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11 Summary, Findings, and Recommendations This chapter summarizes the operating characteris- tics of the seven technology packages and then pre- sents general findings and recommendations that have broad applicability across the technologies. (Findings specific to each technology package are presented in Chapters 3 through 9.) SUMMARY OF THE OPERATING CHARACTERISTICS OF TH E TECH NOLOGY PACKAG ES Each of the seven proposed technology packages represents a unique combination of technologies for destroying assembled chemical weapons. In Chapters 3 through 9, these packages were examined in detail. Because the information contained in those chapters is quite extensive, the committee decided it would be use- ful to highlight some of the key points in a general summary. Thus, Table 1 1-1 has been developed to sum marize the fundamental operational characteristics of the seven technology packages. GENERAL FINDINGS AND RECOMMENDATIONS Because the munitions contain both chemical agents and energetic materials in various configurations, the destruction of assembled chemical weapons is an ex- tremely complex undertaking. The committee has ex- amined the packages proposed by the seven technol- ogy providers in detail and evaluated them according to the criteria set forth in Chapter 2. The following gen- eral findings and recommendations are applicable to all of them. Recommendations are listed at the end of 172 the section, with references to the associated findings. These findings and recommendations should be con- sidered together and not quoted out of context. General Findings General Finding 1. The chemistries of all four of the primary technologies, (hydrolysis, SILVER II, plasma arc, and SET) as proposed, can decompose the chemi- cal agents with destruction efficiencies of 99.9999 per- cent. However, each technology package raises other technical issues that must be resolved. One of the cru- cial issues is the identity and disposition of by-products. General Finding 2. The technology base for the hy- drolysis of energetic materials is not as mature as it is for chemical agents. Chemical methods of destroying energetics have only been considered recently. There- fore, there has been relatively little experience with the alkaline decomposition of ACWA-specific energetic materials (compared to experience with chemical agents). The following significant issues should be re- solved to reduce uncertainties about the effectiveness and safety of using hydrolysis operations for destroy ing energetic materials: · the particle size reduction of energetics that must be achieved for proper operation · the solubility of energetics in specific alkaline solutions · process design of the unit operation and the iden- tification of processing parameters (such as the de gree of agitation and reactor residence time) nec- essary for complete hydrolysis
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SUMMARY, FINDINGS, AND RECOMMENDATIONS . . . the characterization of actual products and by- products of hydrolysis as a function of the extent of reaction the selection of chemical sensors and process con- trol strategies to ensure that the unit operation following hydrolysis can accept the products of hydrolysis development of a preventative maintenance pro- gram that minimizes the possibility of incidents during the cleanup of accumulated precipitates "Neutralization" (i.e., decomposition and detoxifi- cation) of chemical agents has been studied since World War I as part of the chemical weapons defense program for the protection of U.S. troops and protec- tion in the event of accidental releases. Hydrolysis, the first approach selected, was used on a large scale to neutralize the satin (GB) in cluster bombs destroyed at Rocky Mountain Arsenal in the 1970s. However, the standard method of destroying explo- sives and propellants has been open-air burning or deto- nation. Because chemical methods of destroying ener- getics have only been considered recently, there has been relatively little experience with the alkaline decom- position of ACWA-specific energetic materials (com- pared to experience with chemical agents). Most of the work on base hydrolysis of TNT focused on its precipi- tation from "pink water" (see Appendix E). Almost all of the literature on the base hydrolysis of other ener- getic materials was conducted with dilute solutions that were well within the solubility limits of these materi- als. Even though, several undesirable products and pre- cipitates resulted, the qualitative (rather than quantita- tive) understanding of these reactions suggests that the use of strong base is probably the most efficient way to ensure that hydrolysis is driven to completion. As shown in Appendix E, the reaction of some ener- getics with bases is much slower than the reaction of chemical agents. In most cases, the rate of reaction is limited by the rate of dissolution of the energetic mate- rials, which are only slightly soluble in water. General