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4 Technologies for Cleanup of CWM Sites • TECHNOLOGY WORK FLOW Digital radiography and computed tomography (DRCT), This chapter describes the current supporting technolo- • Portable isotopic neutron spectroscopy system gies that might be used for the cleanup of sites containing (PINS), and chemical warfare materiel (CWM). To put these technologies • Raman spectrometry. in context, a scenario is developed for a site with known or suspected CWM. If chemical agent fill is determined, the RCWM is again Suspected subsurface CWM is located by geophysical placed in interim storage to await assessment by the Mate- technologies, typically magnetometers or active electromag- riel Assessment Review Board (MARB). In this case, the netic sensors, which are in common use for the detection of next IHF may be off-site, so the RCWM is packaged into a conventional munitions and explosives of concern (MEC). multiple round container (MRC), which has been certified U.S. Army Corps of Engineers (USACE) contractors erect by the U.S. Department of Transportation, and transported a containment structure over the detected anomaly and dig on public roads by CARA. toward the object by mechanical or manual means, or both, After review by the MARB, destruction or treatment that are commonly used for conventional MEC. Upon dis- occurs by one of the following destruction technologies: covery of a suspected CWM, work stops in the area until military explosive ordnance disposal (EOD) technicians • Explosive destruction system (EDS), or Chemical Biological Radiological Nuclear (enhanced) • Transportable detonation chamber (TDC), Analysis and Remediation Activity (CARA) civilian person- • Detonation of ammunition in a vacuum integrated nel respond. EOD/CARA personnel complete the removal chamber (DAVINCH), or and evaluation of the suspected CWM and package it in a • Static detonation chamber (SDC). container approved for on-site transport to an interim hold- ing facility (IHF). Secondary waste is transported to a commercial facility Typically, the initial characterization by EOD/CARA will for final disposal. involve using field X-ray equipment to determine whether These topics are presented in sequential order, from the the ordnance is filled with liquid before it is placed in the point of initial detection through excavation and initial evalu- overpack and stored in an IHF. ation; packaging, storage, and transportation; treatment by If the recovered chemical warfare materiel (RCWM) is SCANS if CAIS items are found; spectroscopic or X-ray a chemical agent identification set (CAIS), the single CAIS assessment; assessment by the Army’s Materiel Assessment access and neutralization system (SCANS) is used to treat Review Board; destruction; and treatment of secondary it and the SCANS is then sent off-site to a Resource Con- waste. Three overarching topics—personal protective equip- servation and Recovery Act (RCRA) treatment, storage and ment (PPE), air monitoring, and air control systems—are disposal facility (TSDF). presented between detection and excavation because that is Otherwise the suspected CWM is removed from the IHF where they first come into play. That is, geophysical detec- and a mobile munitions assessment system (MMAS) is tion is completely nonintrusive, so PPE and air monitoring sent to the site to provide a nonintrusive assessment of the are typically not required. As soon as a shovel is put in the contents of the suspected RCWM. The key MMAS tools ground, however, PPE and air monitoring must be considered are these: 49
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50 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL in view of the potential for exposure to CWM from contami- CWM projects employ the geophysical technologies used nated media or shell fragments. for conventional MEC, which are adequate for detection of both individual MEC CWM and mass burials. Munitions constituents that may be associated with CWM, GEOPHYSICAL DETECTION on the other hand, are much more difficult to detect because Under the definitions associated with the Defense Envi- the metal casing of the MEC is not present. Typically, ronmental Restoration Program (DERP) Munitions Response sampling and either field or laboratory analysis is required Program (MRP), CWM can be found as intact munitions and to detect munitions constituents. Munitions constituents within partially exploded shells and fragments that may still consisting of, for example, chemical agents, heavy metals, contain MEC or munitions constituents.1 energetic compounds, or breakdown products of agent or MEC CWM includes the CWM that is contained in energetic compounds that are absorbed onto or into soils, can ordnance, and it has both a chemical agent and an explo- be detected only by field or laboratory analytical techniques. sive hazard component. The munitions constituent would The suite of CWM agent detectors and monitors used in include agent found outside the ordnance, for example, the field for detecting chemical agent and some breakdown products are described later in this report.2,3 agent leaked into and absorbed by soil; it would also include other hazardous constituents associated with the munition, including heavy metals, energetic compounds—TNT, for PERSONAL PROTECTIVE EQUIPMENT instance—and breakdown products of both agent and ener- getic compounds. PPE required to be worn on non-stockpile CWM proj- MEC CWM presents the greatest hazard because it con- ects is the same as the PPE approved by OSHA for other tains both an explosive and a chemical agent hazard. Because hazardous and toxic material handling operations. The the ordnance casing is made of steel, it is easily detected various OSHA levels of PPE (Levels A, B, C, and D and using common geophysical techniques. OSHA-approved modifications) have been demonstrated The geophysical sensors used to detect MEC CWM are to be adequate on numerous non-stockpile CWM projects, the same as those used for detecting conventional (high- including projects at Camp Sibert, Alabama; Spring Valley, explosive) MEC. The sensors used include magnetometers Washington, D.C.; and Schofield Barracks, Hawaii; and for and active electromagnetic systems. VX building demolition at Newport, Indiana. Government and private research has resulted in con- sistent improvements in the ability to detect MEC. These AIR MONITORING DURING EXCAVATION, INTERIM advances include improved sensors and signal processing, STORAGE, AND DESTRUCTION which in some cases allow us to “classify” or determine whether a buried object contains MEC or is a non-MEC Air monitoring for chemical agent is conducted whenever object based only on the object’s geophysical signal without there is a risk that workers or the general public could become having to excavate it and identify it visually. exposed to chemical agent during or due to site operations MEC CWM can be found individually or in mass burials. and whenever it is included as part of a comprehensive Work An example of where individual MEC CWM has been found Plan to establish the policies, objectives, procedures and is the former Camp Sibert, Alabama, Site 8, which was a responsibilities for the execution of a site-specific response CWM ordnance impact area. Some of the 4.2-in. mortars action. Detailed policies and safety and health requirements that were fired into Site 8 failed to function and remained for RCWM response actions are contained in U.S. Army in the subsurface to be detected individually, excavated, and publications, including manuals, regulations, and pamphlets disposed of. (U.S. Army, 2004c, 2004b, 2006, 2007b, 2007c, 2008b, Other MEC CWM is found in mass burials from previous 2008e). A large part of the RCWM response process uses the disposal operations, as was the case at the Spring Valley site same response procedures required for other MEC. There- in Washington, D.C. Such mass burials are relatively easy to fore, RCWM response actions are conducted in accordance detect using geophysics because the multiple MEC CWM with MEC response procedures (U.S. Army, 2006, 2007b). buried together present a large geophysical target. However, it is usually not possible to determine the contents of the subsurface-buried mass from the geophysical data because 2Karl E. Blankenship, FUDS Project Manager, Mobile District U.S. individual objects cannot be distinguished within the large Army Corps of Engineers, “Remediation of Contaminated Soil at Camp buried mass. Sibert, Alabama: The Installation Manager’s Perspective,” presentation to the committee on November 3, 2011. 3Herbert H. Nelson, Manager, Munitions Response Program Strategic En- vironmental Research and Development Program, Environmental Security 1Formal definitions of MEC and munitions constituents are in the Site Pri- Technology Certification Program, Department of Defense, “Geophysical oritization Protocol (SPP) at http://www.denix.osd.mil/mmrp/Prioritization/ Detection of RCWM: Capabilities and R&D,” presentation to the committee MRSPP.cfm. on January 17, 2012.
