1. Chemicals to be monitored under CWC
REGIONAL TRAINING COURSE FOR CUSTOMS AUTHORITIES OF STATES PARTIES IN ASIA ON TECHNICAL ASPECTS OF THE TRANSFERS REGIME OF THE CHEMICAL WEAPONS CONVENTION NEW DELHI, INDIA 10 – 13 DECEMBER 2012
Chemicals to be monitored under CWC
Declarations Branch/Verification Division
ORGANISATION FOR THE PROHIBITION OF CHEMICAL WEAPONS

2. Objectives By the end of this session participants should:
Be aware of the key CWC definitions of a chemical weapon and a toxic chemical
Understand the concept of the dual use nature of chemicals
Be familiar with the 3 Schedules of chemicals monitored by the CWC
Be familiar with some of the uses of the most common scheduled chemicals 2

3. What is a chemical weapon?

4. Chemical Weapon (Article II, Para 1)
Means the following, together or separately:
Toxic chemicals and their precursors, except where intended for purposes not prohibited under this Convention (*)
Munitions and devices, specifically designed to cause death or other harm through the toxic properties of those toxic chemicals specified in paragraph a)
Any equipment specifically designed for use directly in connection with the employment of munitions and devices specified in paragraph b)
(*) General purpose criterion defined by purpose and not by properties 4

5. Toxic Chemicals (Article II, Para 2)
TOXIC CHEMICAL means any chemical
which through its chemical action on life processes
can cause death, temporary incapacitation or
permanent harm to humans or animals. This includes
all such chemicals, regardless of their origin or of the
method of production, and regardless of whether
they are produced in facilities , in munitions or
elsewhere. 5

6. Article VI of CWC
Establishes the right of a State Party to manufacture and use toxic chemicals and their precursors for activities not prohibited under the Convention
Creates legal bases for Declaration, Verification and Transfer regimes related to such chemicals, facilities and activities.
Verification Annex Parts VI to IX
Article VI has two basic functions in the Convention:
It establishes the right of SP to manufacture and use toxic chemicals and precursors for activities not prohibited under the Convention and simultaneously creates the legal bases for the Declaration, Verification and Transfer Regimes related to such chemicals, facilities and activities.
The specifics of these regimes are set forth in Parts VI to IX of the Verification Annex. 6

7. Activities not Prohibited under the Convention
ARTICLE II, P9
Industrial, agricultural, research, medical, pharmaceutical or other peaceful purposes
Protective purposes
Military purposes not connected with the use of chemical weapons
Law enforcement including riot control purposes
Article VI relates to activities not prohibited under the Convention. Article VI is thus a consequence of the very nature of chemicals having dual-use. Toxic chemicals can be used as chemical weapons or in the chemical industry. 7

8. Dual Use Nature of Chemicals
Many chemicals covered by CWC can be used for legitimate peaceful purposes as well as chemical weapons (CW) purposes.
Cannot just define a list of “banned” chemicals.
Need to define chemicals and activities to be monitored
Remember the CWC does not just cover toxic chemicals but also many non-toxic precursors that can be used to make toxic chemicals for CW purposes. 8

9. Annex on Chemicals to the CWC
Sched 1
Sched 2
General Purpose Criterion
Activities
not
prohibited
Dual-use chemicals
Sched 3
DOC 9

10. Schedule 1 Chemicals
It has been developed, produced, stockpiled or used as a chemical weapon ...;
It poses otherwise a high risk to the object and purpose of this Convention by virtue of its high potential for use in activities prohibited under this Convention … ;
It has little or no use for permitted purposes 10

11. Schedule 1 Chemicals 12 entries – families or individual chemicals
Schedule 1A: toxic chemicals - Includes well known chemical weapons agents such as
Sarin, Soman, VX
Sulfur and nitrogen mustards
S1A also includes toxins Ricin and Saxitoxin
Schedule 1B - key precursors 11

