Due to events following September 11th, the focus of recent ASA Newsletter issues has been predominantly on bio and terrorism. Now, with John Hart's piece on the current treatment of PFIB under the CWC, the Newsletter is able to shift back towards the problems within the chemical arena. PFIB will be familiar to most as a potential CW agent. It is also produced in significant quantities by the fluoropolymer industry as a temporary by-product. The article shows CWC implementation at the working-level and gives readers background information on how the chemical might be captured by the CWC. As always the ASA Newsletter would welcome your comments on this significant area.

The Treatment of Perfluorisobutylene under the Chemical Weapons Convention
by John Hart, SIPRI*

Introduction:
          Perfluoroisobutylene (PFIB) is produced as a common by-product, in tens of thousands of ton quantities, in the fluoropolymer industry, including the production of 1,1,1,3,3,3-hexafluoro-2-propanol (HFP) and tetrafluoroethylene (TFE) and processes involving the pyrolysis of polytetrafluoroethene (PTFE), more commonly known by its trade name Teflon. As an unwanted by-product with apparently no known commercial uses above 1 metric ton [1], it is generally eliminated through scrubbing or thermal treatment. PFIB can cause pulmonary edema and those affected must then be treated for "polymer fume fever."[2] It can also act as a "mask breaker". Because PFIB is nonpolar it cannot be adsorbed by carbon. [3] PFIB's toxicity and effect are similar to those of phosgene and, like phosgene, no treatment for exposure is currently available with the exception of complete avoidance of physical activity. Based on publicly available literature, it seems impossible to state with certainty whether the compound has ever actually been weaponized and incorporated into an offensive chemical weapon (CW) program.
          There are, however, intriguing published references along with occasional oral statements, which suggest that it has. [4] Various national defense establishments have also undertaken measures to protect against it.[5] In addition, Chemical Weapons Convention (CWC) negotiators felt strongly enough about its potential misuse to include it in Schedule 2A of the treaty's Annex on Chemicals.[6] In early 2002 the Organization for the Prohibition of Chemical Weapons (OPCW) gave renewed attention to the issue of whether and how PFIB should be declared and subject to systematic inspections. Some parties tried to effectively exclude it from systematic verification and others attempted to ensure that this does not occur. The Secretariat has argued that PFIB should be declared and subject to systematic inspections.[7] Draft text is being prepared for the Seventh Conference of the States Parties (CSP), to be held on 7-11 October, which will determine the low concentration declaration threshold for Schedule 2A and 2A* chemicals (see below). The main reason why consensus has not been achieved on a low concentration threshold for Schedule 2A is because of disagreements on how to handle PFIB.