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51 TECHNOLOGIES FOR CLEANUP OF CWM SITES When a client organization—say, the Non-Stockpile 2 005a). MINICAMS was used at Camp Sibert, Alabama, with mixed results.5 It is expected that a Chemical Materiel Project (NSCMP)—identifies the need for new analytical or operating procedures for its chemi- similar experience will be encountered during other cal operations, the Edgewood Chemical Biological Center remediation efforts. (ECBC) is generally responsible for their development. —The MINICAMS was used in the location of an At the U.S. Army Engineering Support Center, Huntsville anomaly as that anomaly was being investigated (USAESCH) RCWM projects, ECBC is typically respon- and removed. As part of the MINICAMS calibra- sible for preparing the plan for air monitoring and analysis tion procedure, a midday challenge was used. This methodologies for chemical agents (and other hazardous procedure can cause a delay in field operations of 2 chemicals, if required) in accordance with U.S. Army stan- to 3 hours if the initial calibration is unsuccessful. dards (U.S. Army, 2007c, 2008e) for setting up stations that —The MINICAMS is not sufficiently robust to be monitor the air for chemical agents during all phases of the moved from anomaly to anomaly. This results in response action, supporting USACE to maintain any filter long downtimes. A more rugged, portable system units for vapor containment and conducting on-site analysis for near-real-time air monitoring is needed. for headspace samples collected from media suspected of —In a certain part of Camp Sibert called the “mus- being contaminated with chemical agent. The committee tard soaking pit,” the presence of trichloroethylene judges vapor containment facilities and filtering techniques (probably used as a decontamination fluid or as a to be adequate and thus does not discuss them in detail in component of decontamination fluid) interfered this chapter. with determination of mustard by MINICAMS. • Open-path systems such as fence-line Fourier t ransform infrared spectrometry air monitoring Monitoring Equipment (OP-FTIR) send a beam of light through the open air, The choice of monitoring equipment is based on the to a reflector and then back to a receiver. If gases that type of monitoring to be performed and the types of agent absorb light are present in the beam path, they can be involved. Air monitoring equipment systems have been identified and quantified. This technology will have described in detail previously (NRC, 2005a). Monitoring limited applicability to nonstockpile cleanup opera- systems and their associated operating procedures used at tions because of its limited sensitivity. It is marginal non-stockpile sites must be appropriately certified before for detection at the short-term exposure limit (STEL) use. The following monitoring equipment systems may be level (NRC, 2005b). • used for the detection of chemical agents present in the air The depot area air monitoring system (DAAMS) is at non-stockpile disposal sites, at stockpile disposal sites, a portable air-sampling unit that is typically used for and at storage facilities (U.S. Army, 2004c; NRC, 2005a): agent confirmation sampling (following a positive result using MINICAMS, for example). It is designed • The Miniature Chemical Agent Monitoring System to draw a controlled volume of air through a glass (MINICAMS) is an automatic air monitoring sys- tube filled with a solid sorbent collection material. tem that collects compounds on a solid sorbent trap After sampling for the predetermined period of time (typically a porous polymer) and thermally desorbs and flow rate, the tube is removed from the vacuum line and transferred to a suitable laboratory facility6 them into a capillary gas-chromatography column for separation and detection. It is a lightweight, por- for gas chromatography analysis to determine the table, near-real-time, low-level monitor with alarm presence, type, and quantity of agent. This technique capability, designed to respond to G-series nerve is sufficiently sensitive and will allow analysis down agents, VX nerve agent; mustard; nitrogen mustard; to the appropriate AEL for the relevant agent. • and lewisite. Alarm levels for MINICAMS used at A new air monitoring system, the multiagent meter, is non-stockpile sites are typically set at 0.70 of the being developed by Sandia Livermore under NSCMP appropriate airborne exposure limit (AEL)4 (NRC, sponsorship (Rahimian, 2010). This is a handheld device that can simultaneously analyze for mustard 4Airborne exposure limits (AELs) are levels of exposure to hazardous materials to which workers and the unprotected general population can be experiencing any adverse health effects; and the immediately dangerous exposed without experiencing adverse health effects. AELs are established to life or health (IDLH) limit, the level of exposure that an unprotected by the Centers for Disease Control and Prevention (CDC). They include the worker can tolerate for 30 minutes without experiencing escape-impairing short-term exposure limit (STEL), the level at which an unprotected worker or irreversible health effects. 5Karl E. Blankenship, FUDS Project Manager, Mobile District U.S. can operate safely for one or more 15-minute periods (depending on the agent) during an 8-hour workday; the worker population limit (WPL), the Army Corps of Engineers, “Remediation of Contaminated Soil at Camp concentration at which an unprotected worker can operate safely 8 hours a Sibert, Alabama: The Installation Manager’s Perspective,” presentation to day, 5 days a week, for a working lifetime, without adverse health effects; the the committee on November 3, 2011. 6One example of a suitable analytical laboratory facility is the mobile general population limit (GPL), the concentration at which the unprotected general population can be exposed 24 hours a day, 7 days a week, without analytical platform used by ECBC.
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52 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL • agent and G-series agents at levels near the AELs. Decontamination monitoring. Personal decontamina- The cycle time is 10 minutes, and (reportedly) no tion station monitoring is used to verify that complete calibration is needed unless the detector is replaced. decontamination of a worker or piece of equipment Testing near the short-term exposure limits (STELs) has been conducted. Decontamination monitoring has been carried out, and the meter will be used with will typically be conducted using a MINICAMS. • the steam injection testing in the new EDS-2 test Surface monitoring. Performed on equipment and fixture during 2012.7 See the EDS discussion later in remediation waste that is suspected of being con- this chapter for more information on the test fixture taminated by chemical agent, in accordance with U.S. and the multiagent meter. Army standards (U.S. Army, 2007b, 2008e). • Headspace monitoring. This is conducted on envi- ronmental samples suspected of being contaminated Types of Monitoring with chemical agent before they are shipped off-site Monitoring can be classified into the following types: for analysis. This type of analysis is conducted to pre- vent samples contaminated above the vapor screen- • Background monitoring. This monitoring is con- ing level (VSL) from being shipped by commercial carrier.8 ducted prior to initiation of site operations to provide a baseline reference for subsequent analyses and to determine if there is any interference in the area. EXCAVATION EQUIPMENT AND TECHNIQUES DAAMS tubes and/or MINICAMS are generally used for this type of monitoring for the chemical Excavation equipment for use on CWM projects can be agents of concern. classified into two categories: conventional and robotic. • Area monitoring. General area monitoring provides an early warning to personnel that there is a problem Conventional Excavation Equipment and that action must be taken. The monitoring device or sampling port is placed in strategic locations in the Conventional methods of excavation, including by hand work area where there is a potential for encountering and using mechanical equipment, are routinely used on MEC agent vapors. The sample locations are determined projects to access conventional MEC. The same tools and based on factors such as the agent involved, the air- techniques are used on CWM projects to access subsurface flow patterns in the area, the operation(s) being per- CWM. When accessing shallow-buried, single-item CWM formed, and the location of the source of the potential (for example, at Camp Sibert, Alabama, where CWM 4.2-in. release. A MINICAMS and/or commercially avail- mortars were fired into target areas for training), hand tools, able monitors are used for this type of monitoring. such as shovels and hand trowels, are used by trained techni- The new multiagent meter (see the last bullet item cians to uncover the subsurface anomalies that were detected in the previous section) may also prove valuable for by geophysical methods. area monitoring. DAAMS may be used to confirm a For mass burial sites, mechanical equipment will most positive MINICAMS result. l ikely be used. USACE regulations allow mechanical • Perimeter monitoring. This type of monitoring is not equipment, such as backhoes and excavators, to be used to designed to give rapid warning of hazardous condi- excavate MEC with the caveat that the mechanical excavator tions but is instead used to document conditions over may not work closer than 1 ft from the MEC (U.S. Army, time and to confirm a hazardous condition as alarmed 2004a). In this case the mechanical excavation equipment by the MINICAMS. DAAMS tube sampling stations is used to remove the bulk of the overburden soil from the and/or the OP-FTIR are placed at the perimeter of MEC/CWM and the final 1-ft. of soil is removed using hand the work area to record any chemical agent release excavation tools. beyond the safety zone established around the MEC Applying conventional equipment excavation to CWM work area (exclusion zone). projects requires that the project managers determine the • Mobile area monitoring. This is a method of sam- appropriate PPE to be used by the field teams to ensure their pling airborne levels of contaminants in the work- safety in the event that there is an unexpected release of place. Samples are taken over the entire workday CWM during the excavation process. Appropriate PPE has using a sampling train of DAAMS tubes that are con- been selected and successfully used on numerous projects, nected to a dual-port sampler attached to a portable air pump calibrated to a specified airflow rate. 8A VSL (vapor screening level) is a control limit used to clear materials for off-site shipment based on agent concentration in the atmosphere above the packaged waste materials. The VSL depends on the permit for the par- 7Laurence G. Gottschalk, PMNSCM, “Non-Stockpile Chemical Materiel ticular facility involved but is often set at either the short-term exposure limit Project Status and Update,” presentation to the committee on September (STEL) or at the short-term limit (STL), which is numerically the same as 27, 2011. the STEL but does not have the 15-minute time component (see NRC, 2007).
