Public Law 102-484, the National Defense Authorization Act for Fiscal Year 1993, section 176. 6 William R. Brankowitz, Deputy PMNSCM, at a meeting of the committee, Washington, D.C., November 29, 2005. 7 Information provided to the committee by the NSCMP. 8 No attempt was made in this report to address recovery or treatment of chemical weapons materiel that was disposed of in the ocean in the decades following World War II. However, the technologies described in this report could conceivably be used for such materials recovered in the future.
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel TABLE 1-1 Examples of Known or Potential Large Sites of Buried CWM Identified by the U.S. Army Type of Site Name of Site Description Issues Possible Approaches to CWM Disposal Live-fire sites Camp Sibert, Ala. Firing range for live CWM, 4.2-in. mortars Likely to contain dud-fired CWM (potentially shock sensitive) 1. Detect subsurface geophysical anomalies 2. Hand excavate anomalies in a containment structure 3. Dispose of CWM in EDS (low volume, less than 100 CWM expected) Schofield Barracks, Hawaii CWM live-fire range Likely to contain dud-fired CWM (potentially shock sensitive) 1. Detect subsurface geophysical anomalies 2. Hand excavate anomalies in a containment structure 3. Dispose of CWM in EDS (volume unknown) Large burial sites Pueblo, Colo. Suspected to contain buried M70 bombs in burn/burial pits Site will be closed under Base Realignment and Closure 1. Excavate pits (using appropriate methods, either manual or robotic) 2. Identify potential CWM as it is uncovered 3. Assess potential CWM using x-ray and portable isotopic neutron spectroscopy 4. Dispose of CWM in appropriate system(s) staged at the site Tooele/Deseret Chemical Depot, Utah Approx. 25 pits where CWM bombs and 4.2-in. mortars were burned and buried Many CWM munitions at this site are expected to be empty due to burn/burial process Redstone Arsenal, Ala. 50-60 pits, 100 yards long × 20 ft wide; used by technical escort unit to dispose of U.S. and foreign CWM after World War II; CWM stacked, burned, and buried Large quantity of CWM expected, but most are likely to be empty due to burn/ burial process; significant amount of foreign CWM is expected Black Hills, S.D. Large CWM storage facility in WWII Potential large burial site Large burial sites with records of decision (RODs) Old “O” Field, Aberdeen Proving Ground, Md. Multiple pits, contain U.S. and foreign CWM in various states and conditions Extremely dangerous sites, spontaneous deflagrations observed presumably due to mixing of incompatible chemicals and explosives Site is capped under a regulatory ROD. Remedy is a bentonite barrier, sand cap, and a pump-and-treat system; remedy appears to be working well and is reviewed periodically for effectiveness; ROD is reviewed periodically and further remedial action is possible Rocky Mountain Arsenal, Basin A, Colo. Large (1 sq. mi) site, numerous burial trenches suspected to contain CWM, vehicles, scrap, equipment, etc. Site used for disposal by commercial chemical manufacturers making pesticides Site is stabilized under an ROD; barrier wall and pump-and-treat system installed; ROD is reviewed periodically and further remedial action is possible SOURCE: William R. Brankowitz, Deputy PMNSCM, presentation to the committee on November 29, 2005. Chapters 4 through 6 as the capabilities of the international destruction technologies are discussed and compared with the capabilities of the current suite of NSCMP equipment, with particular emphasis on the EDS. Explosive Destruction System The EDS is capable of treating munitions regardless of whether or not they are energetically configured.9 The heart of the EDS system is an explosion containment vessel mounted on a flatbed trailer (see Figure 1-1). The EDS Phase 1 unit (EDS-1) has an inside diameter of 20 inches (51 cm), is 36 inches (91 cm) long, and can process munitions containing up to 1 pound TNT-equivalent of explosives. The EDS Phase 2 (EDS-2) has an inside diameter of 28 inches (71 cm) and a length of 56 inches (142 cm) and is designed to handle munitions containing up to 3 pounds TNT-equivalent of explosives, with occasional uses up to 5 pounds TNT-equivalent of explosives. The EDS is intended for use with World War I and World War II vintage CWM produced before 1945. In general, post-World War II munitions have bursters that exceed the capacity of the system. 9 Unless otherwise noted, material from this section was drawn from NRC (2001, 2002).