The treatment of PFIB under the CWC:
          Informal discussions on PFIB have taken place during Executive Council (EC) and Industry Cluster meetings and between interested parties at the margins.[8] The PFIB question has been discussed within the framework of several unresolved or partially resolved implementation issues dating from the time of the OPCW's Preparatory Commission (PrepCom) which met in 1993-97. The principal issues affecting how PFIB is treated under the CWC are: (a) determination of quantitative declaration thresholds for Schedule 2 and 3 chemicals in mixtures at "low concentration," (b) consistent application of a single set of guidelines governing "ease of recovery" of Schedule 2 and 3 chemicals in mixtures at low concentration and (c) determining the "boundaries of production" at chemical industry plant sites.
          The chemicals that are listed on Schedule 2 and 3 of the CWC's Annex on Chemicals need not be declared if they appear in mixtures at "low concentration."[9] During the PrepCom and the period immediately following the treaty's entry into force on 29 April 1997, most parties supported a 30 percent threshold for Schedule 3 chemicals and 10 percent threshold for Schedule 2 chemicals. In May 2000 the Fifth CSP agreed on guidelines that the low concentration limit for Schedules 2B and 3 be 30 percent or less. Parties were requested to take measures to implement the guidelines by 1 January 2002.[10] As of February 2002, the parties are still applying different low concentration thresholds (ranging from zero to 80 percent) for both schedules.[11] Most parties, however, are applying limits ranging between 10 and 30 percent. The issue is complicated by the fact that some parties calculate their low concentration thresholds by weight, some by volume and some by a combination of weight and volume. The US Department of Commerce's Bureau of Export Control (BXA), for example, requires companies to make their calculations by either volume or weight, whichever yields the lower number.[12] While these actions have the desired effect of limiting the treaty's scope, it has also introduced inefficiencies in data collection and analysis.
          The Secretariat has identified 18 facilities which produce PFIB as a by-product, but only six facilities have been declared to the OPCW.[13] The number of plants where PFIB is present, however, is probably in the thousands.[14] Some parties have proposed that the low concentration limit be set above 0.5 per cent. If adopted, two-thirds of the PFIB producers known to the Secretariat could be eliminated from parties' declarations. Furthermore, if all the plant sites were to modify their production configuration to allow for in-line destruction, it is possible that no PFIB would be declared.[15] Whether this happens depends, in turn, on how the CWC term "captive use" is understood and implemented.[16] Captive use discussions center on whether 3-Quinuclidinyl benzilate (BZ), a hallucinogenic CW that is also produced as a by-product in the production of chemicals for peaceful purposes, should be declared.[17] Some parties declare BZ since it is an intermediate chemical which could be isolated, while other parties do not declare it because the compound is not isolated.[18]
          A related set of discussions, also dating from the PrepCom period, has centered on the concept of "ease of recovery" of scheduled chemicals in mixtures at low concentration.[19] The issue was discussed intensively during the first two years of the PrepCom and then was dropped mainly because negotiators found it impossible to draft, much less agree on, guidelines. There have since been occasional discussions, mostly at the margins.
          Finally, "boundary of production" refers to where production begins and ends. It may be understood to include a single reactor only or may also include other production equipment up to and including that used for the production of the final chemical product. If the boundaries of production are drawn so as to include only the reactor vessel, this can have the effect of eliminating the need to declare scheduled chemicals produced as by-products. One method for the production of acylonitrile, for example, involves the production of hydrogen cyanide (HCN), a Schedule 3 chemical that has been used as a CW agent, in concentrations of less than 1 percent. Since the low concentration declaration limit generally applied to Schedule 3 chemicals is around 30 percent, the HCN would not be declared. If, however, the boundaries of production are extended to include ancillary equipment used in the recovery and concentration of purified HCN, then the chemical should be declared and would be subject to inspection.[20]

CWC negotiations:
          The CWC negotiations on how to define chemicals and regulate them, including their production and use by chemical industry, were long and complex. The initial concept was to categorize militarily significant chemicals as "super-toxic chemicals," "other lethal chemicals" or "other harmful chemicals."[21] Discussions initially focused on a chemical's toxicity and included efforts to define "militarily significant" quantities of chemical agents and their deviation ranges, effective dosages, ratios of agent weight to body weight, median lethal dose (inhalation) and median lethal dose (subcutaneous).[22] This resulted in detailed discussions on the methodologies used in toxicity studies and how differences in assumptions, test animals and control parameters affect results.
          Negotiators finally decided that efforts to reconcile the toxicity of a chemical with its potential use as a CW agent and its utility to chemical industry were impractical. It was instead decided to list chemicals in schedules not according to toxicity per se, but in terms of the threat they pose to the object and purpose of the treaty and the extent to which they were used for peaceful purposes. Thus Schedule 1 chemicals are deemed to pose a "high" risk to the convention with few, if any, peaceful applications, while Schedule 2 chemicals pose a "significant" risk and Schedule 3 chemicals "some" risk and have wider uses for peaceful purposes. To help address concerns that the treaty's depth and scope not be overly restricted, provision was made to include "other" chemical production facilities that produce certain unscheduled discrete organic chemicals which may include the elements phosphorus, sulfur or fluorine (DOC/PSFs). By 1989 PFIB was listed in the rolling text of the CWC, for the most part under Schedule 2B where it appears to have remained until shortly before the treaty text was finalized at the end of 1992. It should also be noted that there was some support among parties for listing PFIB under Schedule 1.