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53 TECHNOLOGIES FOR CLEANUP OF CWM SITES including Camp Sibert, Alabama; Spring Valley, Washington, acknowledged experts in performing this function in both D.C.; and Schofield Barracks, Hawaii. emergency and planned CWM removal scenarios. CARA is dedicated to this mission, its personnel are well trained, and they perform the packaging and transportation function Robotic Excavation Equipment adequately. Robotic excavation equipment makes site workers safer The non-stockpile CWM is then overpacked in one of three types of containers used for this purpose:12 by separating them from the hazard. The operator can be far enough away from the excavation location to be out of • harm’s way in the event of a CWM release or accidental deto- Propelling charge canisters. These are reused carbon nation. Another benefit of robotic excavation equipment is steel canisters originally designed for shipping indi- that the operator can be located in the comfort of a building, vidual 8-in. projectile smokeless powder propelling protected from the elements, and not required to wear PPE. charges. They have an O-ring sealed lid designed Many commercial and Department of Defense (DOD) to keep moisture and dirt from entering the canister programs are working on developing and fielding robotic and they serve as an inexpensive CWM overpack; in excavators for CWM and conventional MEC excavation.9 this application, the O-ring seal keeps minor leaks New robotic excavation equipment is being made more of agent inside the canister. However, they are not reliable and robust through DOD and privately funded designed for this purpose, are not Department of research and has been available for use on CWM projects Transportation (DOT)-certified for off-site transpor- since it was extensively used on the Old O-Field CWM tation of CWM, and, while commonly used, are best encapsulation project at Aberdeen Proving Ground, Mary- suited to short-term storage and limited transporta- land, in 1995.10 tion to an on-site IHF. • There have been rapid strides in the use of conventional Single round containers (SRCs). These are DOD- and robotic systems to perform a variety of complex indus- designed military specification (MIL-SPEC) over- trial tasks. For example, robotics systems are now used in packs designed and intended for the containeriza- medical applications, in civilian bomb removal, and for tion of CWM. SRCs were tested to DOT and DOD surveillance and disarming of improvised explosive devices requirements but are not DOT certified (Teledyne in combat. Future developments in robotic systems are Brown, 1998). They are made of carbon steel and expected to improve the ability to perform a wide variety are O-ring sealed to prevent vapor leakage. Several of tasks. sizes are used in the chemical stockpile destruction program and are considered to be an all-purpose CWM overpack option for on-site transportation and PACKAGING, TRANSPORTATION, STORAGE (ON-SITE storage. AND INTRASTATE) • Multiple round containers (MRC). MRCs are DOD- Frequently, non-stockpile CWM must be packaged, trans- designed MIL-SPEC overpacks specifically designed ported, and placed in storage prior to disposal. Packaging, to accept various sizes of CWM covering most of transportation, and storage of CWM has been classified by the potential non-stockpile CWM. Table 4-1 lists the the Army as an “inherently governmental operation”11 and, MRCs and their intended contents. They are made of as such, is performed by military service member experts and stainless steel and are designed to contain any leak- specialized civilian federal government employees. age and vapors from an overpacked CWM. MRCs are transported in a wood overpack shipping box for handling convenience and for blocking and bracing CWM Packaging and Transportation considerations. The MRCs in their wooden overpack Packaging of CWM is also an “inherently governmental have been tested to meet DOD and DOT require- operation” and is performed by CARA. Prior to packaging, ments. (See for example 12-in. by 56-in. Multiple non-stockpile CWM containers must be checked for leaks Round Container Approval Documentation, Defense and, if found to be leaking, sealed. CARA personnel are the Ammunition Center, A02-0003.1, August 1998.) As the only DOT-certified overpacks for CWM, they are required for off-site transportation and are the 9Available at http://www.globalsecurity.org/military/systems/ground/ preferred overpack when shipping over a significant aoe.htm, http://www.army.mil/article/16473/U_S_Army_Demonstrates_ distance is required. Robotic_Technologies/, http://roboticrangeclearance.com/uploads/R2C2_ Robo_Clearance.pdf. Each site last accessed April 11, 2012. 10Available at http://pubs.usgs.gov/wri/wri00-4283/wrir-00-4283.pdf. Last accessed March 30, 2012. 11Laurence G. Gottschalk, PMNSCM, “Non-Stockpile Chemical Mate - 12 Franklin D. Hoffman, Chief, Operations Team, NSCMP, “Non- riel Project Status and Update,” presentation to the committee on September Stockpile Chemical Materiel Project Equipment and Capabilities Over- 27, 2011. view,” presentation to the committee on September 27, 2011.
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54 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL TABLE 4-1 Multiple Round Containers 4-1). Details of the IHFs currently used by NSCMP are given in “Property Identification Guide, Revision 0” (U.S. Army, Maximum Contents 2011e) and “Interim holding facility overview fact sheet” MRC Typea Weight (lb) Potential Contents (U.S. Army, 2011c). Construction and safety features were 5 × 25 32 4-in. Stokes and 4.2-in. developed by NSCMP (U.S. Army, 2011e). Very detailed mortars; 75-mm projectiles; information on the construction design, safety issues, citing, M139 and M125 bomblets physical security planning, and vulnerability assessment for 7 × 27 100 4.2-in. mortar; 75-mm and an IHF are given by USACE (U.S. Army, 2004c). Informa- 4.7-in. projectiles; 155-mm tion on IHF features and past use were provided by Laurence and 2.36-in. rockets G. Gottschalk, PMNSCM, in a presentation to the committee 9 × 41 200 Livens, 155-mm, 175-mm, on September 27, 2011. and 8-in. projectiles The primary reason for using IHFs is to provide security 12 × 56 200 CAIS PIGs; M47, E46, E52, for RCWM. To this end, high security locks, fencing, and a M70, M70A1, and M113 lighting system can be employed, and the IHF is constructed bombs from fireproof and corrosion-resistant materials. Munitions 18 × 5.5 61 Mines placed in IHFs are first placed in an appropriate overpack (a 26 × 79 1,000 500- and 1,000-lb bombs propelling charge canister, an SRC, or an MRC). 30 × 40 850 50-gal drums For environmental protection, the interiors include sec- ondary containment in the form of a sump beneath the floor a The first number is the inner diameter in inches and the second is the length in inches. NOTE: PIG, package in-transit gas shipment container. grating to collect liquids should leaks occur in waste con- SOURCE: Individual MRC fact sheets provided by NSCMP. tainers. Electrical switches and fixtures are of nonexplosive design to reduce the possibility of fires. Agent monitoring and the use of air pollution control systems, e.g., activated carbon adsorption systems, can be used to reduce the risk that Currently the CWM must be removed from the overpack chemical agent or hazardous fumes are released to the envi- prior to treatment in an explosive destruction system (EDS). ronment. Air conditioning can be provided to control vapor NSCMP is developing a universal munitions storage con- pressures. Monitoring ports are provided to allow measuring tainer (UMSC) made of high-density polyethylene that will the concentrations of materials of interest—for example, allow the overpacked CWM to be treated in an EDS without chemical warfare agents—in the vapor space before the removal from the overpack.13 The UMSC will contain an RCWM enters the IHF. internal centering system to consistently position the CWM IHFs are factory-built and are purchased by NSCMP from within the overpack. Then the explosive shaped charges can Carber-Rambo Associates, Inc.; HAZ SAFE; and United be placed on the outside of the overpack and the prepared States Chemical Storage. They feature a steel frame, with overpack will be placed in the EDS. The UMSC will be interior surfaces constructed from unpainted 304 stainless sacrificed upon detonation of the shaped charges. When steel. The exteriors are constructed from carbon steel and are fielded, the UMSC will offer improved safety because it painted. IHFs can be purchased in various sizes, but are all eliminates the need to manually remove the CWM from the designed to be transported by truck without special permits. overpack prior to placement of the explosive shaped charges IHFs are inspected periodically, and repairs are documented. and placement in the EDS. The USMC is not intended to be The NSCMP has used IHFs at its operations at Spring DOT certified—it will only be used on-site but will fit into Valley, Washington, D.C.; Dover Air Force Base, Delaware; a DOT-certified container if off-site shipment is required. and Camp Sibert, Alabama. Future deployment of IHFs None of the above overpacks are able to contain an acci- is planned at Fort Glenn, Alaska, and Black Hills, South dental detonation. Therefore, part of the CARA mission is to Dakota.14 The NSCMP has used igloos approved for storage ensure the explosive safety of the CWM prior to overpacking of RCWM at several other sites. and shipping. Transportation of CWM is also performed by Three holding facilities are used at Spring Valley.15 When CARA as one of the “inherently governmental operations.” first recovered, a munition is placed in the assessment hold- ing facility. It remains there until the MMAS arrives on CWM Storage site and the data needed for assessment of the munition are recorded. The munition is then placed in a second holding When buried munitions or other hazardous materials are removed from the ground, they are preferably placed in an 14Laurence existing magazine (bunker or igloo) or in an IHF (Figure G. Gottschalk, PMNSCM, “Non-Stockpile Chemical Mate- riel Project Program Status and Update,” presentation to the committee on September 30, 2011. 13Laurence G. Gottschalk, PMNSCM, “Non-Stockpile Chemical Mate - 15Dan G. Noble, Project Manager, Spring Valley, Baltimore District, U.S. riel Project Program Status and Update,” presentation to the NRC Commit - Army Corps of Engineers, comments to committee members during the tee on Chemical Demilitarization on November 30, 2011. committee’s tour of the Spring Valley site on November 2, 2011.
