Identification of Hazardous Activities Identification of hazardous activities - requirements and link to the SEVESO II Directive

Identification of Hazardous Activities

 For the purpose of implementing the Convention hazardous activities have to be identified  Legal basis – Article 4(1) - the Party … shall take measures, as appropriate, to identify hazardous activities within its jurisdiction  Article 1(b) - “Hazardous activity” means any activity in which one or more hazardous substances are present or may be present in quantities at or in excess of the threshold quantities listed in Annex I hereto, and which is capable of causing transboundary effects  Combination of two criteria  Quantity of hazardous substances over predefined thresholds  Possibility of transboundary effects Identification of Hazardous Activities

Hazardous substances and respective thresholds – Annex I  Generic hazard categories  Named substances  Possibility of transboundary effects  Consequence assessment according national requirements  Guidelines to facilitate the identification of hazardous activities for the purposes of the Convention (Guidelines for Location Criteria) (decision 2000/3 in ECE/CP.TEIA/2, annex IV)  Subject to consultation Identification of Hazardous Activities

 There should be mechanisms for: Collection of data on hazardous substances from operators Analysis and validation of data by the Competent Authority Review/update of data  Including evaluating potential transboundary effects! Annex I of the Convention and Annex I of the SEVESO II Directive

 Annex I to the Convention and Annex I to the Seveso II Directive, define substances and threshold qualties (qualifying criteria)  Hazard categories and named hazardous substances  There is difference in the structure and scope of both Annexes! Structure of Annex I of the Structure of Annex I of the Convention SEVESO II Directive

Part I – Categories of substances and Part I – Named substances preparations not specifically

named in Part II

28 Named substances – Substances of high concern /TDI, Methyl isocyanate, Phosgene, Chlorine, Dioxins, Nickel compounds, etc./ Widely used substances /Ammonium nitrate, Part II – Named substances LPG, Petroleum products/

12 Named substances – Part II - Categories of substances Substances of high concern /TDI, Methyl isocyanate, and preparations not specifically Phosgene, Chlorine/ Widely used substances /Ammonium nitrate, named in Part I LPG, Petroleum products/

Annex I of the Convention

Where a substance or preparation named in Part II also falls within a category in Part I, the threshold quantity set out in Part II shall be used

Annex I of the SEVESO II Directive

Where a substance or group of substances listed in Part I also falls within a category of Part II, the qualifying quantities set out in part I must be used Qualifying quantities

Annex I of the Annex I of the SEVESO Convention II Directive

Column 2 (Qualifying quantity) "lower tier "

Column 3 One Column (Qualifying quantity) (Threshold Quantity) " upper tier "

Threshold quantities in Part I and Part II of Annex I of the Convention are in compliance with adequate threshold quantities in Column 3 of Part 1 and Part 2 of Annex I of the SEVESO II Directive (upper-tier establishments) Reservation

 The EC reserves the right as concernes the threshold quantities mentioned in Annex I, Part I, Nos 4, 5 and 6 to the Convention, to apply threshold quantities of 100 tonnes for bromine (very toxic substance), 5000 tonnes for methanol (toxic substance) and 2000 tonnes for oxygen (oxidising substance). Conclusion

 The scope of the Convention follows one-tier approach

 The scope of the Seveso II Directive follows a two-tier approach

 According to Council Decision 98/685/EC of 23 March 1998, for EU member States all establishments covered by article 9 of Council Directive 96/82/EC of 9 December 1996 (Seveso II), i.e. upper-tier establishments, are taken to meet substance and quantity criteria under the Convention.