12. Examples of Schedule 1A Schedules 1A01-03 – Large Families
O-Alkyl (C10, incl. cycloalkyl) alkyl (Me, Et, n-Pr or i-Pr)-phosphonofluoridates
e.g. Sarin (CAS No.: 107‑44‑8) Soman (CAS No.: 96‑64‑0)
1A02
O-Alkyl (C10, incl. cycloalkyl) N,N-dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidocyanidates
e.g. Tabun: (CAS No.: 77‑81‑6)
1A03
O-Alkyl (H or C10, incl. cycloalkyl) S-2-dialkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et, n-Pr or i-Pr) phosphonothiolates and corresponding alkylated or protonated salts
e.g. VX: (CAS No.: 50782‑69‑9)
Schedule 1A01-03 are all nerve agents. They act by disrupting the cholesterinase enzymes in the body and thus making nerve transmission impossible. Many insecticides work in exactly the same way. These are modern agents and are all extremely toxic. The earliest ones found were in the Tabun family (Schedule 1A02), followed by the Sarin family (Schedule 1A01) and the most recent ones are the V family (Schedule 1A03).
All of these compounds are unusual and for the most part do not occur in nature. Like much of phosphorus chemistry, the production is often air sensitive and the compounds are not all that stable in the environment – most of them will react in moist air in and decay in a few days.
Two of these classes has phosphorus attached to methyl, ethyl or propyl (iso or normal). Why stop there? By the time you get to P-propyl or P-isopropy the toxicity of the chemical has dropped significantly.
In addition each of these classes of chemicals has the phosphorus bonded to a oxygen by a double bond and each class has the phosphorus bonded to an oxygen by a single bond and that oxygen bonded to a hydrocarbon with 1 to 10 carbons. Why not more – again the toxicity drops off dramatically as you get to more than about 8 carbons. What about other groups, i.e. something other than hydrocarbons – how about aromatics? Some are unstable, some are not all that toxic and none had been made into weapons at the time of the treaty.
Throughout R1, R2, R3 = Me, Et, n-Pr or i-Pr
R=alkyl or cycloalkyl, with C10 12

13. Effect of Nerve Agents 13

14. Examples of Schedule 1A Sulfur Mustards 1A04 – 9 Specific Chemicals
2‑Chloroethylchloromethylsulfide (2625‑76‑5)
Mustard gas: Bis(2‑chloroethyl)sulfide (505‑60‑2)
Bis(2‑chloroethylthio)methane (63869‑13‑6)
Sesquimustard: 1,2‑Bis(2‑chloroethylthio)ethane (3563‑36‑8)
1,3‑Bis(2‑chloroethylthio)‑n‑propane (63905‑10‑2)
1,4‑Bis(2‑chloroethylthio)‑n‑butane (142868‑93‑7)
1,5‑Bis(2‑chloroethylthio)‑n‑pentane (142868‑94‑8)
Bis(2‑chloroethylthiomethyl)ether (63918‑90‑1)
O‑Mustard: Bis(2‑chloroethylthioethyl)ether (63918‑89‑8)
Mustard or HD
Unlike schedules 1A01-1A03, schedule 1A04 contains only 9 chemicals. Recall that the OR provided for a very large set of chemicals to be covered by the treaty.
Mustard (HD) was widely deployed and used in World War I and there were large stocks of the chemical in many arsenals. For the most part the other mustards are just as toxic, but have different physical properties – they are for the most part less volatile (the Cl(CH2)2S(CH2)Cl is the exception). Note that not all chemicals that look like mustard are even included. The common element is the Cl(CH2)2S- group, but having this does not mean a chemical is classed as Schedule 1A04 – this is in contrast to Schedule 1A01-03 where a structural definition was used.
Some of these higher mustards were used in weapons and the O-mustard (T) was a common impurity of one specific method for making mustard and was produced in very large quantities.
Mustards are easy to produce unlike the other chemical agents. As a result they have been deployed by more countries than the nerve agents.
Note that there are some obvious omissions in the schedule, specifically the chemical 1-Chloro-3-((2-chloroethyl)thio)propane: Cl-(CH2)3-S-(CH2)2-Cl 14 14

