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U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 62 used, and reaction times were as long as weeks, traces of GB remained. However, subsequent research has suggested that this result was probably an artifact of the analytical method used (Beaudry et al., 1992). The large amount of waste that resulted from the tests (predominantly salts from evaporation of the neutralization product solutions that were buried in landfill) was due in part to the use of large quantifies of alkali in attempting to attain complete GB destruction. In the early 1980s, small amounts of GB (38 tons) and VX (8 tons) were destroyed by incineration at the CAMDS facility. Recently, similar amounts of GB (40 tons) and VX (54 tons) were destroyed by incineration at the Johnston Atoll Chemical Agent Disposal System (JACADS) facility during Operational Verification Testing (OVT) campaigns (tests) One and Two (for further discussion see Chapter 1). The main purpose of these campaigns was to observe and debug the moderately complex JACADS operations. Numerous problems were encountered during these tests, as often occurs in initial operation of a new chemical plant. Some problems related to the Army' s demanding standards for low agent concentration in the air within the buildings and the high sensitivity of the agent detection meters. Destruction of H, GB, and VX by incineration has, however, been demonstrated to be technically feasible. CHEMICAL WARFARE AGENT DESTRUCTION IN OTHER COUNTRIES Other countries have experience with destruction of chemical warfare agents of the types held by the United States by technologies of current interest. The basic technologies used, chemical neutralization and controlled incineration, have also been used in the United States. Nevertheless, the experience of others with variations on the basic technologies may prove valuable regarding alternative methods to destroy the U.S. chemical weapons stockpile. Such foreign experience is summarized in Tables 3-8 to 3-18. Among destruction methods used in other countries, the two of greatest interest are variations on the method of chemical neutralization: ⢠reaction with alkali in an alcohol, as used in Canada for neutralization of small quantities of GB and VX (Table 3-10); and ⢠reaction with ethanolamine, as used in the former Soviet Union for neutralization of GB and perhaps mustard (Table 3-12).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 63 TABLE 3-8 Canadian Experience with Mustard Agent Destruction (1974 to 1976) Destruction Method Characteristic Site Data Site Defence Research Establishment Suffield (DRES) Amount About 700 tons Form Bulk agent Separation Pumped from lead-lined vats into steel hydrolysis tank Neutralization Hydrolyze g-ton batches by adding lime. Reaction conducted with agitation at 95° C, keeping pH above 10 (principal products are thiodiglycol and calcium salts) Incineration Batch-incinerated at 1085°C with caustic scrubbing using a liquid incinerator Effluents CO2, H2 O, SO2, and calcium salts in flue discharge Efficiency Data not available Monitoring SO2 stack monitoring;, site monitoring for mustard carried out using liquid impinger (bubblers) Disposal Much of the hydrolysis products incinerated (some spread on prairie land for further degradation; sludge left in the reaction vats to be buried) Duration 3 years, completed October 1976; Incineration program, 10 months Rate 1400 gallons/day (incineration of hydrolyzate) Cost/ton $60/ton (incineration of hydrolyzate) Source: Conference on Disarmament, CD/173, Geneva, April 3, 1981.
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 64 TABLE 3-9 Canadian Experience with Mustard Destruction in 1990 to 1991 Destruction Method Characteristic Site Data Site Defence Research Establishment Suffield Experimental Proving Grounds Amount 12 tons, some thickened or aged Form About 3 tons bulk and 9 tons in munitions Separation Preheated and drained bulk containers; batch-introduced agent into incinerator frozen, in polyethylene-lined cardboard boxes; froze and explosively punctured nonexplosive munitions with shaped charges and incinerated directly; froze and used shaped charges to cut off fuzes of explosive munitions and destroyed fuzes by ass detonation at remote site (freezing achieved by exposure to winter ambient air) Incineration Batch-incinerated at 900°C for about 30 minutes, then at 1200°C for 2 seconds; scrubbed flue gas with aqueous NaOH; passed scrubbed flue gas through 1-µm filter to remove particulate matter Effluents CO2 and H2O in discharged vapor, NaCl and Na2SO4 in scrubber brine, and spent filters Efficiency >99.99999% Monitoring Continuous stack monitoring for mustard, CO, HCl, SO2, NOx, hydrocarbons, and particulate matter, discontinuous for trace metals, TCDDs, and TCDFs; mobile laboratory used to monitor air quality for mustard, CO, HCl, NOx , SO2 , and particulates on a continuous basis Disposal Scrubber brine discharged to impermeable lined pit and allowed to evaporate; resulting salts and spent filters placed in landfill; metal residues sold to commercial foundry and melted down Duration Winter of 1990-1991 Rate Incinerator capacity 1.5 tons/hour (actual rate kept down to 180 kg/hour to reduce particulate emissions) Cost/ton About $5,000 (Canadian) per ton of mustard, scrap metal, dunnage, and neutralized nerve agent solution (not including costs of field ,separation and packaging and public communications programs) and environmental monitoring programs Comments Also incinerated were 375 tons of contaminated shredded metal, 4 tons of dunnage packed in cardboard boxes, 4 tons of neutralized nerve agent solution (cardboard boxes caused excess particulate matter that necessitated use of filters and reduced processing rate; incinerated scrap metal melted in a foundry and recycled); high community participation, including membership on committee to write impact statement; project completed and incinerator removed Source: McAndless (1992a,b).