Two harmonised approaches for the same aim - identification of hazardous activities. Identification of Hazardous Activities – Annex I Structure of Annex I

Part I - Categories of substances and preparations not specifically named in Part II Based on generic toxicological, physical-chemical or ecotoxicological properties

Characteristic endpoints – LD50, LC50, EC50, flashpoint, etc. Part II – Named substances Substances of high concern /TDI, Methyl isocyanide, phosgene, chlorine/ Widely used substances /ammonium nitrate, LPG, petroleum products/  Explanatory Notes History of Annex I

 Introduced with temporary thresholds Amended in 2008 Introduction of single threshold quantities Harmonization with Annex I of the Seveso II Directive Need for second revision Transition to the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) Alignment with the Seveso III Directive Part I – Categories of substances and preparations not specifically named in Part II (Annex I of the Convention)

Category Threshold Quantity (Tones) 1. Flammable (note 2) 50 000 2a. Highly flammable (note 3a and b) 200 2b. Highly flammable (note 3c) 50 000 3. Extremely flammable (note 4) 50 4. Toxic (note 5) 200 5. Very toxic (note 6) 20 6. Oxidizing (note 7) 200 7a. Explosive, where the substance, preparation or article 200 falls under Division 1.4 of the GHS criteria (note 8) 7b. Explosive, where the substance, preparation or 50 article falls under Division 1.1, 1.2, 1.3, 1.5 or 1.6 of the GHS criteria (note 8) 8a. Dangerous for the environment – “Toxic to 500 aquatic organisms” (note 9) 8b. Dangerous for the environment – “Very 200 toxic to aquatic organisms” (note 10) Part II – Named substances (Annex I of the Convention) Substance Threshold Quantity (Tones) 1. Ammonium nitrate (note 11,12,13,14) 10.000/5.000/2.500/50 2. Potassium nitrate (note 15,16) 10.000/5.000 3. Chlorine 25 4. Ethylene oxide 50 5. Hydrogen 50 6. Toluene diisocyanate 100 7. Sulfur-trioxide 75 8. Lead alkyls 50 9. Phosgene 0,75 10. Methyl isocyanate 0,15 11. Liquefied extremely flammable gases (including 200 LPG) and natural gas 12. Petroleum products: gasolines and naphthas; 25.000 kerosens (including jet fuels); gas oils (including diesel fuels, home heating oils and gas oil blending streams) Annex I, Part 1 Annex I – Categories of substances and preparations

PART I. Categories of substances and preparations not specifically named in Part II No Category Threshold Quantity (metric tons) 1. Flammable2 50,000 2a. Highly flammable3(a) and (b) 200 2b. Highly flammable3(c) 50,000 3. Extremely flammable4 50 4. Toxic5 200 5. Very toxic6 20 6. Oxidizing7 200 7a. Explosive, where the substance, preparation or article falls under 200 Division 1.4 of the GHS criteria8 7b. Explosive, where the substance, preparation or article falls under 50 Division 1.1, 1.2, 1.3, 1.5 or 1.6 of the GHS criteria8 8a. Dangerous for the environment – “Toxic to aquatic organisms”9 500 8b. Dangerous to the environment – “Very toxic to aquatic organisms”10 200 Flammable

– LIQUID substances and preparations having a flash point equal to or greater than 21°C and less than or equal to 55°C, supporting combustion – Long chain and/or aromatic hydrocarbons and derivates thereof • xylene, styrene • dibutyl ether • di-n-butylamine – About 130 entries – Solvents, raw materials and intermediates in the chemical industry, paints, etc. Highly Flammable – LIQUIDS – (a) Substances and preparations which may become hot and finally catch fire in contact with air at ambient temperature without any input of energy (are spontaneously flammable in air); – (b) Substances and preparations, which have a flashpoint lower than 55°C and remain liquid under pressure, where particular processing conditions, such as high pressure or high temperature, may create major accident hazards; and – (c) Substances and preparations having a flash point lower than 21°C and which are not extremely flammable. – Shorter chain and/or lower molecular mass liquids • carbon disulphide, heptane, toluene Extremely Flammable – Gaseous and Liquid State – (a) Liquid substances and preparations which have a flash point lower than 0°C and whose boiling point (or, in the case of a boiling range, initial boiling point) at normal pressure is less than or equal to 35°C; – (b) Gases which are flammable in contact with air at ambient temperature and pressure, and which are in a gaseous or supercritical state; and – (c) Flammable and highly flammable liquid substances and preparations maintained at a temperature above their boiling point. – Gaseous methane, propane, butane, hydrogen, diethyl ether, ethylene oxide Toxic – Substances with properties corresponding to those in table 1 or table 2 and having physical and chemical properties capable of creating industrial accident hazards TABLE 1 LD50(oral)(1) LD50(dermal)(2) LC50(3) mg/kg body weight mg/kg body weight mg/l (inhalation) 25 < LD50 < 200 50 < LD50 < 400 0.5 < LC50 < 2 (1) LD50 oral in rats (2) LD50 dermal in rats or rabbits (3) LC50 by inhalation (four hours) in rats