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel FIGURE 1-1 Diagram of EDS-2. SOURCE: Tom Cain, Mitretek, presentation to the committee on February 21, 2006. Large safety factors have been built into the design of the EDS vessel and the procedures for its operation. The mechanical integrity of the vessel was evaluated by Sandia National Laboratories using a combination of small-scale failure analysis tests and computer simulations. This evaluation indicated that the EDS-l containment vessel could withstand several thousand detonations with more than 1 pound of explosive, providing a significant margin of safety for a system with an intended life of 500 detonations (SNL, 2000). The EDS uses explosive shaped charges to access the agent in a munition and to destroy any energetics in the munition, with both processes taking place in a sealed explosion containment vessel. After detonation of the shaped charges, reagents appropriate to the agent to be neutralized are pumped into the vessel and the vessel contents are mixed until the treatment goal has been attained. After the concentration of chemical agent falls below the treatment goal (as determined by sampling the contents of the chamber), the liquid waste solution is transferred out of the chamber into a waste drum. The drummed EDS liquid waste is treated further at a commercial hazardous waste treatment, storage, and disposal facility (TSDF). The EDS-1 can be driven or flown on a C-130 aircraft to a site where non-stockpile chemical materiel is discovered or recovered materiel has been stored. The EDS-2 can be driven but has not been evaluated for air transport requirements. The EDS is considered the U.S. Army’s transportable system of choice for treatment of small quantities of non-stockpile munitions.10 It has an excellent record of regulatory compliance and public acceptance during the multiple deployments that have taken place around the nation, including the Spring Valley, Washington, D.C., cleanup operation, which took place in the middle of a residential neighborhood. Multiple EDS units are currently in use at Pine Bluff Arsenal in Arkansas to destroy recovered non-stockpile munitions that have been in storage there. Rapid Response System The RRS is a system for the treatment of significant quantities of recovered CAIS, of which approximately 110,000 were produced in various configurations from 1928 through 1969.11 A CAIS can be a sealed glass tube containing agent, a glass bottle containing agent, or a glass jar containing agent 10 Sites with a large number (that is, hundreds or thousands) of non-stockpile items were originally expected to be served by semipermanent treatment facilities, although a plan was implemented that replaced the Pine Bluff Non-Stockpile Facility with multiple EDS units for the processing of hundreds of recovered munitions (see NRC, 2004). 11 Unless otherwise noted, the information for this section is derived from NRC (2001, 2002).
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel FIGURE 1-2 Diagram of RRS operations trailer. SOURCE: U.S. Army, 2001a. adsorbed onto granular charcoal for use as a sniff set. The RRS uses a variety of chemical neutralization techniques to destroy agent, the technique depending on the agent. A line drawing of the RRS is shown in Figure 1-2. The RRS occupies three trailers. The operations trailer contains a series of linked glove boxes equipped to remove CAIS vials and bottles from their packages, identify their contents, and treat those that contain chemical agents (CAIS containing industrial chemicals are segregated and repackaged for off-site commercial disposal). The glass containers are then crushed in a reactor containing a chemical formulation that rapidly neutralizes the chemical agent. The contents of the reactor, including reagent, solvents, agent degradation products, and glass fragments, are transferred to sealed containers for disposal at a commercial hazardous waste TSDF. The support trailer contains spare equipment and supplies. The utility trailer carries electrical generators to allow the system to operate without commercial or host power when needed. For a more complete description of the RRS equipment and operations, see Rapid Response System Test Report (U.S. Army, 2001b). The RRS can be either driven to or flown to locations where CAIS have been recovered. Transporting by air requires the use of two C-17 aircraft (one for the RRS operations and utility trailers and one for transporters, a supply trailer, and a mobile analytical support laboratory). The RRS can treat one PIG12 of CAIS per day. The RRS has been successfully deployed to a number of sites around the nation. The first