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 65 TABLE 3-10 Canadian Experience with Nerve Agent Destruction Destruction Method Characteristic Site Data Site Defence Research Establishment Suffield, Willis Centre Complex Agent VX, GA, GB, and other G-type nerve agents Amount 0.3 tons Form Munitions without explosives Separation Munitions drilled and agents drained Neutralization Batch-neutralized in methanolic 20% KOH (1,500 L of neutralized solution) diluted with water to 3X total volume increase (4,500 L total) Incineration Incinerated together with mustard-contaminated scrap metal in transportable unit (see Table 3-9); scrubbed flue gas with aqueous NaOH Effluents CO2 and H2O in discharged vapor and potassium and sodium chloride, fluoride, nitrate and phosphate in scrubber brine Efficiency Neutralization >99.9999%; incineration >99.9999% Monitoring Batch analysis of neutralizing solution to verify destruction of nerve agent; continuous monitoring of incinerator emissions as in Table 3-9; particulate emissions (samples) analyzed for phosphorus content Disposal Scrubber brine discharged to impermeable lined pit and allowed to evaporate; resulting salts and spent falters placed in landfill Duration 4 months intermittent to complete neutralization; 5 days for incineration of neutralized solution (hydrolyzate) Rate 0.8 tons/day as hydrolysate incinerated together with mustard-contaminated scrap metal (Table 3-9) Cost/ton $30,000/ton (includes operating costs, equipment, and supplies) Comments See Table 3-9 Source: McAndless (1992a,b).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 66 TABLE 3-11 erman Experience with Mustard Agent Destruction Destruction Method Characteristic Site Data Site Munster/Oertze Agent Mustard and thickened mustard containing arsenicals Amount About 70 metric tons/year total agent, ongoing program Form Old munitions and bulk containers Separation Cleaned with water jet, explosive ordinance demolition evaluation, transport, x- rayed, and cut, or drilled and drained; drained with steam injection if agent solidified; explosives and fuzes separated; intermediate storage of agent Incineration Batch-incinerated agent (hold at 300°C for 10-12 hours in inert gas atmosphere, then at 1000-1200°C for 2 seconds; empty munitions and containers kept about 12 hours at 1000°C); scrub flue gases with NaOH solution; precipitate arsenic in scrubber brine as ferric arsenate; pass flue gas through aerosol separator Effluents CO2 and H2O in discharged vapor, NaCl and Na2SO4 in scrubber brine, and ferric arsenate Efficiency Data not available Monitoring Continuous monitoring for HCl, SO2 , hydrocarbons, and NOx; discontinuous monitoring for particulates and dioxins in vapor effluent and for sulfate and pH in scrubber brine Disposal Scrubber brine discharged into municipal waste water system; filtered arsenic sludge placed in old salt mine Duration Began 1980, continuing Rate About 70 metric tons/year, total agent; up to 350 kg/day Cost/ton DM 25,000 Comments Highly automated operation (except for loading and unloading furnace wagons); urban facility Source: Conference on Disarmament, CD/CW/WP.374, Geneva, 1991; Martens (1992).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 67 TABLE 3-12 Former Soviet Union Experience with Agent Destruction Destruction Method Characteristic Site Data Site Shikhany Proving Ground and others. Agent GB, GD, and mustard Amount About 300 tonnes (including VX, see Table 3-13) Form Munitions Separation Drilled and vacuum-evacuated Neutralization Batch-neutralized in ethanolamine at 100°C for 30-45 minutes with water or NaOH added to reduce viscosity Incineration Batch-incineration of neutralization reaction products without gas scrubbing Effluents CO2, HCl, NaF, NO2 , PO x, SO2, and sodium salts Efficiency Reportedly 99.99999% (nerve agent) Monitoring Ionization detectors (with sensitivity 10-2 to 10-3 rag/cubic meter) and laboratory analysis Rate Reactor capacity 600 L; average 1980-1990 rate was about 20 tonnes/year Cost/ton Data not available Comments Use of ethanolamine reportedly reduces slag buildup and fouling of burners and incinerator; apparatus is mobile (known as a KUASI system) Source: Conference on Disarmament CD/CW/WP 367, Geneva, October 7, 1991; SFIL-CMT (1992); Manley (1992b).