TABLE 2 Discriminating dose mg/kg body weight = 5 where the acute oral toxicity in animals of the substance has been determined using the fixed-dose procedure •About 420 entries •Endpoints - lethal dose or lethal concentration •No single value – if differing LD50 values are available, take the lowest! •It is up to the operator to prove hazardous properties – substances with propertiesVery corresponding Toxic to those in table 3 or table 4 and which, owing to their physical and chemical properties, are capable of creating industrial accident hazards

TABLE 3

LD50(oral)(1) LD50(dermal)(2) LC50(3) mg/kg body weight mg/kg body weight mg/l (inhalation) LD50 < 25 LD50 < 50 LC50 < 0.5 (1) LD50 oral in rats (2) LD50 dermal in rats or rabbits (3) LC50 by inhalation (four hours) in rats

TABLE 4 Discriminating dose mg/kg body weight < 5 where the acute oral toxicity in animals of the substance has been determined using the fixed-dose procedure. •About 235 entries •Endpoints - lethal dose or lethal concentration •No single value – if differing LD50 values are available, take the lowest! •It is up to the operator to prove hazardous properties Oxidizing

– substances which give rise to highly exothermic reactions when in contact with other substances, particularly flammable substances – About 235 entries – Oxygen, peroxides, nitric acid

Explosives

– (a) Substances or preparations which create the risk of an explosion by shock, friction, fire or other sources of ignition; – (b) Substances or preparations which create extreme risks of explosion by shock, friction, fire or other sources of ignition; or – (c) Substances, preparations or articles covered by Class 1 of the European Agreement concerning the International Carriage of Dangerous Goods by Road (UN/ADR), concluded on 30 September 1957, as amended. Explosives

– 2 subgroups • Explosive, where the substance, preparation or article falls under Division 1.4 of the GHS criteria – 200 – Substances and articles which present only a slight risk in the event of ignition or initiation during carriage. The effects are largely confined to the package and no projection of fragments of appreciable size or range is to be expected. An external fire shall not cause virtually instantaneous explosion of virtually the entire contents of the package • Explosive, where the substance, preparation or article falls under Division 1.1, 1.2, 1.3, 1.5 or 1.6 of the GHS criteria – 50 – Mass explosion, blast or projection hazard – Commercial and military explosives, detonators Dangerous for the environment – “Toxic to aquatic organisms” toxic to aquatic organisms with long-term adverse effects in the aquatic environment with: (a) Acute toxicity: (i) 96 hr LC50 (for fish): 1 mg/l < LC50 ≤ 10 mg/l, or (ii) 48 hr EC50 (for daphnia): 1 mg/l < EC50 ≤ 10 mg/l, or (iii) 72 hr IC50 (for algae): 1 mg/l < IC50 ≤ 10 mg/l; and (b) Persistency: the substance is not readily degradable or the log Pow (log octanol/water partition coefficient) ≥ 3.0 (unless the experimentally determined bio-concentration factor BCF ≤ 100). Over 800 entries Dangerous to the environment – “Very toxic to aquatic organisms” (a) Substances very toxic to aquatic organisms, with acute toxicity: (i) 96 hr LC50 (for fish) ≤ 1 mg/l, or (ii) 48 hr EC50 (for daphnia) ≤ 1 mg/l, or (iii) 72 hr IC50 (for algae) ≤ 1 mg/l (b) Substances very toxic to aquatic organisms with long-term adverse effects in the aquatic environment with: (i) Acute toxicity: - 96 hr LC50 (for fish) ≤ 1 mg/l, or - 48 hr EC50 (for daphnia) ≤ 1 mg/l, or - 72 hr IC50 (for algae) ≤ 1 mg/l; and (ii) Persistency: the substance is not readily degradable or the log Pow (log octanol/water partition coefficient) ≥ 3.0 (unless the experimentally determined bio-concentration factor BCF ≤ 100).