Finding 3. The conditions under which aro- matic nitro compounds, such as trinitrotoluene (TNT) or picric acid, will emulsify in the aqueous phase and not be completely hydrolyzed are not well understood. Therefore, this type of material could be present in the output stream from an energetic hydrolysis step. 173 In Appendix E, the products of pressurized alkaline hydrolysis of some typical propellants are shown to be dependent on the additives in the compositions. Some additives in propellants P1-P5 did not completely re- act. For example, diphenylamine (DPA) and centralite precipitated as solid residues or appeared as emulsions in the liquid phase. The most problematic component was found to be dinitrotoluene (DNT). In experiments performed with pure 2,4-DNT, only 7 percent of the nitrogen was found as nitrite in the liquid phase. No DNT was found in the solid residue. It is believed that the DNT was not completely decomposed and might still have been present as an emulsion in the aqueous phase (Bunte et al., 1997~. Emulsified components, such as DNT and DPA, would have to be removed be- fore any subsequent unit operations (e.g., aerobic biotreatment) could proceed. Compounds such as TNT and tetryl (both of which are present in assembled chemical weapons) as well as picric acid, nitrated phenols, or nitrated cresols (all of which could be formed during hydrolysis of the energetics in these weapons) are expected to behave in a similar fashion. General Finding 4. The products of hydrolysis of some energetic materials have not been characterized well enough to support simultaneous hydrolysis of dif- ferent kinds of energetic materials in the same batch reactor. Lead stearate, an additive in M28 propellant, is in- soluble in water at ambient temperature, but soluble in hot alcohol (Sax and Lewis, 1987~. If lead stearate dis- solves in hot alkaline solution, then the lead cations could combine with other anionic substrates in a batch reactor and precipitate out sensitive compounds. This possibility is supported by the results of testing on pro- pellant P3 (Bunte, et al., 1997) discussed in Appendix E. For example, picric acid will be formed during hy- drolysis of the TNT or tetryl contained in the M55 rocket bursters. If bursters and propellant are hydro- lyzed simultaneously, lead from the propellant could either precipitate out or form lead picrate. In the hy- drated form, lead picrate is not particularly sensitive. However, enough heat could be produced from this exothermic process to heat and dehydrate the lead pi- crate deposited on vessel walls. As indicated in the TNT hydrolysis section of Appendix E, dry lead pi- crate is an extremely sensitive explosive and is very
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178 ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS dangerous to handle. Therefore, the committee believes that, to avoid forming sensitive compounds such as lead picrate, hydrolysis of bursters and propellant should be performed in separate vessels. General Finding 5. The primary chemical decomposi- tion process in all of the technology packages produce environmentally unacceptable reaction products. Therefore, all of the packages are complicated pro- cesses that include subsequent treatment stepts) to modify these products. General Finding 6. The waste streams of all of the ACWA technology packages could contain very small amounts of hazardous substances (besides any residual chemical agent). These substances were not fully char- acterized at the time of this report; therefore, all waste streams must be characterized to ensure that human health and the environment are protected. If more than one phase (gas, liquid, or solid) is present in a waste stream and, each phase should be characterized separately. All of the alternative technology packages appear to be capable of meeting the current destruction efficiency limits for agent and hazardous materials of regulatory concern. However, they may create new pollutants that could have adverse environmental effects. Therefore, complete characterizations of the process effluents (sol- ids, liquids, and gases) from the secondary-treatment waste streams will be essential. Characterization may require pilot-scale operation of the integrated processes before a final conclusion can be determined on envi- ronmental acceptability. The waste streams of all of the proposed technology packages (gas, liquid, and/or solid) may contain small amounts of hazardous materials, even under normal operating conditions (this is a characteristic of virtu- ally any industrial chemical process). To ensure that no toxic effluent is accidentally discharged, all waste streams must be monitored. In the committee's opin- ion, all of the packages are fundamentally capable of being monitored to ensure the protection of human health and the environment. (Although the detection and analysis of trace substances can be done to very low levels, no monitoring or analytical method can guarantee a true zero level of any known or unknown