15. Examples of Schedule 1A Lewisites 1A05 – 3 Specific Chemicals
Lewisite 1: 2‑Chlorovinyldichloroarsine
Lewisite 2: Bis(2‑chlorovinyl)chloroarsine
Nitrogen mustards were not a major part of the chemical weapon stockpile, but were used in limited quantities. As with sulfur mustards and lewisites, the schedule is limited to exactly these chemicals.
There is an on going controversy over whether the salts of these chemicals should be considered scheduled. They are not called out as such by the treaty, whereas other salts of amines are called out.
There is a very limited use of these chemicals in cancer treatment.
Lewisite 3: Tris(2‑chlorovinyl)arsine 15

16. Examples of Schedule 1A Nitrogen Mustards 1A06 – 3 Specific Chemicals
HN-1 = Bis(2-chloroethyl)ethylamine
HN-2 = Bis(2-chloroethyl)methylamine
Nitrogen mustards were not a major part of the chemical weapon stockpile, but were used in limited quantities. As with sulfur mustards and lewisites, the schedule is limited to exactly these chemicals.
There is an on going controversy over whether the salts of these chemicals should be considered scheduled. They are not called out as such by the treaty, whereas other salts of amines are called out.
There is a very limited use of these chemicals in cancer treatment.
HN-3 = Tris(2-chloroethyl)amine 16

17. Effect of Mustard Gas 17

18. Saxitoxin 1A07
Saxitoxin is a neurotoxin naturally produced by certain species of marine dinoflagellates (Alexandrium sp., Gymnodinium sp., Pyrodinium sp.) and cyanobacteria (Anabaena sp., some Aphanizomenon spp., Cylindrospermopsis sp., Lyngbya sp., Planktothrix sp.).
Ingestion of saxitoxin (usually through shellfish contaminated by toxic algal blooms) is responsible for the human illness known as paralytic shellfish poisoning (PSP). 18

19. Red tides

20. Castor Bean (Ricinus communis)
Ricin (1A08)
is a protein toxin extracted from Castor Beans. It is found in many countries around the world

21. Schedule 1 Chemicals B. Precursors: DF: Methylphosphonic difluoride
(9) Alkyl (Me, Et, n‑Pr or i‑Pr) phosphonyldifluorides
e.g. DF: (CAS No.: 676‑99‑3)
(10) O‑Alkyl (H or <C10, incl. cycloalkyl) O‑2‑dialkyl
(Me, Et, n‑Pr or i‑Pr)‑aminoethyl alkyl
(Me, Et, n‑Pr or i‑Pr) phosphonites and
corresponding alkylated or protonated salts
e.g. QL: (CAS No.: 57856‑11‑8)
(11) Chlorosarin: O‑Isopropyl methylphosphonochloridate (CAS No.: 1445‑76‑7)
(12) Chlorosoman: O‑Pinacolyl methylphosphonochloridate (CAS No.: 7040‑57‑5)
QL: Ethyl 2-diisopropylaminoethyl methylphosphonite 21

22. Uses of Schedule 1 Chemicals
No large scale uses
Ricin
Anticancer research
Saxitoxin
Diagnostic kits for Paralytic Shellfish Poisoning
Nitrogen Mustard
Small quantities for skin cancer treatment
Sarin – Sulfur Mustard – VX
Small quantities used for developing protection and detection methods 22

23. Schedule 2 Chemicals
... it possesses such lethal or incapacitating toxicity as well as other properties that could enable it to be used as a chemical weapon;
It poses a significant risk ... by virtue of its importance in the production of a chemical listed in Schedule 1 or Schedule 2, part A;
It is not produced in large commercial quantities for purposes not prohibited under this Convention. 23

24. Virtually never traded
Schedule 2 Chemicals
A. Toxic chemicals:
(1) Amiton: O,O‑Diethyl S‑[2‑(diethylamino)ethyl]
phosphorothiolate (78‑53‑5)
and corresponding alkylated or protonated salts
(2) PFIB: 1,1,3,3,3‑Pentafluoro‑2‑(trifluoromethyl)‑1‑propene (382‑21‑8)
(3) BZ: 3‑Quinuclidinyl benzilate (*) (6581‑06‑2)
Virtually never traded 24