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55 TECHNOLOGIES FOR CLEANUP OF CWM SITES FIGURE 4-1 Interim holding facility.eps FIGURE 4-1 Interim holding facility. SOURCE: Laurence G. BITMAP Gottschalk, PMNSCM, “Non-Stockpile Chemical Materiel Project Program Status and Update,” presentation to the committee on September 27, 2011. FIGURE 4-2 A typical digital radiography and computed tomography scan.eps FIGURE 4-2 A typical DRCT scan. SOURCE: Franklin D. Hoff- 2 BITMAPS man, Chief, Operations Team, NSCMP, “Non-Stockpile Chemical facility, the MARB holding facility. It remains there until Materiel Project Equipment and Capabilities Overview Equipment the assessment is complete, whereupon it is placed in the and Capabilities to NRC,” presentation to the committee on Sep - third holding facility, called the interim holding facility. The tember 27, 2011. munition is held there for up to 2 years, awaiting destruction in an EDS. the object, the greater the attenuation of the X-ray intensity. SINGLE CHEMICAL AGENT IDENTIFICATION SET The object being scanned can be rotated or tilted to produce ACCESS AND NEUTRALIZATION SYSTEM various views of the munition and its internals. A difference in level from tilt view to level view is useful in determining T he single CAIS access and neutralization system the presence of liquids in the suspected CWM. The DRCT (SCANS) is a small polyolefin unit for detoxifying intact can be operated from a remote location, allowing objects to ampoules and bottles from CAIS. These approximately 4-oz be scanned from a safe distance (U.S. Army, 2011a). bottles are placed in the unit with a 1-gal bottle of reagent, A typical DRCT scan is seen in Figure 4-2. The container normally dichlorodimethylhydantoin in solution. After the on the left shows that by tilting the container, the presence of unit is sealed, the bottles are ruptured with a mallet and liquid can be verified by a shift in the liquid level. plunger. The ingredients are mixed by manually shaking the DRCT is a robust, proven technology. It is portable, can unit (U.S. Army, 2011e). The system has been successfully be operated remotely, can determine the presence of liquids, used numerous times; the committee judges that it requires and can be used even if the suspected CWM is in an over- no further research. pack. It cannot be used to determine the type of chemicals in a container. SPECTROSCOPIC AND X-RAY ASSESSMENT The PMNSCM has mentioned that NSCMP is updat- ing the DRCT with newer, commercial capabilities and Digital Radiography and Computed Tomography integrating PINS and DRCT.16 However, the committee did not receive any detailed information on these development Digital radiography and computed tomography (DRCT) activities. is a technology similar to a CAT scan. It uses X-rays to Although the portable isotopic neutron spectrometer vertically scan a suspect CWM on a rotating platform. It (PINS) is considered the most effective tool for determin- produces a digital view of the munition interior, even through ing the presence of CWM inside a chemical munition or an overpack container. The DRCT requires an X-ray source and a detector. The detector records radiation that passes through the object being scanned. The intensity of the radia- 16Laurence G. Gottschalk, PMNSCM, “Non-Stockpile Chemical Mate - tion arriving at the detector is attenuated by the objects in its riel Project Program Status and Update,” presentation to the committee on path as a function of their density: The thicker, more dense September 30, 2011.
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56 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL Raman Spectroscopy container, DRCT has several capabilities that make it an important part of the MMAS. Raman spectrometry is used only to analyze liquids in recovered glass containers.18 These include the vials and Portable Isotopic Neutron Spectroscopy ampoules from CAIS. Raman spectra are generated by the detection of scattered visible radiation. A sample is irradi- PINS is regularly deployed in the field to identify the ated with monochromatic visible or near-infrared light, c ontents of sealed munitions suspected of containing which is absorbed by the electrons. The electrons reemit the chemical warfare materiel. Developed by Idaho National absorbed energy as infrared light, which is detected at an Laboratory, the PINS system has been patented and is com- angle perpendicular to the light source. The spectrum that mercially available through AMETEK, Inc., in Oak Ridge, is generated yields structural information about the sample, Tennessee.17 This self-contained, nondestructive investiga- as shown by the wavelength and intensity of the emitted tive tool is the first step in determining the proper neutraliza- infrared radiation. tion procedure for found non-stockpile chemical weapons. T he PINS system contains a neutron source, MOBILE MUNITIONS ASSESSMENT SYSTEM californium-252. The neutrons pass through a polyethylene block and two tungsten plates, which serve to both slow The MMAS is a transportable system equipped to analyze the neutrons and absorb gamma radiation generated by the and provide on-site information about the contents of uniden- neutron source before passing through the munition mounted tified munitions without opening them (U.S. Army, 2011d). within the instrument (Caffrey et al., 1992). The neutrons It was designed and built by the NSCMP to take instruments pass through the steel walls of the munition and interact with into the field, provide analysis, and communicate informa- the chemicals inside, generating a spectrum of gamma radia- tion to response personnel. tion via neutron capture, followed by prompt gamma-ray As shown in Figure 4-3, the MMAS is an operational emission (Skoog et al., 1998). The gamma-ray emissions are platform that transports and contains the support needed detected using a multichannel analyzer that is able to filter to analyze the content of items. It contains nonintrusive the gamma radiation generated by the steel or aluminum cas- assessment equipment such as instrumentation for PINS, ing. Data are displayed as a spectrum of counts versus the DRCT, and Raman spectroscopy to assess conventional or emitted gamma-ray energy, which is element- and isotope- chemical-filled munitions. It contains an onboard darkroom specific (shown in units of kiloelectron volts, or keV). The to process X-ray film and is equipped with sensors to con- emission energy peaks are analyzed by the software to gener- stantly monitor weather conditions and cameras to monitor ate an elemental ratio, or empirical formula, for the chemical site activities. It includes a portable electric generator, which materiel. The spectrum is then compared against a library of provides a constant power supply. known spectra of chemical agents to identify the contents Data generated by the MMAS are stored in redundant of the munition (Caffrey et al., 1992). computer systems equipped with battery backup. Satellite Significant advantages of the PINS system include porta- links, cellular phones, and shortwave radio ensure local bility and user-friendly automation. The setup for this system emergency responders can be contacted in the case of an includes a daily background scan to account for local envi- emergency. The MMAS contains equipment for decontami- ronmental factors, such as high hydrogen concentrations in nation of personal protective equipment (U.S. Army, 2005). wetland areas, high chlorine concentrations in coastal areas, The MMASs are operated by CARA on behalf of NSCMP. and so on. In addition, the peak energies and relative intensi- There are three MMAS units located in the United States, ties are unaffected by the possible degradation or polymer- two of which are at Aberdeen Proving Grounds in Maryland ization of the chemical materiel, rendering the technology and one at Pine Bluff Arsenal in Arkansas.19 applicable to any intact chemical weapon. Lastly, PINS does The DRCT and PINS data, pictures of munitions, and his- not generate low-level radioactive material. The neutron torical and other data are evaluated by the Materiel Assess- capture method generates only very short-lived radionuclei ment Review Board (MARB), which then recommends a (Caffrey et al., 1992). method of disposing of the CWM. Chapter 2 describes the While PINS is an essential tool in the assessment of MARB’s activities. recovered munitions, it is not totally reliable. See Chapter 7 for a discussion of this subject and for findings and recom- mendations related to PINS. 18Laurence G. Gottschalk, PMNSCM, “Non-Stockpile Chemical Mate- riel Project Program Status and Update,” presentation to the committee on September 30, 2011. 19 Franklin D. Hoffman, Chief, Operations Team, NSCMP, “Non- 17Available at http://www.inl.gov/research/portable-isotopic-neutron- Stockpile Chemical Materiel Project Equipment and Capabilities Over- spectroscopy-system/. Accessed on March 15, 2012. view,” presentation to the committee on September 27, 2011.