compound.) General Finding 7. None of the proposed technology packages complies completely with the hold-test-re- lease concept for all gaseous effluents (both process and ventilation effluents). General Finding X. Hold-test-release of gaseous ef- fluents may not ensure against a release of agent or other hazardous material to the atmosphere. No evi- dence shows that hold-test-release provides a higher level of safety than current continuous monitoring methods for gaseous streams with low levels of con- tamination. Furthermore, none of the technologies pro- vides for hold-test-release of effluents from ventilation systems that handle large volumes of gases from con- taminated process areas. In an earlier report on alternative technologies the NRC noted that, The risk of toxic air emissions can be virtually eliminated for all technologies through waste gas storage and certifi- cation or treatment by activated-carbon adsorption. Ei- ther of these options can be combined with methods to reduce the volume of gas emissions (NRC, 1993~. Some of the technology packages include hold-test- release steps of gaseous process effluents (1) when the effluent stream flow rates are relatively low or (2) when the effluent streams occur in batches that can be easily contained. For continuous gaseous effluent streams that have high flow rates (e.g., from SCWO units and ex- haust gas from biotreatment units), elaborate designs would be required to incorporate a hold-test-release step. The committee believes that the hold-test-release step Is not a panacea for ensuring that gaseous effluents are free of agent or other hazardous materials. Some low-concentration hazardous volatile materials may adsorb onto internal tank surfaces or be absorbed into liquids or solids in holding tanks where they may es- cape detection. When the holding tank is vented to the atmosphere, these undetected materials may be des- orbed and released to the environment. To the com- mittee's knowledge, no experiments have been per- formed to demonstrate that these phenomena do not occur. Moreover, if a process upset contaminates the holding tanks, decontamination (and verification of decontamination) may present significant technical difficulties.
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SUMMARY, FINDINGS, AND RECOMMENDATIONS All of the ACWA technology packages include the baseline continuous monitoring and filtering systems (ACAMS and DAAMS) for air ventilation in process areas where contamination is expected. To add hold- test-release steps for this large volume of air flow would be very difficult and probably would entail very expensive (and impractical) design. Continuous monitoring coupled with interlocks that shut down the process quickly if concentration limits are exceeded may be just as reliable as hold-test-re- lease steps for protecting human health and the envi- ronment, especially for large-volume effluent streams. Whatever approach is adopted will require additional testing to demonstrate its viability and effectiveness. Tests may very well show that hold-test-release steps do not ensure safety any better than simpler continuous monitoring methods combined with robust process con- trols (i.e., continuous performance assurance). General Finding 9. Solid salts will be hazardous waste, either because they are derived from hazardous waste (see Chapter 2) or because they leach heavy met- als above the levels allowed by the Resource Conser- vation And Recovery Act Toxicity Characteristic Leaching Procedure. Stabilization mixing waste with a reagent or reagents to reduce the leachability of heavy metals will probably be required before the salts can be sent to a landfill. The potentially high chloride and nitrate content of these salts will make the waste diffi . . ... cult to size, and treatability studies will be neces- sary to determine a proper stabilization formula. General Finding 10. Testing, verification, and inte- gration beyond the 1999 demonstration phase will be necessary because the scale-up of a process can present many unexpected challenges, and the ACWA demon- strations were limited in nature. The reasons supporting this finding are discussed below. The ACWA demonstrations tested only the unit operations that DOD believed were most criti- cal or least proven for that technolo~v nacka~e .. .. OF ~ O However, other unit operations may also require addi- tional development before full-scale implementation can proceed. Second, the accelerated ACWA schedule required that the demonstrations be relatively short. Thus, the longer-term reliability of the processes could not be evalu- ated. In addition, the duration of the demonstrations 179 may have been too short to characterize fully the steady-state operational behavior the huildun of trace · . · . - . . , ~ materials In recycling loops, and problems with corro- sion. Longer lasting tests with the full range of materi- als to be processed will be necessary for identifying the best materials of construction. Third, the demonstrations did not