25. Schedule 2 Chemicals Precursors:
(4) Chemicals, except for those listed in Schedule 1, containing a phosphorus atom to which is bonded one methyl, ethyl or propyl (normal or iso) group but not further carbon atoms,
e.g. Methylphosphonyl dichloride (676‑97‑1)
Dimethyl methylphosphonate (756‑79‑6)
Exemption: Fonofos: (944‑22‑9)
. . .
(10) N,N‑Dialkyl (Me, Et, n‑Pr or i‑Pr) aminoethyl-2-chorides
and corresponding protonated salts
(13) Thiodiglycol: Bis(2‑hydroxyethyl)sulfide (111‑48‑8)
(14) Pinacolyl alcohol: 3,3‑Dimethylbutan‑2‑ol (464‑07‑3)
R= Me, Et,
Pr or iPr

26. Examples of Uses of a Specific Schedule 2 Chemical
Thiodiglycol
Carrier for Dyes in Textile & Printing Industry
Co-solvent in Water-based Pen Inks
Manufacture of Some Types of Plastics, Resins and Adhesives
Lubricant Additive
BUT 1 STEP FROM MUSTARD GAS 26

27. Examples of Uses of a Specific Schedule 2 Chemical
Dimethyl methylphosphonate (DMMP)
Used as flame retardant for foamed polyurethane plastics and as flame retarding impregnant e.g. for textiles
Several other chemicals from Schedule 2B04 used in similar applications (e.g. diethyl ethylphosphonate)
BUT KEY PRECURSORS FOR THE NERVE AGENTS 27

28. Examples of Sch 2 Commercial Uses
Was a commercial pesticide withdrawn
due to toxicity
Amiton
PFIB
Waste Constituent BZ
Pharmaceuticals, Medical Research
Flame retardants, Anti-Foam agents,
Gasoline/Oil Additives
Viscosity depressants, Textiles, Drugs,
Schedule 2B4 Family
Dialkylphosphoramidic
Dihalides Family
None
Dialkyl N,N-dialkyl-
Phosphoramidates Family
Polyamide Fibers, Fireproofing agents 28

29. Examples of Sch 2 Commercial Uses
Purifying Arsenic, Semiconductor manuf.
Catalyst in CFC Manuf.
Organoarsines/Chloroarsines
Arsenic Trichloride
Polishing stainless steel, Catalyst for
Urethanes, Hydantoin manufacture
Antichigger Clothing Treatment
Diphenyl-2-hydroxyacetic
acid
Organic Ammonium Bromides
Drug Research
Laboratory Reagent/Catalyst
Quinuclidin-3-ol
N,N-Dialkylaminoethane-
2-ols Family
Manufacturing organic thiols
N,N-Dialkylaminoethane-
2-thiols Family
Drugs, Food Flavourings, Antibacterials 29

30. Examples of Sch 2 Commercial Uses
Drugs, Agrochemicals, Dyes,
Calcium Filler for Paper/Plastics
N,N-Dialkylaminoethyl-
2-chlorides Family
Wetting agent in textile dyeing,
Dye solvent,
Antioxidant, Anticorrosives,
Inks, Epoxy resins, Fabrics
Thiodiglycol
Organic synthesis
Pinacolyl alcohol 30

31. Schedule 3 Chemicals
It has been produced, stockpiled or used as a chemical weapon;
… it possesses such lethal or incapacitating toxicity as well as other properties that might enable it to be used as a chemical weapon;
It poses a risk by virtue of its … importance in the production of one or more chemicals listed in Schedule 1 or Schedule 2B;
It may be produced in large commercial quantities for purposes not prohibited under this Convention. 31

32. Schedule 3 Chemicals A. Toxic chemicals: B. Precursors:
(1) Phosgene: Carbonyl dichloride (75‑44‑5)
(2) Cyanogen chloride (506‑77‑4)
(3) Hydrogen cyanide (74‑90‑8)
(4) Chloropicrin: Trichloronitromethane (76‑06‑2)
B. Precursors:
(5) Phosphorus oxychloride (10025‑87‑3)
(6) Phosphorus trichloride (7719‑12‑2)
. . .
(16) Methyldiethanolamine ( )
(17) Triethanolamine (102‑71‑6) 32