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57 TECHNOLOGIES FOR CLEANUP OF CWM SITES FIGURE 4-3 Mobile munitions assessment system. Contents include heating and air conditioning system; electrical power supply and distribution system; PINS system; radiography systems; Raman spectroscopy system; data acquisition and handling system; audio/video equipment; communications equipment; and support equipment. SOURCE: Laurence G. system.eps FIGURE 4-3 Mobile munitions assessment Gottschalk, PMNSCM, “Program Status and Update to NRC,” presentation to the committee on September 27, 2011. BITMAP DESTRUCTION TECHNOLOGIES and where there is no need for placing donor and shaped charges to access the agent cavity in munition bodies, the In this section, four systems, each employing one of use of the EDS, TDC, or DAVINCH may not be warranted. three technologies that have been used to destroy chemical At such sites, it is probably more practical to use an alterna- munitions are described. Each has been used abroad and/or tive method—for example, metal parts treatment, heating in the United States. One system, the EDS, uses explosive in an SDC, or chemical neutralization—to destroy remain- charges only to access the agent cavity in the munition body ing agent residue and heels. For sites at which some of the and uses a liquid reagent to neutralize the agent. Second- RCWM consists of munitions and containers that are still ary wastes include a liquid neutralent, rinsates, and metal filled with agent, one or more of the technologies summa- fragments. Another system, the SDC, does not use external rized above may be used, depending on site-specific needs explosives at all but depends on electric heating or heat from and technology capabilities. previous detonations to detonate or deflagrate the munition and destroy the agent in a sealed chamber. Primary effluents Explosive Destruction System are metal fragments, treated off-gases, and dry spent scrubber solution salts from the spray dryer. The EDS is a system designed by NSCMP. Sandia The remaining two systems, the TDC and the DAVINCH, National Laboratories has built five to date, for on-site are similar in that they both use external charges to access destruction of recovered chemical weapons or treatment the agent cavity in a sealed chamber (as does the EDS), but of other chemical warfare materiel. Two versions, the EDS unlike the EDS, they also use the detonation to destroy the Phase 1 (EDS-1) and the EDS Phase 2 (EDS-2) (see Figure agent. These technology variants differ in terms of detonation 4-4), have been built and operated, with the EDS-2 being a conditions, off-gas treatment, explosion containment capac- later design and, in general, able to destroy more and larger ity, and other operating parameters. Their primary effluents munitions than the EDS-1. Information on the two systems are metal munition fragments, treated off-gases, and, in the is available from several sources, including NRC, 2006, case of the TDC, also gravel dust and spent lime. 2009a, and 2010b. An overview of the four systems, showing several key Both EDS-1 and EDS-2 employ shaped cutting charges to differences and similarities between them, is provided in explosively open one or more containers or munitions placed Table 4-2. In the text that follows, the systems are described within a closed, sealed containment vessel, thereby releasing in greater detail and their experience to date in destroying the agent contained within the container(s) or munition(s). chemical munitions is summarized. Any energetics contained within a munition before treatment At sites where some RCWM consists of munition bodies, will be destroyed by the explosive shaped charge. Chemical containers, and scrap metal that contain only traces of agent
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58 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL TABLE 4-2 Comparison of Destruction Technologies Technology Type Neutralization Explosive Destruction Explosive Destruction Thermal Destruction Technology EDS TDC DAVINCH SDC Attribute Sandia, NSCMP CH2M HILL Kobe Steel Dynasafe Agent contained in: Sealed cylindrical vessel on Rectangular detonation Double walled cylindrical Spheroid double walled static truck bed chamber detonation vessel kiln Agent in munition accessed Shaped charges on Donor charge placed Shaped and donor charges Heating of munition, followed by: munition or munition around munition or on munition or munition by deflagration or detonation overpack munition overpack overpack Reaction with reagenta Agent destroyed by: Detonation: Heat and Detonation: Shock wave, Heating to 550°C resulting in pressure from controlled compression, thermal agent decomposition in vessel at 60°C for 1 hr detonation at 700°-1000°C destruction in fireball at followed by 2-hr hot water 2000°C rinse 100 minutesb Typical cycle time (varies 48 hr 35-40 minutes 20-30 minutes with munition) Off-gas treatment None. Agent and reagent Catalytic oxidizer with Cold plasma oxidizer Thermal oxidizer at 1100°C, react until agent is max temperature of (Glid-Arc) at 600°C, 2 sec residence time; acid destroyed. No off-gas 1095°C; reactive bed 0.5-1.0 sec residence scrubber at approx. 80°C; produced. filter with hydrated lime time; in-line gas scrubber IONEX filter containing HEPA or sodium bicarbonate with NaOH washdown to filter, sulfur-impregnated for acid neutralization; neutralize the gas; sulfur- carbon, and activated carbon; carbon adsorption system; impregnated carbon and baghouse filter and HEPA for particulatesc ceramic filter and HEPA for activated carbon; HEPA particulates filters for particulates Waste streams Liquid neutralent and Exhaust gas, metal Metal fragments, exhaust Metal fragments, scrubbed rinsate, scrap metal fragments, gravel dust, gas, dust, activated carbon, off-gas, dust, salts, activated (munition fragments). spent lime, activated carbon. scrubber condensate water. carbon. Scrap metal suitable Discharged scrap metal is Discharged scrap metal is Discharged scrap metal is for release for unrestricted use ≤1 VSLd (formerly 3X) ≤1 VSL (formerly 3X) ≤1 VSL (formerly 3X) (formerly 5X) Ability to recycle or further N.A. No gas stream is None. Has expansion tank Yes. Can recycle off-gas Yes. If operated in batch treat off-gas produced. for off-gas but no ability to through cold plasma mode, off-gas in the static recycle oxidizer after holding and kiln can be held at 550°C testing in off-gas retention and tested until agent is not tank detected Transportability Transportable on one trailer Transportable on 8 trailers, Fixed facility but vessel Fixed facility but can 10 days can be moved on three be moved in 20-25 ISO flatbed trailers (one each containers for the outer chamber, the inner chamber, and the lid) plus two trailers for the off-gas treatment unit and additional trailers as needed for supporting equipment Explosive containment 5 lb for EDS-2, including 40 lb including donor 99-143 kg, including donor 5 lb in munition capacity, TNT-equivalent shaped charges charge and shaped charges Largest munition 155-mm projectile 210-mm projectile 8-in. projectile, overpacked 8-in. projectile M55 rocket NOTE: ISO, International Standards Organization; HEPA, high-efficiency particulate air filter; NaOH, sodium hydroxide; IONEX, a research company; 3X, level of agent decontamination suitable for transport for further processing (obsolete); 5X, level of agent decontamination suitable for commercial release (obsolete); TNT, trinitrotoluene. aReagent is monoethanolamine for mustard and NaOH for phosgene and other fills. bBased on experience to date of six cycles per 10-hr day. cIn this report, IONEX refers to an off-gas treatment system that contains particulate filters and activated carbon adsorbers (NRC, 2010b). dVSL is a control limit used to clear materials for off-site shipment based on agent concentration in the atmosphere above the packaged waste materials. The numerical value of the VSL can depend on the permit issued by the regulatory authority for the particular facility involved, but it is often set at either the STEL or the short-term limit (STL), which is numerically the STEL but without the 15-min time component. See Chapter 3 of reference NRC, 2007 for an in-depth discussion of the issues surrounding off site shipment of partially decontaminated waste.
