OPCW Schedule

Van der Schans, M.J., Fidder, A., Van Oeveren, D., Hulst, A.G., Noort, D. (2008a). Verification of exposure to cholinesterase inhibitors generic detection of OPCW Schedule 1 nerve agent adducts to human butyrylcholinesterase. J. Anal. Toxicol. 32(1) 125-30. 

Because of the low concentration of the biomarkers, the analyses are target-directed because a full scan would be at the cost of sensitivity, which means that low-level exposures cannot be detected. However, this is a serious problem in the case when the identity of the nerve agent is not known beforehand. Some progress has been achieved to solve this problem. The number of different OPs exceeds several ousand, but the number of different masses is only 170. Because the OPCW Schedule 1 nerve agents consist only of saturated alkyl groups with mass increments of 14 units, the number of mass possibilities can be further reduced to 36 masses, which means that only 36 multiple reaction monitoring (MRM) transitions have to be recorded (van der Schans... 

Two types of portable analytical equipment were approved by the Conference of State Parties for on-site analysis, that is, GC/MS and Fourier transform infrared (FTIR). Initially, it was anticipated that FTIR might be used in storage, destruction and Schedule 1 facilities for screening purposes to confirm the presence of declared chemicals. While FTIR analysis is suitable to identify pure chemicals or certain chemicals in mixtures at varying detection limits, FTIR cannot be used to analyze for absence of undeclared scheduled chemicals, for which the IT would have to carry in addition to the FUR a GC/MS. For GC/MS analysis samples are analyzed at very low concentration contrary to FTIR analysis, which minimizes the risk of contamination in the on-site laboratory and reduces the risk of exposure of OPCW inspectors and on-site personnel. Considering the limitations of FUR and the fact that GC/MS can cover the field of application of the FUR for OPCW purposes, a decision was taken in 2000 to focus on the use of GC/MS in the OPCW mobile laboratory subject to future developments. 

The list of chemicals approved to be brought by the IT and to be used in the OPCW mobile laboratory on site contains no scheduled chemicals in order to prevent any contamination of on-site samples. Therefore, the IT cannot compare analytes detected by GC/MS analysis to reference standards or synthesize these standards on site. 

The content of the OCAD is currently limited to scheduled chemicals, their degradation products and some derivatives, and depends on the data contributed to the OPCW by Member States. The current version of the OCAD (June 2004) is sufficient for on-site analysis it contains the mass spectra of about 2000 chemicals. A detailed description of the OCAD can be found in Chapter 7. 

Table 1. Schedule of OPCW proficiency-testing scheme...

The schedule of the first 10 official OPCW proficiency tests is presented in Table 1. 

Retention Index pinacolyl alcohol is based on 6 measurements performed by the OPCW Laboratory), CAS registry No. [464-07-3], Schedule 2.B.14 ... 

The definitions and criteria that determine whether a chemical falls within the scope of the CWC or not, leaves a large number of chemicals in the gray area. One example of a group of chemicals that are excluded from the OCAD on the basis of purposes not prohibited under this Convention , is given by the Riot Control Agents . There are other examples, which need to be addressed in the future to determine how they can be regulated by the CWC as these have been seen to be very useful in the verification activities of the OPCW. Efforts are underway to find a way for the inclusion in the OCAD, of chemicals that are relevant to the CWC but are not covered by the schedule list (Scientific Advisory Board (SAB) and Validation Group (VG)). 

To facilitate the validation process on the basis of the above approach, the MS electronic data is contributed to the OPCW Laboratory in any of the following electronic formats JCAMP, NIST ASCII, AMDIS, and NIST MS Database. Contributing laboratories provide mostly the NIST MS Database format, with structures. The OPCW Code and the Schedule number are placed in the synonym field of the database. The file is submitted to the OPCW Laboratory either as the NIST MS User Database or the corresponding set of text files representing the MSP (Spectral) and MOL (Structure) information. The NIST MS Search/Analysis programs are used for the management of the MS electronic data and also GC(RI) once merged with the MS data. 

Table 2. An extract from the MS ANALYTICAL DATA spreadsheet PDFIndex showing the OPCW Code, Chemical name, CAS number, Schedule number, Link to PDF files and link to the electronic MS data in the NIST MS Database...

OPCW code Chemical name CAS Schedule Link to PDF file Link to NIST MS search... 

The Schedule 3 list contains only 17 discrete chemicals, of which four represent toxic chemicals. One of them is too simple (HCN) to produce an informative mass spectrum and some of the precursors (chlorinating chemicals) cannot be analyzed by GC/MS. Mass spectra are contained in the OPCW Analytical Database and in commercially available databases. The mass spectrum of trichloroni-tromethane (chloropicrin, CAS 76-06-2) is almost identical to that of trichloromethane (chloroform), apart from a peak at mlz 30. Not scanning this low... 