33. Examples of Uses of a Specific Schedule 3 Chemical
Triethanolamine (1)
Desulfurisation in Petroleum Refining
Intermediate in Manufacture of Surface Active Agents, Textile Specialties, Waxes, Polishes, Herbicides, Petroleum Emulsifiers, Cement Additives, Cutting Oils
Making Emulsions with Mineral & Vegetable Oils, Paraffin & Waxes
Solvent for Dyes 33

34. Examples of Uses of a Specific Schedule 3 Chemical
Triethanolamine (2)
Manufacture of Synthetic Resins
Increasing Penetration of Organic Liquids into Wood & Paper
Production of Lubricants for the Textile Industry
PH balancer in cosmetics
BUT 1 STEP FROM NITROGEN MUSTARD 34

35. Examples of Sch 3 Commercial Uses
Polyurethanes, Polycarbonates, Drugs,
Perfumes, Fumigants, Dyes,
Chlorinating agent
Phosgene
Herbicides, Dyes, Vitamins,
Rubber vulcanization, Laboratory reagent
Cyanogen chloride
Adiponitrile, Acetone cyanohydrin, Drugs,
Sodium Cyanide, Cyanuric chloride,
Methionine, Plastics, Pesticides, Bleaches,
Sanitizers, Fumigants
Hydrogen cyanide
Chloropicrin
Fumigants, Rodenticides, Antioxidants 35

36. Examples of Sch 3 Commercial Uses
Flame retardants, Plasticizers, Plastics,
Elastomers, Surfactants, Pesticides,
Lube Oils, Greases, Catalyst
Phosphorus oxychloride
Phosphorus trichloride
Catalyst, Chlorinating agent, Polymers,
Flame retardants, Surfactants, batteries
Phosphorus pentachloride
Insecticides, Adhesives, Polyolefins,
Flame retardants, Other phosphites
Trimethyl phosphite
Pesticides, Plastic additives, Antioxidants,
Flame retardants, Corrosion inhibitors,
Viscosity depressant
Triethyl phosphite
Corrosion Inhibitor, Antioxidant, Stabilizer
Adhesives, Pesticides, Antifungals,
Fire retardants
Dimethyl phosphite 36

37. Examples of Sch 3 Commercial Uses
Catalyst, Antifungals, Insecticides,
Lube oil additives, Color preventative
Diethyl phosphite
Vulcanizing rubber, Lube oil additives,
Antioxidants, Crosslinking, Solvent,
Catalyst
Sulfur monochloride
Chlorinating agent, Antibiotics, Pesticide,
Lube oil additives, Antioxidants,
Funguicide
Sulfur dichloride
Acid chlorides, Herbicides, Insecticides,
Fumigants, Thermoplastics, Surfactants,
Drugs, Vitamins, Dyes, Catalyst, Batteries,
Chlorinating agent, Photography
Thionyl chloride 37

38. Examples of Sch 3 Commercial Uses
Surfactants (cosmetics, detergents,
cleaners)
Gas Purification
Electroplating
Lubricants
Derusting
Pickling steel
Coagulants
Softening agents
Antistatic agents
Synthetic fibers
Flame retardants
Urethanes
Pesticides
Propellants
Ethyldiethanolamine
Methyldiethanolamine
Triethanolamine 38

39. Scheduled Chemicals Schedule 1 - 12 families or individual chemicals
Theoretically over 2 million individual chemicals
approx 950 individual chemicals declared
Traded in very small amounts (often grams or less)
Schedule families or individual chemicals
Theoretically millions of individual chemicals
300 individual chemicals declared
20 regularly traded in moderate volume
Schedule individual chemicals
15 regularly traded - some very large volume
Other 2 not generally traded but produced and used onsite. 39

40. DOC/PSF Chemicals DISCRETE ORGANIC CHEMICAL
Any chemical belonging to the class of chemical compounds consisting of all compounds of carbon except for its oxides, sulfides and metal carbonates, identifiable by chemical name, by structural formula, if known, and by Chemical Abstracts Service registry number, if assigned
PSF-Chemical
Any unscheduled discrete organic chemical containing the elements phosphorus, sulphur or fluorine 40

41. DOC/PSF Chemicals (2)
Vast range of chemicals – interest in capabilities of plants producing them rather than chemicals themselves
Hence no import/export provisions 41

42. Questions ?