deployment was to Fort Richardson, Alaska, in July 2003. The RRS is currently destroying CAIS items at Pine Bluff Arsenal (PBA), having destroyed 1,000 of 5,000 CAIS items scheduled for destruction at PBA as of November 2005. The PBA deployment is scheduled to end by February 2007.13 Single CAIS Accessing and Neutralization System The SCANS reactor is a small, disposable container used to access and treat individual CAIS vials or bottles containing chemical agents (see Figure 1-3).14 Its process chemistry is similar to that of the RRS neutralization. It is intended for use only where a limited number (80 or fewer) of loose CAIS vials or glass bottles are recovered. Because SCANS does not have the glove box necessary to open a CAIS PIG safely, it could not be used for destruction of a CAIS PIG. The SCANS is a hand-held device. It requires neither the elaborate system of trailers that supports the RRS nor its large operating crew. It is a relatively inexpensive destruction system. The SCANS is used in conjunction with an analytical system such as a portable Raman spectrometer or a portable isotopic neutron spectrometer to identify the agent inside a vial or bottle so the correct reagent can be selected to neutralize it. A 4-liter bottle of reagent is placed in the reactor case, 12 A PIG is a metal canister with packing material designed to protect CAIS during transport. 13 See Rapid Response System at Pine Bluff Arsenal, <http://www.cma. army.mil/docviewerframe.aspx?docid=003671063>. 14 Unless otherwise noted, information is drawn from NRC (2002).
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel FIGURE 1-3 Photograph of SCANS. SOURCE: Tom Cain, Mitretek, presentation to the committee on February 21, 2006. along with a single CAIS item. The reactor is sealed and a breaker rod manually driven through the reactor, breaking the containers holding the CAIS agent and reagent. The agent mixes and reacts with the reagent to form a neutralent solution. The neutralent-containing reactor is then shipped to a permitted hazardous waste TSDF. Neutralization and Hydrolysis Other technologies currently used in non-stockpile operations, and also in stockpile operations, are neutralization and hydrolysis for destruction of chemical agent. This report employs the term “neutralization” for the use of an organic reagent to destroy agent and “hydrolysis” for the use of an aqueous reagent to destroy agent.15 The use of nonaqueous neutralization in the EDS, RRS, and SCANS was noted earlier in this chapter. As previously mentioned, the baseline incineration system is being used to destroy the U.S. stockpile of obsolete chemical agents and munitions at four continental U.S. storage sites. The U.S. Army Chemical Materials Agency has used or is planning to use hydrolysis technolo gies at the four remaining storage sites in the continental United States. Hydrolysis with hot water at 90C (194F) was used to destroy the stockpile of bulk mustard agent (HD) stored in ton containers at the Aberdeen, Maryland, site, with a destruction efficiency for mustard agent of more than 99.9999 percent. The resulting hydrolysate was sent offsite for biotreatment. Hydrolysis with a caustic NaOH solution at 90C (194F) will be used to destroy the bulk stockpile of VX nerve agent at the Newport, Indiana, site. At the Pueblo, Colorado, site, where mustard agent (HD and HT) is contained in nearly 8,000 projectiles, the agent will be removed from the assembled weapons and then hydrolyzed with hot water at 90C (194F) (NRC, 2005a). As currently planned, the hydrolysate will be biotreated at the site. At the Blue Grass site, both nerve agents (GB and VX) and mustard agent (H) are contained in a variety of munitions. Hydrolysis-based technology similar to that described above will be used (NRC, 2005b). See Table 1-2 for a list of some process parameters for neutralization of the agents at the Blue Grass, Kentucky, site. The chemistry of the hydrolysis reactions has been extensively studied (Yang et al., 1992; Yang, 1995). A good agent-by-agent summary of hydrolysis/neutralization is given by Pearson and Magee (2002). As shown in Table 5-1 in Chapter 5, neutralization and hydrolysis of agent have been used extensively in past operations in the United States and other countries. 15 The terms “neutralization” and “hydrolysis” are often used interchangeably in the literature on chemical agent demilitarization. Hydrolysis is the more appropriate term from a chemical process perspective. Neutralization is more in keeping with the notion of “to neutralize” and thereby render innocuous. It may be found in the literature to refer to hydrolysis in either aqueous or nonaqueous media.