Reproducibility of the relative intensities in El mass spectra is a concern, despite the fact that spectra are recorded under standardized conditions. Different mass spectrometers produce spectra with, sometimes, large spreads in the relative intensities. An impression of the possible variation is given in Table 2. In this table, the relative intensities of major fragments in the El mass spectra of three nerve agents, taken from three different sources, are presented. It is clear that there exist no reference mass spectra of these Schedule 1 chemicals, which can be considered as true physical constants. A compilation of more than one spectrum of the same compound in the OPCW Analytical Database gives an indication of the possible spread. 

OPCW proficiency tests currently require the identification of between six and nine analytes (scheduled compounds or their degradation products) in matrices such as water, soil, and organic extracts. Identification must be confirmed by two independent techniques, and both identification and reporting must be in accordance with strict criteria. Although not mandatory, most laboratories rely on comparison with authentic compounds to confirm identification in order to minimize any chance of a false positive. If the authentic compound requires synthesis, then these tests are demanding in terms of time as well as in terms of detection and identification. 

The hydrolysis products (23-25) of the three nitrogen mustards listed in Schedule 1 of the CWC were included in the general LC/APCI/MS screening procedures of Black and Read, 14 26 . These procedures, and those of other laboratories, have successfully identified Af-methyldiethanolamine (23) and N-clhyldiclhanolaminc (24) in OPCW proficiency tests. More specific methods based on LC/ESI/MS have been reported for the trace analysis of ethanolamines in environmental residues (66) and biomedical samples (67). 

This procedure was used once during the initial years of treaty implementation. A second proposal for a change has recently been submitted. This has shown that the OPCW is indeed capable of going through a technical/administrative change (against some resistance by States Parties that feared the precedent for possible other adjustments, including to amendments to the Schedules) and that the machinery can in fact be utilized to adjust the technicalities of CWC implementation to new (or previously unknown or ill-understood) conditions in the real world. 

This chapter discusses the negotiation of the provisions of the CWC related to Review Conferences, and then considers the preparations for, and the conduct of, the first Review Conference (RevCon), which was convened at the headquarters of the Organisation for the Prohibition of Chemical Weapons (OPCW) in The Hague from 28 April to 9 May 2003. The outcomes of the RevCon are then considered, followed by an assessment of the potential value of the RevCon in guiding the activities of the OPCW until the next RevCon, which is scheduled to take place in 2008. 

There will be a substantial increase in the inspection workload for verification of CW destruction facilities (CWDFs) in the next few years because several additional CWDFs are scheduled to commence destruction operations. There are concerns that there will not be enough resources in the OPCW inspectorate to provide the level of verification of destruction based on currently agreed procedures. As pointed out to the Rev-Con by the Director-General, the verification methodology applied at CWDFs needs to be reviewed if the verification regime as a whole is to remain sustainable and affordable . ... 

However, the SAB has recommended that the OPCW expand the database to cover other chemicals, including certain non-scheduled chemicals that have the potential to be used in chemical warfare. See Note by the Director-General, OPCW document RC-1/DG.2, para. 5.10. 

The categories surveyed by the OPCW are Article I prohibitions Article I penalties Eixtra-territorial application Article 11(1) penalties Schedule 1 penalties Schedule 2 penalties Schedule 3 penalties Schedule 3 EUC Penalty for failure to declare and Obstacles to Article VII(2). See OPCW National Legislation Report, Annex 3. 

Bans and restrictions on transfers by States Parties to States not Party of the toxic chemicals and precursors listed in Schedules 1, 2 and 3 of the CWC s Annex on Chemicals are also set out in Parts VI, Vn and Vin, respectively, of the Verification Annex. Such measures can provide incentives for States not Party to join the CWC sooner rather than later, particularly as certain chemicals listed in the Schedules have many important commercial applications that are relevant to development needs. Finally, other potentially positive aspects of OPCW membership, in addition to the disarmament and non-proliferation elements of the CWC re-... 

Based on figures from OPCW annual report for 2002 (i), rounded to the nearest tonne. Excludes chemicals declared in quantities of less than one tonne. One such chemical was the nreve-gas O-ethyl 5-2-dimethylaminoethyl methylphosphonothiolate, also known as medemo or EA 1699. The CWC Verification Annex, in Part IV(A) para. 16, defines Category 1 as chemical weapons on the basis of Schedule 1 chemicals and their parts and components . 

The majority of substances listed on Schedule 1 of the Chemical Weapons Convention are considered to be percutaneous hazards (OPCW, 1993). In particular, sulphur mustard (HD) and VX are the most extensively studied agents of this genre and are representative of chemical warfare agents that exhibit mainly local or systemic percutaneous toxicity, respectively (Table 1). 

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