Has PFIB been weaponized?
          PFIB is listed in various casualty management manuals and civil defense handbooks, including those oriented towards meeting possible terrorist attacks.[23] It is also appeared on some export control lists. A recent news item describing environmental clean-up efforts by the US Environmental Protection Agency states that in addition to disposing of 23 canisters filled with 72 pounds (32.7 kg) of PFIB, "several decaying cylinders" (apparently empty) of PFIB were also discovered.[24] However, part of the reason why PFIB appears in some publications is because of defensive measures not only against intentional use, but also because PTFE (i.e., Teflon) has a wide variety of commercial and military applications given its lubricity and chemical inertness. It is therefore used in the manufacture of military vehicles, including tanks, armored personnel carriers and aircraft. If these items are hit by shell fire or are otherwise subjected to high levels of heat leading to pyrolysis of teflon components, PFIB would be generated.

Conclusion:
          There does not appear to be any "smoking gun" in the public literature clearly linking PFIB to an offensive program. Such evidence would include documented use on the battlefield, large-scale weaponization, internal policy documentation and user manuals. It seems probable that the chemical was evaluated as a potential CW agent to stockpile. The US, for example, has reportedly systematically tested over 600 000 chemicals for CW purposes since WW I.[25]
          It is also unclear to what extent the focus on PFIB is due to concern regarding the compound itself and to what extent other factors, such as the treaty's cost and scope and whether PFIB serves as a marker for other toxic fluorochemicals, may be playing a role.[26] The US appears to favor a low concentration threshold above 0.5 percent for Schedule 2A chemicals. An indication of the reasoning behind the US position may be found in the minutes of the US Government's Materials Technical Advisory Committee meeting, held in December 2000, which state: "OPCW is looking at Schedule 2 and Schedule 2a (perfluoroisobutylene, PFIB) materials in an effort to decrease the declaration threshold. The US position is that the action should be related to the threat of proliferators and the universality of production."[27] This could be interpreted to imply that "proliferators" have expressed little, if any, interest in incorporating PFIB into prohibited programs and that the reporting of the compound in national (cont. p. 22 - PFIB) (PFIB - from p. 21) declarations to the OPCW is uneven.
          If PFIB is not captured under the low concentration threshold selected for Schedule 2A, it can still be captured under DOC/PSF inspections or under the treaty's "general purpose criterion."[28] However, it has been estimated that under the current frequency of inspection algorithms governing DOC/PSF inspections and given the sheer number of such plants that have been declared (over 4000 thus far), any given plant would receive an inspection once every 100 to 300 years.[29] If the capture of possible prohibited activities involving PFIB is left to the general purpose criterion, this would probably involve the use of "national technical means," including information derived from parties' intelligence services. In such a scenario, one or more states would approach the OPCW with a specific compliance concern which could then be addressed through Article IX's informal consultation, cooperation and fact-finding provisions or a challenge inspection.[30] The criterion is implemented unevenly, however. In addition, use of NTM and the decision to conduct a challenge inspection are politically sensitive issues. In general, a well-informed, high-level political and financial commitment is required to ensure the CWC's continued relevance and effectiveness. However, as the PFIB case shows, treaty implementation can sometimes prove difficult.

References:

1. Personal communications, Nov. 2001 and Feb. 2002. It is interesting to note that part of the language defining a chemical weapon production facility in the CWC states that one of the factors which would constitute such a facility would be if it produced "any chemical listed in Schedule 1 of the Annex on Chemicals; or any other chemical that has no use, above 1 tonne per year on the territory of a State Party or in any place under the jurisdiction or control of a State Party, for purposes not prohibited under the Convention, but can be used for chemical weapons purposes." Article II, para. 8(a)(i). The language "any chemical that has no use, above 1 tonne" may in fact refer to a chemical process dating from the 1950s which results in the production of PFIB as a by-product.
2. The literature on polymer fume fever is extensive. An early reference is Harris, D. K., Lancet (1951), pp. 1008-1015
3. Bovenkamp, "The development of penetrant protective carbon (PPC)," ASA Newsletter (12 Apr. 1996), no. 53.
4. "Chemical warfare agents," in John Eldridge (ed.), Jane's Nuclear, Biological and Chemical Defence, 12th edition (1999-2000), (Biddles Ltd.: Guildford, England, 1999), p. 25.
5. Bajgar, J., "Some toxic chemicals as potential chemical warfare agents - the threat for the future?," ASA Newsletter (22 Dec. 1998), no. 69, Patocka, J. and Bajgar, J., "Toxicology of perfluoroisobuten," ASA Newsletter (1998); and Wang, H. et al., "Perfluoroisobutylene-induced acute lung injury and mortality are heralded by neutrophil sequestration and accumulation," Journal of Occupational Health (2001), vol. 43, pp. 331-38, URL .
6. The other chemicals listed in Schedule 2A are: amiton and 3-Quinuclidinyl benzilate (BZ). PFIB's Chemical Abstract Service (CAS) registry no. is 382-21-8. For a historical review of the development of amiton and related compounds for chemical weapon (CW) purposes, see The Problem of Chemical and Biological Warfare, the Rise of CB Weapons (Almqvist & Wiksell: Stockholm, 1971), vol. 1, pp. 74-75. A description of the US BZ stockpile and its destruction is given in United States of America, "A report on the destruction of 3-Quinuclidinyl benzilate (BZ)," Conference on Disarmament document CD/CW/WP.336, 20 Mar. 1991.
7. See, for example, "Opening statement by the Director-General to the Executive Council at its Twenty-Seventh Session," OPCW document EC-XXVII/DG.10, 4 Dec. 2001, para. 34.
8. The Industry Cluster is an informal group of experts that considers industry-related matters.
9. Part VII of the Verification Annex, para. 5 and Part VIII of the Verification Annex, para. 5.
10. "Decision, guidelines regarding low concentration limits for declarations of Schedule 2 and 3 chemicals," OPCW document C-V/DEC.19, 19 May 2000.
11. The United States Senate set the Schedule 3 low concentration at 80 percent. Federal Register, vol. 64, no. 250, p. 73762.
12. US regulations for CWC implementation by chemical industry state "Declaration and reporting requirements apply also to Schedule chemicals contained in mixtures. Note, however, that the quantity of a Schedule 2 chemical contained in a mixture must be counted for declaration and report purposes only if the concentration of the Schedule 2 chemical in the mixture is 30% or more by volume or by weight, whichever yields the lesser percent." It goes on to say that "the quantity of a Schedule 3 chemical contained in a mixture must be counted for declaration and reporting purposes only if the concentration of the Schedule 3 chemical in the mixture is 80% or more by volume or by weight, whichever yields the lesser percent. If the mixture contains 80 percent or more of the Schedule 3 chemical, you must count only the amount (weight) of the Schedule 3 chemical contained in the mixture, not the total weight of the mixture." Federal Register, vol. 64, no. 250, (30 Dec. 1999), p. 73762.
13. Personal communication with a National Authority official, Feb. 2002.
14. In addition, it can be readily removed as a precipitate if the reaction stream is diverted and cooled. PFIB is also extremely stable, in the complete absence of moisture, in metal and glass containers.
15. "Opening statement by the Director-General to the Executive Council at its Twenty-Seventh Session," OPCW document EC-XXVII/DG.10, 4 Dec. 2001, para. 34.
16. "Captive use" has been defined by some as "the case of the production of a Schedule 2 chemical and its subsequent further conversion without isolation in the same reaction vessel/unit to form another product."
17. BZ is typically produced by the reaction of 3-quinuclidinol with diphenylchloroacetyl chloride in a stirred reactor at low concentration. It is frequently converted to clindinium bromide without further isolation by adding ethylene dibromide to the reactor.