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Review of International Technologies for Destruction of Recovered Chemical Warfare Materiel TABLE 1-2 Agent Neutralization Parameters for the Blue Grass Chemical Agent Destruction Pilot Plant Agent GB VX H Agent process feed concentrations Agent (wt %) 7.5 16.6 8.6 Caustic (wt %) (from 50% NaOH) 11.34 17.44 Added after to adjust pH to 10-12 Water (wt %) 81.16 65.96 91.4 System parameters and performance specifications Operating temperature (°F) 140 194 194 Peak rate baseline (units per hour) 40 GB rockets 48 VX rockets 26 H projectiles 15 GB projectiles 26 H projectiles Peak rate (lb agent/day)a 15,540 15,379 7,301 Total time per batch (min) 168 516 243 Throughput (batches per reactor per day) 6 2.5 2.5 Total weight of agent to be destroyed (tons) 305.7 127.2 90.63 Maximum agent concentration to achieve 99.9999 percent destruction efficiency (ppb) 75 160 85 aThe peak rate is the maximum expected rate during a campaign. Normal operating rates will be lower. Peak rate agent volumes have been multiplied by a safety factor of 1.25 for the purpose of sizing the tanks and other critical materials handling equipment. The total number of batches per day is less than what can be processed in 24 hours, again providing a design safety margin. SOURCE: Bechtel-Parsons, 2004; NRC, 2005b. REFERENCES Bechtel-Parsons. 2004. System Design Description (SDD) for Agent Collection and Neutralization, Blue Grass Chemical Agent Destruction Pilot Plant (BGCAPP) Project, Rev. A, July 26. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. Department of Defense (DOD). 2003. The Chemical Demilitarization Program: Increased Costs for Stockpile and Non-Stockpile Chemical Materiel Disposal Programs (D-2003-128), September 4. Arlington, Va.: Department of Defense Inspector General. NRC (National Research Council). 1999. Disposal of Chemical Agent Identification Sets. Washington, D.C.: National Academy Press. NRC. 2001. Evaluation of Alternative Technologies for Disposal of Liquid Wastes from the Explosive Destruction System. Washington, D.C.: National Academy Press. NRC. 2002. Systems and Technologies for the Treatment of Non-Stockpile Chemical Warfare Materiel. Washington, D.C.: National Academy Press. NRC. 2004. Assessment of the Army Plan for the Pine Bluff Non-Stockpile Facility. Washington, D.C.: The National Academies Press. NRC. 2005a. Interim Design Assessment for the Pueblo Chemical Agent Destruction Pilot Plant. Washington, D.C.: The National Academies Press. NRC. 2005b. Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant. Washington, D.C.: The National Academies Press. Pearson, G.S., and R.S. Magee. 2002. “Critical evaluation of proven chemical weapon destruction technologies (IUPAC Technical Report).” Pure and Applied Chemistry 74(2): 187-316. SNL (Sandia National Laboratories). 2000. Explosive Destruction System Fatigue/Life Cycle Analysis. Albuquerque, N.M.: Sandia National Laboratories. U.S. Army. 1996. Survey and Analysis Report. 2nd ed., December. Aberdeen Proving Ground, Md.: Program Manager for Chemical Demilitarization. U.S. Army. 2001a. Final Programmatic Environmental Impact Statement, Transportable Treatment Systems for Non-Stockpile Chemical Warfare Materiel, February. Aberdeen Proving Ground, Md.: Product Manager for Non-Stockpile Chemical Materiel. U.S. Army. 2001b. Rapid Response System Test Report. Final. October. Aberdeen Proving Ground, Md.: Program Manager for Chemical Demilitarization. U.S. Army. 2004. Recovered Chemical Warfare Materiel (RCWM) Response Process, EP 75-1-3, November 30. Available online at <http://www.usace.army.mil/usace-docs/eng-pamphlets/ep75-1-3/entire.pdf>. Last accessed February 14, 2006. Yang, Y-C. 1995. “Chemical reactions for neutralizing chemical warfare agents.” Chemical Industry 9: 334-337. Yang, Y-C., J.A. Baker, and J.R. Ward. 1992. “Decontamination of chemical warfare agents.” Chemical Reviews 92(8): 1729-1743.