Nearly 400 entries Annex I, Part 2 Annex I – Named Substances

Substance Threshold Ammonium nitrate 10,000/5,000/2,500/50 Potassium nitrate 10,000/5,000 Chlorine 25 Ethylene oxide 50 Hydrogen 50 Toluene diisocyanate 100 Sulphur trioxide 75 Lead alkyls 50 Phosgene 0.75 Methyl isocyanate 0.15 Liquefied extremely flammable gases (including LPG) and 200 natural gas Petroleum products: gasolines and naphthas; kerosenes 25,000 (including jet fuels); gas oils (including diesel fuels, home heating oils and gas oil blending streams) – Threshold – 10,000/5,000/2,500/50 t. – Identification • CAS No – 6484-52-2 • EC No – 240-827-6 – Hazard ClassificationAmmonium Nitrate • Oxidising, decomposes at 210°C, with evolution of toxic fumes of nitrogen oxides, it may explode under confinement and high temperatures, forms heat or shock sensitive explosive mixtures with a wide range of substances (e.g. organic fuel, powdered metals, acetic acid, sugar), can react vigorously with reducing materials, ignites on contact with a number of substances, for instance sodium chloride. – Uses • Production of fertilisers and explosives. Potassium Nitrate

– Threshold – 10,000/5,000 t. – Identification • CAS No – 7757-79-1 • EC No – 231-818-8 – Hazard Classification • Strong oxidizer, Harmful if swallowed, May cause reproductive disorders. – Uses • Fertilizer, Food preservation, fire stabilizer, heat treatment of metals, Glass industry. Chlorine – Threshold – 25 t. – Identification • CAS No – 7782-50-5 • EC No – 231-959-5 – Hazard Classification • Toxic by inhalation, Irritating to eyes, respiratory system and skin, Very toxic to aquatic organisms. – Uses • manufacture of synthetic rubber and plastics (polyvinyl chloride, neoprene), chlorinated hydrocarbons, hydrogen chloride, metallic chlorides, also used for water purification, in processing of food and in shrinkproofing wool. Ethylene Oxide

– Threshold – 50 t. – Identification • CAS No – 75-21-8 • EC No – 200-849-9 – Hazard Classification • May cause cancer, May cause heritable genetic damage, Extremely flammable, Toxic by inhalation, Irritating to eyes, respiratory system and skin. – Uses • chemical intermediate for ethylene glycol (intermediate for the manufacture of polyester), nonionic surfactants, glycol ethers, ethanolamines, triethylene glycol and polyethylene glycol, used as a fumigant for foodstuffs and textiles, for sterilising instruments and as an agricultural fungicide. Hydrogen – Threshold – 50 t. – Identification • CAS No – 133-74-0 • EC No - 215-605-7 – Hazard Classification • Extremely flammable – Uses • Production of ammonia and methanol, hydrocracking, hydroforming and hydrofining of petroleum, hydrogenation of vegetable oils, hydrogenolysis of coal, reducing agent for organic synthesis and metallic ores, as oxyhydrogen flame for high temperatures, making hydrochloric and hydrobromic acids. In liquid form is used as coolant and missile fuel. Toluene diisocyanate