18. The issue is further complicated when concentrates are placed into "day tanks" (a temporary chemical holding tank) since it is sometimes argued that such tanks are in fact "storage tanks."
19. Part VII of the Verification Annex, para. 5 and Part VIII of the Verification Annex, para. 5.
20. Personal communication with national authority official, June 2001.
21. See, for example, "Report of the Committee on Disarmament to the United Nations General Assembly," Committee on Disarmament document CD/421, 1 Sep. 1983, p. 66.
22. They were based on consultations held in Mar. 1982 among 32 experts from 25 countries. These experts unanimously agreed to recommend a standardized operating procedure for acute subcutaneous toxicity and acute inhalation toxicity determinants. "Annex on chemicals, introductory note by the Chairman of Working Group 4," Conference on Disarmament document CW/Group4/3 (rev. 3), pp. 18-22.
23. See Logan County Health Department (Lincoln, Illinois), medical information sheet "Terrorism," URL and United States Army Medical Research Institute of Chemical Defense, Medical Management of Chemical Casualties Handbook (third edition), URL .
24. The article states "The Flura Corp., which purchased the Rock Hill Laboratories site on the outskirts of Newport in the late 1980s, was shut down by the EPA early last year. An emergency response team from the EPA and the U.S. Coast Guard took physical control of the site, and they found thousands of containers loaded with chemicals like phosgene, cyanide and phosphoric acid, officials said. Also found at the site were several decaying canisters of perfluoroisobutylene, or PFIB, an industrial chemical that fell into general disuse decades ago but found its way into the arsenal of the former Soviet Union as a chemical weapon, according to EPA officials." It goes on to say that "According to the company's owner, Dr. Edward Tyczkowski, Flura Corp. manufactured specialty gases for industrial uses as well as chemical weapons for the U.S. Army. The Army initially denied making any purchases from the company but later recanted after records were found showing that several transactions did, in fact, take place. An Army spokeswoman, however, said it was unclear exactly what was purchased from Flura Corp." Stambaugh, J. J., "Discussion," News Sentinel (Knoxville, Tennessee, 23 May 2001, URL .
25. Hart, J., "A review of sea-dumped chemical weapons (with an annex on the decommissioning of Russian nuclear-powered submarines)", p. 10, fn. 54. Paper presented at "The Environment and the Common Fisheries Policy, Threats to and Constraints on Sustainability" Greenwich Forum, 27 Jan. 2000, London, Great Britain.
26. In a similar way, saxitoxin and ricin in the Annex on Chemicals serve as markers indicating that toxins are covered by the treaty.
27. "Minutes: Materials Technical Advisory Committee Meeting 14 Dec 2000," URL . Other language in the document seems to indicate that, as far as the US is concerned, PFIB is not a declarable chemical: "To add a chemical to Schedule 2 or Schedule 3, all OPCW members must agree. The chemical has to be identified as a precursor or as having been used in or as a weapon. A recommendation would go through the US government, then the Western Group, then to OPCW. PFIB was cited as an example. The US and OPCW would consider what the equities are, what effect adding the chemical to a Schedule would have on other member states' declarations, and what the effects on US declaration requirements would be."
28. The general purpose criterion prohibits the development, production, stockpiling and use of all toxic chemicals except for peaceful purposes. CWC, Article II, para. 1.
29. The level of verification applied to DOC/PSFs is the lowest of all chemical industry inspections. Such inspections are "random" and are intended to act primarily as a confidence-building measure. The intrusiveness of DOC/PSF inspections is therefore also the lowest of all OPCW inspections.
30. To date, the OPCW has not carried out a challenge inspection.

* The views expressed in this paper are the author's and do not necessarily reflect those of SIPRI. The author also wishes to thank Barbara and Richard Price for their comments and assistance. Any errors are the responsibility of the author.

Editor's Note: John Hart is now a researcher with the Stockholm International Peace Research Institute, SIPRI. John's expertise on chem bio issues, especially as they relate to the treaties and protocols, makes him not only an invaluable asset for SIPRI but also for ASA where he is one of our outstanding correspondents for science and technology.