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 68 TABLE 3-13 Former Soviet Union Experience with VX Destruction Destruction Method Characteristic Site Data Site Shikhany Proving Ground and others. Amount About 30 tonnes (including GB, GD, and mustard, see Table 3-12) Form Munitions Separation Munitions drilled and agent drained Neutralization Batch-neutralized with 1:1 mixture of ethylene glycol and phosphoric acid Incineration Batch-incineration of neutralization reaction products without gas scrubbing Effluents CO2, NO2, POx , and SO2 Efficiency Reportedly 99.99999% Monitoring Data not available Duration Data not available Rate Reactor capacity 600L; average 1980-1990 rate was about 20 tonnes/year Cost/ton Data not available Comments Mobile apparatus (known as the KUASI system) Source: Conference on Disarmament CD/CW/WP.367, Geneva, October 7, 1991; SFIL-CMT (1992); Manley (1992b).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 69 TABLE 3-14 U. K. Experience with Destruction of Mustard and World War I Gases Destruction Method Characteristic Site Data Site CBDE Porton, Wiltshire Amount Small, variable each year Form Old munitions from diverse sites (shells, grenades, mortars) Separation Overpacked, trucked, x-rayed, remotely cut, drilled and drained Incineration Batch-incinerated 2-3 seconds at 1200°C; quenched and then scrubbed flue gas with aqueous NaOH Efficiency >99.9999% Monitoring Analysis for CO, HCl, SO2, and trace organics in vapor', analysis for trace organics in brine Disposal After analysis transferred to effluent treatment plant of municipal sewer system Duration 20 years and continuing Rate Incineration capacity 1-2 tons/day Cost/ton Data not available Comments Incinerator used for other hazardous wastes Source: Manley (1992a,b).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 70 TABLE 3-15 U.K. Experience with GB Destruction Destruction Method Characteristic Site Data Site CDE Nancekuke, Cornwall Amount About 20 tons Form Bulk agent Separation Vacuum transfer from bulk tanks Neutralization Batch-neutralized with aqueous 20% NaOH; diluted with water to <200 ppm fluoride Effluents Sodium isopropyl methylphosphonate, NaOH and NaF; final volume increase of effluents 4-5X greater than volume of agent destroyed Efficiency >99.9999% Monitoring For each batch, measurement of pH, fluoride, acetylcholinesterase activity, and toxicity to brine shrimp before disposal Disposal Discharge at depth into coastal sea Duration 2 years, 1967-1968 Rate 250 kg/batch, 2-3 hours/cycle Cost/ton Data not available Comments Outside environmental review after completion; destruction carried out in converted GB production plant Source: Manley (1992a, b).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 71 TABLE 3-16 U. K. Experience with Mustard Destruction Destruction Method Characteristic Site Data Site Several sites within the United Kingdom Amount About 6,000 tons Form Bulk agent Separation Pumped from storage tanks Incineration Continuous, at well above 600°C; flue gas scrubbed with aqueous NaOH Effluents CO2 and H2O in discharged vapor, NaCl and Na2 SO4 in scrubber brine Efficiency Not stated Monitoring Analysis for mustard Disposal Not stated Duration 1958-1960 Rate Data not available Cost/ton Not stated (pilot operation in 1956 estimated as 18 current pounds sterling per ton) Comments Data not available Source: Toler (1990).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 72 TABLE 3-17 U.N. Experience with Destruction of Mustard in Iraq Destruction Method Characteristic Site Data Site Al Muthanna Amount Estimated 400-500 tonnes with about 90% purity Form Bulk agent, aerial bombs, and 155-mm projectiles (some agent partly polymerized) Separation Vacuum-transferred from bulk storage tanks; munitions vacuumed drained through filling plugs or when necessary through holes creating by drilling or explosives charges Incineration Continuous, at 1100°C for 3-4 seconds; quenched and scrubbed flue gas with aqueous NaOH Effluents CO2, H2 O, and SO2 in discharged vapor, NaCl and Na2 SO4 in scrubber brine Efficiency Estimated >99.9999% Monitoring Continuous for CO, CO2, and O2 in flue gas, as indicators of combustion efficiency; continuous for pH of scrubber brine; discontinuous for mustard in flue gas and scrubber brine Disposal Scrubber brine discharged to pit containing limestone (to be covered after evaporation) Duration Estimated 9 months for incineration, 1992-1993 Rate 360 kg mustard/hour (maximum) Cost/ton Data not available Comments Same incinerator to be used to destroy other agents, probably including GA Source: Barrass (1992).
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 73 TABLE 3-18 U.N. Experience with Destruction of Nerve Agents in Iraq Destruction Method Characteristic Site Data Site Al Muthanna Agent GB and GB/GF mixture Amount Estimated 70 tonnes Form Bulk agent, aerial bombs, and ballistic missile warheads Separation Munitions vacuum-drained through filling plugs or through holes created by drilling explosive-shaped charges when necessary Neutralization Batch hydrolysis with excess aqueous NaOH in recirculating reactor Effluents Aqueous NaF and sodium salts of phosphonic acids with about 3% excess NaOH Efficiency <1 ppm Monitoring Continuous for temperature; continuous for reactor room ambient air for nerve agent; measurement of measurement of excess NaOH and analysis of each batch at end of reaction to verify agent level below detection limit of 1 ppm Disposal Spent reaction liquor discharged to impermeable lined pit (to be covered with concrete after evaporation) Duration Estimated six months for neutralization, 1992-1993. Rate One tonne/day Cost/ton Data not available Comments Data not available Source: Barrass (1992).