– Threshold – 100 t. – Identification • CAS No – 91-08-7, 584-84-9, 26471-62-5 • EC No – 202-039-0, 209-544-5, 247-722-4 – Hazard Classification • Very toxic, Irritating to eyes, respiratory system and skin, Limited evidence of a carcinogenic effect, May cause sensitization by inhalation and skin contact, Harmful to aquatic organisms, may cause long-term adverse effects in the aquatic environment. • Explosive in the form of vapour when exposed to heat or flame, when heated to decomposition it emits toxic fumes of nitrogen oxides. – Uses • manufacture of polyurethane foams, elastomers and coatings. Crosslinking agent for nylon 6 Sulphur Trioxide – Threshold – 75 t. – Identification • CAS No – 7446-11-9 • EC No – 231-197-3 – Hazard Classification • Oxidising agent, toxic by inhalation and corrosive to skin, eyes and mucous membranes, fire risk in contact with organic materials, combines with water, forming sulphuric acid and evolving light and a large amount of heat. Violent reactions also with e.g. acetonitrile, formamide, dimethyl sulphoxide, iodine, metal oxides. – Uses • Sulphonation of organic compounds, especially nonionic detergents, and for solar energy collectors. Lead Alkyls

– Threshold – 50 t. – Identification • Triethyl lead, tetraethyl lead and tetramethyl lead – Hazard Classification • toxic to the central nervous system, cumulative poison, experimental teratogens and have effects on reproduction, When heated to decomposition they emit toxic lead fumes. – Uses • used as octane enhancers for petrols, also in ethylation operations Phosgene

– Threshold – 0,75 t. – Identification • CAS No – 75-44-5 • EC No – 200-870-3 – Hazard Classification • Very toxic by inhalation, Causes burns. – Uses • Chemical intermediate for toluene diisocyanate, methyl isocyanate, diphenylmethane-4,4’-diisocyanate, chloroformate esters, diethyl carbonate, dimethyl carbamoyl chloride, polymethylene polyphenylisocyanate, polycarbonate resins. Also used for manufacture of dyes, pesticides and herbicides. Methyl Isocyanide – Threshold – 0,15 t. – Identification • CAS No – 624-83-9 • EC No - 215-605-7 – Hazard Classification • Highly flammable, Harmful by inhalation, Harmful in contact with skin, Harmful if swallowed. Reacts violently with e.g. water (polymerisation, exothermic reactions). Container may explode violently in heat of fire. When heated to decomposition, hydrogen cyanide, nitrogen oxides and carbon oxides may be produced. – Uses • intermediate in the manufacturing of N-methylcarbonate ester and N-methylurea insecticides and herbicides. Liquefied extremely flammable gases (including

– Threshold – 200LPG) t. and natural gas – Identification • LPG: colourless flammable, noncorrosive, nontoxic gas obtained as a by- product in petroleum refining or natural petroleum manufacture, e.g. butane, propane, propene and their mixtures. • Natural gas: colourless flammable, asphyxiant gas composed of 85% methane, 10% ethane, the balance being made up of propane, butane and nitrogen. – Hazard Classification • Extremely flammable, Risk of fire and explosion. – Uses • LPG: domestic, industrial and automotive fuel, in welding, brazing and metal cutting, and as an intermediate. • Natural gas: fuel and cooking gas, in ammonia synthesis, petrochemical feedstocks, carbon black manufacture. Petroleum products: gasolines and naphthas; kerosenes (jet fuels); gas oils (diesel fuels, home heating oils and gas oil blending streams) – Threshold – 25000 t. – Identification • Complex mixtures of hydrocarbons • Concawe Guidance Notes – Hazard Classification • Flammable, Toxic for the environment – Uses • Fuels and solvents Thank you for your attention!

Nikolay Savov Assistance Programme Manager Convention on Transboundary Effects of Industrial Accidents UNECE, Geneva Tel: +41 22 917 1980 email: [email protected]