include interfac- ing the unit operations into a complete system (i.e., when the output stream of one process step becomes the input stream of the next) when unexpected prob- lems often arise. For example, scheduling is especially difficult to design when a batch or semibatch process (e.g., the hydrolysis reactors) is coupled with a con- tinuous process (e.g., the SCWO reactor). Incomplete processing in one stage may cause contamination or a materials incompatibility in a later stage. Also, a bottle- neck can be created if one step does not achieve the expected throughput. Therefore, for each piece of equipment, the implications of operating with input streams that are off specification, that are not moving at the design flow rate, or that are completely blocked must be tested. Fourth, scale-up of a process is not always linear. Although the scale-up of some types of standard chemi- cal process equipment can be straightforward, the scale-up of new equipment designs can raise problems if not all parts of the process scale in the same way. For example, many mass-transfer processes scale with length. Surface wash-out, heat transfer, and other sur- face phenomena scale with surface area. Homogeneous chemical reactions scale with reactor volume. When all these phenomena occur simultaneously (in a hy- drolysis or SCWO reaction vessel), the different scal- ing properties must be accommodated in the design. Fifth, impurities that are not detected in small-scale tests may be evident in larger scale tests. Because of the limited quantities used in the small-scale and dem- onstration-phase tests, trace impurities in the waste streams may not be detectable. The impurities and small amounts of intermediates that are produced in a full-scale (or near full-scale) plant are not necessarily the same as those observed during laboratory or bench- scale experiments, or even during demonstration-scale tests. Small excursions or variations in the conditions under which a reaction is run can also alter the nature or the amount of trace impurities that are produced. Because the scale of the demonstration testing is
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180 ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS limited, the quantity of trace impurities in the reaction products may be too small for detection analysis. Operation at near full-scale would reveal trace impuri- ties that mav require process chances to mitigate or eliminate them. --a ---1----- r __c, _ _ _ _ ____ __~) _ Sixth, materials-handling equipment was generally not evaluated during the ACWA demonstrations. In the scale-up operations of waste treatment facilities, the materials-handling equipment, such as equipment for sizing and feeding waste, has been the weak link in the operational chain. The materials-handling equipment will have to be tested and evaluated prior to full-scale implementation to ensure that integrated facilities operate properly. This additional testing, verification, and integration could be done in a pilot-scale facility. However, even the construction and operation of a pilot-scale facility will not necessarily ensure a trouble-free start-up of a full-scale facility. Industrial experience suggests that unanticipated problems will occur at full-scale in spite of pilot-plant experience. General Finding 11. Although a comprehensive quan- titative risk assessment (QRA), health risk assessment (HRA), and ecological risk assessment (similar to as- sessments performed for the baseline process) cannot be completed at this stage of process development, these assessments will have to be performed and re- fined as process development continues. All of the proposed destruction systems are in the conceptual design stage, which means that many de- sign details have not been developed. At this stage, only qualitative risk assessments could be done, and all of the technology providers prepared preliminary hazard analyses that qualitatively describe potential accidents. General Finding 12. The "optimum" system for a par- ticular chemical weapons storage depot might include a combination of unit operations from the technology packages considered in this report. The technology packages proposed for the ACWA program address the destruction of assembled chemi- cal weapons at the hypothetical depot described in the REP. The actual depots under consideration have very different munition inventories. For example, the Pueblo Chemical Depot has only mustard-filled projectiles and mortars in its inventory. The Blue Grass Army Depot in Richmond, Kentucky, however, has a large inventory of M55 rockets, which contain GB or VX. Some of the components and processes in the proposed systems are very effective for one or another portion of the overall demilitarization process. Technology packages may also differ in their applicability to particular munitions and particular chemical agents. This discussion notwithstanding, the committee's task is to evaluate the technology packages, as pro- posed, for the hypothetical depot. The