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59 TECHNOLOGIES FOR CLEANUP OF CWM SITES FIGURE 4-4 The EDS-2 vessel on its trailer. SOURCE: NRC, 2009a. FIGURE 4-4 Drawing of the EDS-2 vessel on its trailer.eps reagents are then added to the vessel to neutralize the agent BITMAP WITH VECTOR the EDS, & ARROWSopened with a shaped explosive In TYPE the munition is released from the munition. The EDS-1 containment vessel charge. For HD, most of the agent is destroyed by react- (Type is converted it with a 90 percent MEA/10 percent water solution at to outline.) has a 1-lb TNT-equivalent net explosive weight (NEW) limit, ing with the NEW limit including both the explosives contained 60°C while rotating the vessel for 1 hr. In a subsequent step, in the munition and those in the cutting charges; the EDS-2 water at 60°C is added to the vessel, the vessel contents are containment vessel has a 4.8-lb TNT-equivalent NEW limit. heated to 100°C, and the vessel is rotated for 2 hr. This step The EDS-1 has been used in a number of field operations, is needed to disperse or dissolve the solid or semisolid heels including those at Rocky Mountain Arsenal, Colorado [10 that occur in many mustard-filled munitions and to remove sarin (GB) bomblets]; Camp Sibert, Alabama [11 muni- the mustard from the chunks or globules of heel and other tions]; and Spring Valley in Washington, D.C. [16 mustard solid residues. The water-mustard chemical reaction is very agent (HD) 75-mm artillery projectiles, 1 lewisite 75-mm fast, with a half-life of about 2.3 sec at 90°C (NRC, 1993), projectile, and 3 arsine-containing 75-mm projectiles]. One but the diffusion operations involved in this step are much EDS-1 and two EDS-2s were then employed at the Pine Bluff slower, often resulting in a much slower rate of destruction Arsenal to destroy 1,227 recovered chemical munitions. of mustard than implied by the mustard-water chemical reac- Many of the munitions at Pine Bluff were degraded from tion. Further, use of still higher temperatures or changing burial and not considered safe for dismantling. other operational parameters will not appreciably increase Several steps in the EDS operational procedures involve the rate of these diffusion operations. waiting for analytical results or for heating and cooling, The entire mustard destruction step takes 9 to 10 hr. The resulting in a cycle time of 2 days. equivalent steps in the TDC and DAVINCH are practically Relative to other transportable whole-munition destruc- instantaneous. Changes can be made to speed up some of tion systems, such as the Dynasafe static detonation chamber, the steps in the EDS process—for example, steam injection the CH2M HILL transportable detonation chamber, and the to reduce vessel heating time—but it will always be slow DAVINCH system, the EDS-1 and -2 have long cycle times. relative to the TDC and DAVINCH.
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60 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL To address the slow processing rate and other issues, the could allow the processing of leaking munitions more NSCMP has begun product improvements to the EDS: safely. • Steam injection. Injection of steam into the EDS • Impulsively loaded vessels.20 The chambers of all vessel is to be tested. Expected advantages of using existing EDS chambers are certified as pressure ves- steam injection include faster heating than is now sels. The American Society of Mechanical Engineers obtained, by heating with external band heaters only, has established a new category, impulsively loaded and reduced liquid waste. Steam injection is being vessel, with a code stamp U3. Future EDS-2 vessels installed and tested on the EDS-2 test fixture men- will have the U3 stamp and will have a 9-lb NEW tioned above. Testing with live agent was planned for rating. The Department of Defense Explosives Safety 2012. • Board (DDESB) will require testing with explosive The EDS-3. Simulation studies and modeling are charges to certify this rating. under way on a potential new EDS design, termed the • EDS-2 test fixture. This is a functional but nonmo- EDS-3. It would be similar to the EDS-2 but would bile EDS-2 that will allow for more rapid testing of be able to accommodate a complete M55 115-mm product improvements. It utilizes an existing EDS-2 rocket contained within an overpack. vessel. Construction was completed in the fourth quarter of 2011. Testing with agent was planned for In addition to these product improvements, efforts are the first quarter of 2012. under way on the identification of a reagent that will be effec- • Three-piece clamp. This is a previously designed tive for all agents. Testing of 10 reagents on mustard and GD but never implemented end closure for the EDS. It (soman) agents has begun, with results pending. offers automated bolt tightening. Its advantages over the current design include less operator stress, better Transportable Detonation Chamber alignment between the end closure and the vessel, and a significant saving of time. A clamp of this The TDC was first described in the NRC report on interna- design is to be installed on the new EDS-2 test fixture. tional technologies for destruction of RCWM (NRC, 2006). • Liquid analyzer. A near-real-time analyzer that deter- A subsequent report outlined the updates, with an emphasis mines whether or not the neutralizing reactions are on the Blue Grass and Pueblo chemical agent destruction sufficiently complete to allow EDS vessel draining is pilot plants (NRC, 2009a). The TDC was designed by CH2M being developed. A 10-sec cycle is anticipated. Semi- HILL Demilitarization, Inc. quantitative testing was reported to be successful for The TDC is a true explosive destruction system, as it uses mustard and lewisite agents. Plans called for using the heat and pressure generated by an explosion to destroy the analyzer during the testing of steam injection in most of the chemical agent fill. The current system was exten- the first quarter of fiscal year 2012. These tests were sively tested and modified between 2003 and 2006 at Porton also to include the addition of cold water to more Down, England. This system evolved into the TC-60, with rapidly cool the vessel after the 2-hr water rinse at a DDESB NEW rating of 40 lb TNT-equivalent. The TC-60 100°C. This will decrease the duration of the 1-hr unit was used in 2008 to destroy several dozen munitions at liquid analysis time, which now starts at 1145 and the Schofield Barracks in Hawaii. It was then returned to the ends at 1245 on Day 1. Aberdeen Proving Ground for substantial additional testing • Use of a laser for surface decontamination. A com- and development work. It was most recently employed in mercially available laser from ADAPT Laser is being Columboola, Queensland, Australia. The current configura- evaluated for removal of heavy metals from the EDS tion of the TC-60 system is shown in Figure 4-5. The system vessel interior and for similar applications elsewhere. has demonstrated the ability to destroy mustard, phosgene, Testing on moderately contaminated surfaces was chloropicrin, white phosphorus, smoke, and the vomiting agent Clark.21 successful. As of September 2011, testing on more heavily contaminated surfaces was planned. As shown in the figure, the detonation chamber is fol- • Processing munitions in overpacks. Use of improved lowed by an extensive pollution control system, includ- linear shaped charges to cut through the overpack and ing a catalytic oxidizer, a heat exchanger, carbon filters, the munition was planned as of September 2011. This and a HEPA filter. The gas is discharged into the system enclosure, which has an additional carbon filtration system, before exhausting into the atmosphere. The munitions are wrapped in an explosive charge and oxygen is injected prior 20Impulsive loading is defined as a “loading whose duration is a frac- to detonation. tion of the periods of the significant dynamic response modes of the vessel components. For the vessel, this fraction is limited to less than 35 percent of the fundamental, membrane-stress dominated (breathing) mode.” From 21Brint ASME Case 2564-1. Available at http://cstools.asme.org/csconnect/pdf/ Bixler, Vice President, CH2M HILL, “Controlled Detonation R081171.pdf. Chamber,” presentation to the committee on December 13, 2011.