committee did not, therefore, consider "mixing and matching" com- ponent technologies for specific sites or munitions. General Finding 13. Some of the ACWA technology providers propose that some effluent streams be used commercially. New or modified regulations may have to be developed to determine if these effluent streams can be recovered or reused. According to current Army standards, a solid mate- rial that has not been subjected to 5X treatment can only be disposed of in a hazardous-waste facility. If a process under consideration produces a waste stream that could be reused by, for example, a metal reclaimer or a fertilizer plant, this waste stream would have to be subjected to 5X treatment. To date, liquids and gases from chemical demilitarization processing have not been recycled or reused commercially; therefore, ex- isting standards may have to be reexamined. General Finding 14. An extraordinary commitment of resources will be necessary to complete the destruction of the assembled chemical weapons stockpile in time to meet the current deadline using any of the ACWA technology packages. This would demand a concerted national effort. It is unlikely that any of the technology packages could meet this deadline. The chemical-hydrolysis destruction of bulk agents at Aberdeen Proving Ground, Maryland, and Newport, Indiana, are examples of how much time could be re- quired to bring any of the alternative destruction sys- tems from its present state of development to the pilot- plant stage and finally to the production stage. The schedules for the design, construction, and operation of the destruction facilities at these two sites (see Figures 1 1-1 and 1 1-2) indicate that the destruction of munitions will be completed by the end of 2004. The ACWA program is approximately three years behind the Aberdeen and Newport schedules, and the develop- ment of an acquisition design package for ACWA is
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SUMMARY, FINDINGS, AND RECOMMENDATIONS 1996 1 1997 T 1998 | 1999 | 2000 1 2001 | 2002 1 2003 | 2004 1 1 1 1 1 1 1 1 181 1995 2005 2006 2007 · _ Complete NRC study of alternatives 1 1 ~ 1 ~ complete 60% desian for acquisition roacknae FIGURE l l-l Schedule for the Aberdeen Chemical Agent Disposal Facility as of January 6, 1999. Source: Adapted from Pecoraro, 1999. not likely to begin before October 1999; for Aberdeen and Newport, it began in November 1996. The programs at Aberdeen and Newport are less complex than those required for other sites because the stockpiles at those two sites contain only bulk agents in one-ton containers. Only one agent is stored at each site, and there are no munitions to be disassembled and no energetics to be treated. Thus, the committee ex- pects that the development cycle at other sites such as Richmond, Kentucky, and Pueblo, Colorado, could take even longer because of modifications to the disas- sembly process and the numerous interfaces between unit operations. In addition, the number of munitions at Pueblo suggests a much longer operating period than at Aberdeen or Newport. Therefore, meeting the April 2007 CWC treaty deadline will be very difficult. (A recent report [Arthur Andersen, 1998] concluded that the baseline incineration technology will also have dif- ficulty meeting the April 2007 deadline. This comm~t- tee did not evaluate the methodology used by Arthur Andersen to reach this conclusion.) A "crash program" to expedite the implementation of any of the alternative technology packages is possible, 1995 of course. However, this would require significantly more financial resources than have been planned for the disposal sites. (Note that the Aberdeen and New port designs have already been put on a fast track to conduct pilot-scale testing concurrent with the cons~uc- tion of full-scale facilities to reduce the time to start-up.) General Finding 15. The Dialogue process for identi- fying an alternative technology is likely to reduce the level of public opposition to that technology. The com- mittee believes that the Dialogue has been and contin- ues to be a positive force for public acceptance of alter- natives to incineration. Although the Dialogue process requires a significant commitment of time and re- sources, it has been a critical component of the ACWA program to date. Reducing opposition by the general public or by or- ganized interest groups could reduce the time and re- sources required to obtain state and federal permits for constructing and operating disposal facilities. For ex- ample, the speed with which the Aberdeen facility re- ceived permits can be partly attributed to the lack of public opposition (Hammerberg, 1998~. The ACWA 2000 1996 T 1997 | 1998 | 1999 T T 1 2002 1 2003 T 2004 1 2001 2005 2006 2007 ~ _ Complete N RC study of alter Natives Complete 60% design for acquisition package ~ Set up system and run pilot tests Operating period FIGURE l 1-2 Schedule for the Newport Chemical Agent Disposal Facility as of January 6, 1999. Source: Adapted from Pecoraro, 1999.