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61 TECHNOLOGIES FOR CLEANUP OF CWM SITES FIGURE 4-5 Process flow in the large mobile transportable detonation chamber TC-60. SOURCE: Brint Bixler, Vice President, CH2M HILL, “Controlled Detonation Chamber,” presentation to the committee on December 13, 2011. FIGURE 4-5 Process flow in large mobile transportable detonation chamber (TC-60).eps BITMAP There have been a number of lessons learned and upgrades ended with treatment of 144 mustard-filled munitions, many to the system, including the following:22 with heels.23 ECBC staff who observed its use in Columboola praised it as “elegant” to operate.24 There were no problems • Additional chamber floor protection was added. with the unit other than the cracked welds. The operator • The efficiency of the final filtration was improved believed the unit was a good transportable system with a with the addition of a HEPA filter. throughput midway between that of the EDS (slower) and • Internal welds for the fasteners attaching the armor that of the Dynasafe SDC (faster). plate to the chamber walls were upgraded. • The firing system was improved by changing the fir- Dynasafe Static Detonation Chamber ing plug/cable design and replacing the system every 70 detonations. The SDC was described in three earlier reports (NRC, 2006, 2009a, and 2010b). It is the only one of the four sys- At Aberdeen Proving Ground, 29 cylinders of HD were tems that does not require any preparation of the CWM prior destroyed, for a total of 282 lb HD between March 2009 to destruction, which gives it an important safety advantage and March 2010. Included were two cylinders in double over the other systems. Moreover, the scrap metal produced overpacks, with 11.7-lb of HD (155-mm projectile equiva- is suitable for release for unrestricted use (formerly termed lent). Overpack test results showed that the outer and inner “5X”), and no donor explosives are required. overpacks had been penetrated and that there was sufficient The design and operation of the SDC 2000 system in heat to destroy the chemical fill. Munster, Germany, were described in detail in previous NRC An additional upgrade was made just prior to transport reports (NRC, 2006 and 2009a). An SDC 1200 was deliv- ered to the JFE Steel Corporation in Japan in 2009.25 It will to Columboola. Improved bearings were added to two control valves, one 3-in. and the other 10-in. The unit had be used for the destruction of RCWM in Chiba Prefecture, been in storage for a while and moisture buildup was caus- Japan. Another SDC 1200 was delivered to Kawasaki Heavy ing the valves to seize. The unit was set up in Columboola and ready within 10 days. The typical schedule included 23Ibid. 2 days of destruction followed by one-half day of “scrap 24Timothy A. Blades, Deputy Director, Directorate of Program Integra - management.” Operations then continued. Destruction rates tion, ECBC, teleconference with Richard Ayen, committee chair; Doug Medville and JoAnn Lighty, committee members; and Nancy Schulte, NRC stabilized at eight munitions per day. Scrap was removed study director, January 4, 2012. from the detonation chamber twice per week. The campaign 25Harley Heaton, Vice President-Research, UXB International, “Dy - nasafe Static Detonation Chamber,” presentation to the committee on 22Ibid. December 13, 2011.
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62 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL FIGURE 4-6 Process flow diagram for front components of the Dynasafe SDC 1200 installation for Anniston Army Depot. SOURCE: FIGURE 4-6 Process flow diagram for front components of Dynasafe SDC 1200.eps Adapted from personal communication between Holger Weigel, Vice President, Dynasafe International, and Managing Director, Dynasafe Germany, and Richard Ayen, committee chair, May 12, 2010. BITMAP • Industries and is now undergoing systemization. It will be Agent leaks from the buffer tank into the solids col- used for the destruction of Second World War–era Japanese lection drum below the buffer tank were eliminated RCWM in Haerba-ling, China. by blind-flanging the connection to the solids collec- The NRC letter report “Review of the Design of the tion drum from the buffer tank. • Dynasafe Static Detonation Chamber (SDC) System for The leaking of agent from loading chamber 2 into the Anniston Chemical Agent Disposal Facility-August the process air system was alleviated by modifying 25, 2010” describes the Dynasafe SDC 1200 system now the loading chamber 1/loading chamber 2 pressure installed at the Anniston Chemical Agent Disposal Facility equalization procedure during munitions feed to the (ANCDF), in Alabama (see Figure 4-6). detonation chamber. • The Dynasafe 1200 used at ANCDF had a NEW contain- Agent was detected at the process air monitors during ment capacity of 5 lb, all of which consists of explosives in emptying of the detonation chamber. This was allevi- the munition since no donor charge is needed. As of Sep- ated by controlled venting of loading chamber 2 and tember 1, 2011, this system had destroyed 2,322 munitions, the detonation chamber before beginning to empty consisting of normally configured and overpacked 4.2-in., the chamber. • 105-mm, and 155-mm mustard-filled rounds.26 Agent was escaping from one or more of the flange During operations at ANCDF, a number of problems with connections between the detonation chamber and the the system became evident, the most significant being agent thermal oxidizer. This was being investigated as this migration into secondary containment.27 Agent was leaking report was being written, with emphasis on different at a number of locations. The actions taken to alleviate the gasket materials or use of sealants. leaking were these: The unsteady nature of events in the detonation chamber during operations in 2011 appeared to be causing CO excur- sions in the off-gases from the thermal oxidizer. The short residence time in the thermal oxidizer might also have been 26Timothy K. Garrett, Site Project Manager, ANCDF, “Dynasafe Static Detonation Chamber,” presentation to the committee on September 29, contributing to the problem (NRC, 2010b). The instability 2011. in the detonation chamber was apparently causing unsteady 27Charles Wood, ANCDF Deputy Operations Manager, URS, ANCDF, flow through the thermal oxidizer: The problem was allevi- presentation to the committee on September 29, 2011.
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63 TECHNOLOGIES FOR CLEANUP OF CWM SITES enlarged the thermal oxidizer for its SDC 1200s.29 ated by installing a smaller orifice between the detonation chamber and the thermal oxidizer to smooth flow to the This is expected to allow better control of excess oxidizer. Also, the flow rates of the spray dryer atomizing oxygen and hence more reliable combustion of CO. • air and the barrier air were reduced, allowing more air at Occasional failure of loading gate 2 seals was being the thermal oxidizer. (See the fourth bullet item in the list of investigated. • issues being addressed for further discussion of this topic.) Degradation of the spray dryer temperature control Rapid depletion of carbon was attributed to the presence valve was addressed by installing a redundant system of sulfur dioxide in the offgases fed to the carbon beds. The to be tested during the TRAM assessment. • excessive sulfur dioxide emissions problem, and hence the A process water piping degradation problem was rapid carbon depletion problem, was resolved by adjusting addressed by upgrading materials to stainless steel. the pH in the scrubbers. The new piping was to be installed before the TRAM As of January 2012, effort was continuing at the ANCDF assessment. • to eliminate or further alleviate the problems described Bridging of solids in the baghouse was being above, as well as to satisfy other identified development addressed by designing and installing an automated needs.28 Conventional munitions were of necessity being vibrator. • employed in this critical development effort since Anniston Accumulation of solids in the spray dryer was alle- no longer had any chemical munitions. This work was being viated by system tuning and better pH control. The carried out jointly with Dynasafe, and the lessons learned and situation was to be monitored and further evaluated the resulting design changes were being incorporated into during the TRAM assessment. • future SDC 1200 systems. As of January 2012, the following The bypass between loading chamber 2 and the deto- issues were being addressed: nation chamber occasionally became clogged. This situation was still being evaluated as of January 2012. • Process gases were leaking through the knife valves at the bottom of the buffer tank. New valves of an This unit completed its intended operation on chemical improved design had been received and were to be munitions at ANCDF and is available for use by NSCMP for installed before start-up of an assessment of through- the destruction of RCWM. put, reliability, availability, and maintainability (TRAM) for the system. Detonation of Ammunition in a Vacuum Integrated • Agent vapor from the upper portion of the detonation Chamber chamber was escaping to the process air system as the chamber was emptied. In addition to implement- DAVINCH is a controlled detonation system for the ing a controlled venting procedure, as previously disposal of chemical munitions. It is yet another destruction described, a new nozzle was being installed to keep system where an explosion consumes most of the agent. the top of the chamber hotter, minimizing agent vapor The DAVINCH technology was developed by Kobelco, generation at the interface between loading chamber a subsidiary of the Japanese company Kobe Steel, a manu- 2 and the detonation chamber. facturer of large steel pressure vessels. DAVINCH was • Agent was escaping from one or more of the flange developed to destroy Japanese chemical bombs, some con- connections between the detonation chamber and the taining a mustard/Lewisite mixture and others containing thermal oxidizer. It was planned to inspect, measure, vomiting agents. Munitions placed in the DAVINCH vessel and adjust all connections to ensure proper alignment are detonated in a near vacuum using linear shaped charges and gasket seating before the start of the TRAM and a donor charge that is placed on the munitions overpack assessment. to open the munitions and access the chemical agent (see • CO excursions in the offgases from the thermal Figure 4-7). oxidizer were being experienced. The problem was The agent is destroyed by the high temperatures (3000°K) greatly reduced by the actions already described. In and pressures (10 GPa) that result from the detonation and addition, design studies were begun aimed at provid- from the fireball in the chamber. The use of a vacuum reduces ing additional gas flow through the system by upgrad- noise, vibration, and blast pressure, thus increasing vessel ing the induced draft fan and the fan in the filter life. The off-gases that are produced are treated in a cold system between the induced draft fan and the stack plasma oxidizer followed by treatment in activated carbon (the IONEX Research Corporation system). Since filters. The explosion containment capability of DAVINCH the ANCDF SDC was manufactured, Dynasafe has chambers varies from 99-143 lbs TNT-equivalent NEW, depending on the application. Detailed descriptions of the 28Timothy Garrett, Site Project Manager, Anniston Chemical Agent Dis - 29Harley posal Facility, personal communication to Nancy Schulte, study director, Heaton, Vice President-Research, UXB International, personal National Research Council, January 26, 2012. correspondence to Nancy Schulte, NRC study director, March 16, 2012.
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64 REMEDIATION OF BURIED CHEMICAL WARFARE MATERIEL Area of Compression Chemical Agent Chemical Ammunition Donor Charge Step Chemical Agent Destruction Mechanism 1 Instant compression by propagating shock wave pressure of 10 GPa. A similar phenomenon is observed in cavitation bubbles when bubbles collapse (sonochemistry). 2 High-speed mixing of chemical agent with detonation gas at high pressure and high temperature. 3 Thermal decomposition by the long-lasting fireball FIGURE 4-7 DAVINCH three-stage destruc- at 2000°C for 0.5 sec. tion mechanism. SOURCE: NRC, 2006. People’s Republic of China DAVINCH technology were provided in previous NRC FIGURE 4-7 DAVINCH three-stage destruction mechanism.eps reports (NRC, 2006 and 2009a). BITMAP WITHare being usedTYPE DAVINCH units VECTOR in the People’s Republic of China (PRC) to destroy Second World War–era Japanese United States chemical munitions filled with blister, choking, vomiting, and other agents. These munitions are primarily artillery To date, the DAVINCH technology has not been used in shells and bombs ranging in size from 75 mm to 150 mm. the United States. A DV60 (60-kg TNT-equivalent explosion The site with the most RCWM, Haerba-ling (northeastern containment capacity) had been leased from Kobelco by the China), contains an estimated 300,000-400,000 munitions; U.S. Army for use at the Tooele Chemical Agent Disposal another 47,000 munitions have been recovered at 26 other Facility (TOCDF), in Utah. However, an alternative method locations. At Haerba-ling, both a DAVINCH and a Dynasafe of destroying the munitions became available before the SDC will be used to destroy munitions recovered from pits DAVINCH was due to start up in early 2012. Because this where they are buried. The second largest site in the PRC alternative was successful, it was decided in late 2011 not to is in Nanjing, where 36,000 chemical munitions have been use the DAVINCH at TOCDF. recovered. At this location, two DAVINCH DV-50 units, operating in tandem, are in use. Between September 1, 2010, Japan and June 10, 2011, 25,000 overpacked and boxed munitions were destroyed. The DAVINCH technology was used at Kanda Port in In addition to these transportable (but barely so) units, Japan to destroy recovered Second World War–era bombs Kobelco states that a lighter, more mobile version of containing chemical warfare materiel. Some of the bombs DAVINCH, called DAVINCHlite, is being developed. The contained a mixture of mustard agent and lewisite; others committee believes that, as of early 2012, the DAVINCHlite contained Clark I and Clark II vomiting agents (DC/DA). had not even been manufactured much less used to destroy As of 2009, 2,050 of these bombs had been destroyed (NRC, any RCWM in the PRC. 2009a). SECONDARY WASTE STORAGE AND DISPOSAL Belgium As indicated previously, the treatment technology for The Belgian Ministry of Defense has installed a DAVINCH RCWM will involve either the EDS, one of the EDTs, or system having a 50-kg TNT-equivalent explosion contain- perhaps a combination of these technologies. Each of these ment capacity at a Belgian military facility at Poelkapelle. By technologies will produce a number of secondary waste December 2011, over 4,000 munitions containing chemical streams (see Table 4-2) that will then need to be managed agent had been destroyed.
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65 TECHNOLOGIES FOR CLEANUP OF CWM SITES in accordance with regulatory requirements. The regulatory point at which it can be safely shipped off-site to commercial requirements pertain primarily to the Resource Conservation treatment, storage, and disposal facilities (TSDFs) (NRC, and Recovery Act (RCRA) and its implementing regulations. 2004). At both places, the waste was stored in a less-than-90- RCRA is summarized in Appendix D, along with other regu- day hazardous waste storage area. The waste was placed in latory programs. an enclosed trailer (Spring Valley) or in a vapor containment The secondary wastes produced by the various types of structure (Camp Sibert). The enclosures were within fences, EDTs are similar; they consist of metal casings and frag- with security guards present. Liquid waste was placed in ments, explosive fragmentation protective materials, carbon 55-gal steel drums. filter material, baghouse dusts, miscellaneous wastes (used For the past several years, NSCMP has maintained a waste O-rings, fittings, etc.), and liquid waste streams coming from management contract with Shaw Environmental, Inc. As off-gas treatment, from periodic cleaning and decontamina- explained in NRC, 2004, the waste management contractor tion of the device, or from closure between deployments. The is responsible for teaming with one or more commercial haz- EDS will generate not only the above materials but also a ardous waste TSDFs to transport and dispose of hazardous substantial volume of liquid wastes (hydrolysates and vari- secondary and neutralent wastes from the various NSCMP ous dilute rinsates). CAIS containing dilute or neat agent are projects. Shaw Environmental fulfilled this responsibility for treated and disposed of in a SCANS unit, as discussed above. EDS operations at both Spring Valley and Camp Sibert. The Secondary waste from EDS operations was stored at both project manager at Spring Valley reported that he received the Spring Valley and Camp Sibert sites and then shipped some questions and expressions of concern from the regula- off-site.30,31 At both sites, the project managers followed tors and the community about the nature and amounts of the Army’s general practice of treating the waste only to the reagents and waste entering and leaving the facility, but that this was “nothing really significant.” Otherwise, there were no problems with waste storage 30Karl E. Blankinship, FUDS Project Manager, Mobile District U.S. or disposal at either Spring Valley or Camp Sibert. As a Army Corps of Engineers, personal communication to Nancy Schulte, NRC consequence, the committee could not identify any need for study director, April 4, 2012. targeted research and development in this area. 31Dan G. Noble, Project Manager, Spring Valley, Baltimore District, U.S. Army Corps of Engineers, personal communication to Nancy Schulte, NRC study director, March 30, 2012.