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182 ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS process, as mandated by Congress, has provided a unique opportunity for sidestepping the kind of con- flict that has impeded progress in the baseline incinera- tion program. The Dialogue process initiated by the program manager for ACWA is a basis for building trust between DOD officials and citizen and environ- mental groups that have traditionally been opposed to . . . Incineration. General Finding 16. Although the committee did not have access to scientific data on the attributes of a technology that would be most acceptable to the public, input from members of the active publics and previous research indicates that technologies with the following characteristics are likely to stimulate less public opposition: · minimal emissions, particularly gaseous . continuous monitoring of effluents to verify that the process is operating as designed (process assurance measurement) · provisions for representatives of the local commu- nity to observe and participate in the process assurance measurement General Recommendations General Recommendation 1. If a decision is made to move forward with any of the ACWA technology pack- ages, substantial additional testing, verification, and integration should be performed prior to full-scale implementation (see General Finding 10~. General Recommendation 2. The sampling and analysis programs at each phase of development should be carefully reviewed to ensure that the characteriza- tion of trace components is as comprehensive as pos- sible to avoid surprises in the implementation of the selected technology (see General Finding 6~. General Recommendation 3. If a decision is made to move forward with any of these technology packages, health and safety evaluations should progress from qualitative assessments to more quantitative assess- ments as the process design matures. Quantitative (QRA), health (HRA), and ecological risk assessments should be conducted as soon as is practical. Early ini- tiation of these assessments will allow findings to be implemented with minimal cost and schedule impact. (See General Finding 11.) The QRA is a tool for managing risk in the design as it becomes increasingly well defined. In the early stages, QRAs can indicate the systems or unit opera- tions that appear to be major contributors to risk at that stage of design development. If a pilot-facility is con- structed, preliminary quantitative, health, and ecologi- cal risk assessments should be developed prior to the completion of the pilot facility design. These analyses should then be factored back into the designs and the risk assessments completed before operation of the pi- lot facility begins. If a full-scale facility is constructed, preliminary risk assessments for the full-scale facility should be developed prior to the completion of the fa- cility design. The preliminary analyses should then be factored back into the full-scale design. These risk as- sessments should be completed before operation of the facility begins. The QRA should include assessments of public and worker risk, as well as uncertainties. The specific protocol for the HRA and ecological risk as- sessment will have to be determined in cooperation with state and federal permitting agencies. General Recommendation 4. Any of these technol- ogy packages, or any component of these technology packages, should be selected on a site-specific basis. (See General Finding 12.) General Recommendation 5. Whatever unit operation immediately follows the hydrolysis of energetic mate- rials should be designed to accept emulsified aromatic nitro compounds, such as TNT or picric acid, as con- taminants in the aqueous feed stream. (See General Finding 3.) General Recommendation 6. Simultaneous process- ing of different types of energetic materials should not be performed until there is substantial evidence that the intermediates formed from the hydrolysis of aromatic nitro compounds will not combine with M28 propel- lant additives or ordnance fuze components to form extremely sensitive explosives, such as lead picrate. (See General Finding 4.) General Recommendation 7. The Department of De- fense should continue to support the Dialogue throughout the current ACWA program and should seriously con- sider the participation of the Dialogue in any follow-on programs.
Representative terms from entire chapter: