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Identification of Seveso Sites: Practical Approach

Identification of Seveso Sites: Practical Approach. Preparation of list of industrial activities. Possible sources of information Register of hazardous activities Inventories of establishments working with hazardous substances Register of IPPC sites Inspection reports Other sources.

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Identification of Seveso Sites: Practical Approach

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  1. Identification of Seveso Sites:Practical Approach

  2. Preparation of list of industrial activities Possible sources of information • Register of hazardous activities • Inventories of establishments working with hazardous substances • Register of IPPC sites • Inspection reports • Other sources

  3. Exclusions Article 4 of the directive • military establishments, installations or storage facilities; • hazards created by ionizing radiation; • the transport of dangerous substances and intermediate temporary storage by road, rail, internal waterways, sea or air, outside the establishments, including loading and unloading and transport to and from another means of transportation at docks, wharves or marshalling yards; • the transport of dangerous substances in pipelines, including pumping stations outside the establishments; • the exploration, extraction and processing of minerals in mines, quarries, or by means of boreholes, with the exception of chemical and thermal processing operations and storage related to those operations which involve dangerous substances; • the offshore exploration and exploitation of minerals, including hydrocarbons; • waste landfill sites, with the exception of operational tailings disposal facilities, including tailing ponds or dams, containing dangerous substances, in particular when used in connection with the chemical and thermal processing of minerals.

  4. Seveso does not apply Yes Lower than lower tier Excluded sector? (Article 4) No What is the quantity of dangerous substances?(Annex I) Quantity above the lower threshold • Notification • Major accident prevention policy (MAPP) • Domino effects • Land-use planning • Inspection Quantity above the higher threshold Exclusions • Additionally: • Safety report (including MAPP and safety management system) • Emergency plans (internal and external) • Information to the public

  5. Classification of a Seveso site Step 1 – gathering information on all substances at the site • Step-by-step approach • Including all installations within the establishment • Storage facilities • Production facilities • Loading and distributing facilities • Including all chemicals in the establishment • Raw materials • Intermediates • Byproducts • Finished products • Substances built during chemical reactions or by an accident

  6. Structure of Annex I • Part I – Named substances • Substances of high concern /TDI, Methyl isocyanide, phosgene, chlorine/ • Widely used substances /ammonium nitrate, LPG, petroleum products/ • Part II - 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. • Explanatory Notes

  7. Classification of a Seveso site Step 2 – hazardous chemicals meeting the criteria of Annex I • Classification according the physical, chemical and toxicological properties • The EU chemical legislation • CLP Directive 67/548/EEC until • 2010 for substances • 2015 for preparations/mixtures • GHS Regulation (EC) No. 1272/2008 • New classification rules • Downstream effect • Data from the operator • Even if the substance does not have EU harmonised classification as a dangerous substance, due to its properties it still can be dangerous according p. 1 of Annex I of the Directive The classification of the substances and preparations at the site is a responsibility of the operator!

  8. Classification of a Seveso site Step 2 – hazardous chemicals meeting the criteria of Annex I • International Sources of information • MSDS of the chemicals • ILO Database - http://www.ilo.org/public/english/protection/safework/cis/products/icsc/index.htm • Other recognised sources • Classlab – The JRC of the EU database – http://ecb.jrc.it/classification-labelling/search-classlab/ • Based on Annex I of Directive 67/548/EEC • Gives Seveso classes -> connection to Annex I of the Convention • ESIS database - The JRC of the EU database – http://ecb.jrc.it/esis/ • Substances produced or marketed in the EU • For HPVC and/or substances of high concern – IUCLID dossier with relevant toxicological and physicochemical properties - http://ecb.jrc.it/esis/index.php?PGM=dat • Local legislation for classification of hazardous chemicals • ADR (GHS) Classification of the chemicals - http://www.unece.org/trans/danger/publi/ghs/ghs_welcome_e.html • Other sources • Toxicological properties scientific reports • Physicochemical properties scientific reports • Modeling software - EPISUITE • Websites – Chemfinder, Chemindustry.com, etc. • Industry experience

  9. Classification of a Seveso site Step 2 – Determining the maximum amounts of the hazardous substances • For gaseous and liquid chemicals – the storage and production capacities • For solid chemicals – the amount needed for 100% production capacity, including reserves

  10. Classification of a Seveso site Step 2 – Determining the threshold quantities for the dangerous substances • For named substances • Threshold quantities in Columns 2 and 3 of Part 1 of Annex I • If in preparations • Recalculation to pure substances • As long as the preparations posses hazardous properties

  11. Ammonium Nitrate • Thresholds – 5 000/10 000, 1250/5000 350/2500 10/50 • Identification • CAS No – 6484-52-2 • EC No – 240-827-6 • Hazard Classification • Oxidising, decomposes at 210°C, with evolution of toxic fumes of nitrogen oxides, it may explode under confinementand high temperatures, forms heat or shock sensitive explosivemixtures with a wide range of substances (e.g. organic fuel, powdered metals, aceticacid, sugar), can react vigorously with reducing materials, ignites on contact with anumber of substances, for instance sodium chloride. • Uses • Production of fertilisers and explosives.

  12. Potassium Nitrate • Threshold –5000/10000, 1250/5000 • 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.

  13. Chlorine • Threshold – 10/25 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.

  14. Bromine • Threshold – 20/100 t. • Identification • CAS No –7726-95-6 • EC No –231-599-9 • Hazard Classification • May be fatal if inhaled. Highly toxic by inhalation, ingestion or skin contact. Causes severe burns. Lachrymator. • Uses • Flame retardant, gasoline additive, pesticide production, manufacture of dyes, agrichemicals, and pharmaceuticals , Water purification compounds, Disinfectants .

  15. Formaldehyde (conc.  90 %) • Threshold – 5/50 t. • Identification • CAS No: 50-00-0 EC No: 200-001-8 • Hazard Classification • Causes burns. Very toxic by inhalation, ingestion and through skin absorption. Readily absorbed through skin. Probable human carcinogen. Mutagen. May cause damage to kidneys. May cause allergic reactions. May cause sensitisation. May cause heritable genetic damage. Lachrymator at levels from less than 20 ppm upwards. Very destructive of mucous membranes and upper respiratory tract, eyes and skin. • Uses • Production of resins, paints, explosives, disinfectants and biocides

  16. Ethylene Oxide • Threshold – 5/50 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.

  17. Hydrogen • Threshold – 5/50 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.

  18. Toluene diisocyanate • Threshold – 10/100 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

  19. Sulphur Trioxide • Threshold – 15/75 t. • Identification • CAS No – 7446-11-9 • EC No – 231-197-3 • Hazard Classification • Oxidising agent, toxic by inhalation and corrosive to skin, eyes andmucous membranes, fire risk in contact with organic materials, combines with water, forming sulphuric acid and evolving light and a largeamount of heat. Violent reactions also with e.g. acetonitrile, formamide, dimethylsulphoxide, iodine, metal oxides. • Uses • Sulphonation of organic compounds, especially nonionic detergents, and for solar energy collectors.

  20. Lead Alkyls • Threshold – 5/50 t. • Identification • Triethyl lead, tetraethyl lead and tetramethyl lead • Hazard Classification • toxic to the central nervoussystem, cumulative poison, experimentalteratogens 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

  21. Phosgene • Threshold – 0,3/0,75 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.

  22. 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.

  23. Liquefied extremely flammable gases (including LPG) and natural gas • Threshold – 50/200 t. • 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.

  24. Petroleum products: gasolines and naphthas; kerosenes (jetfuels); gas oils (diesel fuels, home heating oils and gas oil blendingstreams) • Threshold – 2500/25000 t. • Identification • Complex mixtures of hydrocarbons • Concawe Guidance Notes • Hazard Classification • Flammable, Toxic for the environment • Uses • Fuels and solvents

  25. Classification of a Seveso site Step 2 – Determining the threshold quantities for the dangerous substances • For categories of substances and preparations not specifically named in Part 1 of Annex I • Threshold quantities in Columns 2 and 3 of Part 2 of Annex I • If multiple classifications – the lowest threshold • If in preparations • As long as the preparations posses the hazardous properties mentioned • Specific concentrations • Generic concentrations • CLP Directives, to be replaced by the GHS C&L Regulation

  26. Examples • Examples on identification of dangerous substance within the scope of Annex I Parathion-methyl CAS No 298-00-0 • Used as pesticide • ESIS Data • General classification • Classlab Data • specific concentration limits • IUCLID Data • LD50 and LC50 data – 4 mg/kg oral toxicity • Annex I classification – very toxic (LD50 < 25 mg/kg)

  27. ESIS Data for Parathion-methyl CAS No 298-00-0

  28. Classlab Data for Parathion-methyl CAS No 298-00-0

  29. IUCLID Data for Parathion-methyl CAS No 298-00-0

  30. Example Parathion-methyl CAS No 298-00-0 • Seveso substance • substance not specifically named in Part 1 of Annex I • Very toxic – threshold quantities 5/25 t • Specific concentration limits – classification varies

  31. Classification of a Seveso site Step 3 – Addition rule • For generic substances with similar properties • Toxicity, flammability, and eco-toxicity: • substances and preparations named in Part 1 and classified as toxic or very toxic, together with substances and preparations falling into categories 1 or 2; • substances and preparations named in Part 1 and classified as oxidising, explosive, flammable, highly flammable, or extremely flammable, together with substances and preparations falling into categories 3, 4, 5, 6, 7a, 7b or 8; • substances and preparations named in Part 1 and classified as dangerous for the environment (R50 (including R50/53) or R51/53), together with substances and preparations falling into categories 9(i) or 9(ii); • Classify if the Sum Σ = q1/QU1 + q2/QU2 + q3/QU3 + q4 /QU4 + q5/QU5 +... ≥ 1 • Q – threshold quantity for a substance, q – quantity of a substance present • First for lower tier, if Σ≥1, for upper tier

  32. Classification of a Seveso site Step 3 – Addition rule • Example • Chemical plant • Hazardous substances onsite • Chlorine (Part 1 of Annex I, ), R23 R36 R37 R38 R50– 5 t. • Propylene oxide, (Part 1 of Annex I, ), R12 R20 R21 R22 R36 R37 R38 R45 R46 – 3 t. • Epichlorhydrin (generic substance) R10R23/24/25 R34 R43 R45 – 25 t. • Chlorobenzene (generic substance) R10 R20 R21 R22 R51/53100 t. • Perchloroethylene (generic substance) R40 R51/53280 t.

  33. Classification of a Seveso site Step 3 – Addition rule • Toxicity • Chlorine and Epichlorhydrin • Addition rule lower tier 5/10 + 25/50 = 1 • Addition rule upper tier 5/25 + 25/200 = 0.325 < 1 • The establishment is a lower tier Seveso site (for now) for toxic substances • Flammability • Propylene oxide, Epichlorhydrin and Chlorobenzene • Addition rule lower tier 3/5 + 25/5000 + 100/500 = 0.603 < 1 • The establishment is not a Seveso site (for now) for flammable substances • Eco-toxicity • Chlorine, chlororbenzene and perchloroethylene • Addition rule lower tier 5/10 + 100/200 + 300/200 = 2.5 • Addition rule upper tier 5/25 + 100/500 + 300/500 = 1 • The establishment is an upper tier Seveso site for ecotoxic substances The establishment is an upper tier Seveso site!

  34. Classification of a Seveso site The 2 % Rule • Dangerous substances present at an establishment only in quantities equal to or less than 2 % of the relevant qualifying quantity shall be ignored for the purposes of calculating the total quantity present if their location within an establishment is such that it cannot act as an initiator of a major accident elsewhere on the site • Two qualifying criteria • 2% of the total quantity • Location of the substance

  35. Classification of a Seveso site The 2 % Rule - Examples • Example 1 • Chlorine storage • A tank of 4t and two storage areas for chlorine bottles for 0.05t and 0.02 t respectively • The bigger tank is in the south corner of the site • The storage areas are adjacent to each other, but are remote from the main tank, unable to interact • (0.05 + 0.02)/5 = 1.4 % - less than 2% • The establishment is not a Seveso site

  36. Classification of a Seveso site The 2 % Rule - Examples • Example 2 • LPG storage • A tank of 49t and two smaller tanks for 1t each • The bigger tank is in the centre of the site • The smaller tanks are adjacent to each other, but are remote from the main tank, unable to interact • (1 + 1)/50 = 4 % - more than 2% • The establishment is a Seveso site

  37. Classification of a Seveso site The 2 % Rule - Examples • Example 3 • LPG storage • A tank of 49t and two smaller tanks for 1t each • The bigger tank is in the centre of the site • The smaller tanks are remote from each other and are remote from the main tank, unable to interact • For each small tank 1)/50 = 2 % - equal to 2% • The establishment is not a Seveso site

  38. Bulgarian Experience in the Identification of Dangerous Substances • Started 1999 • Elaboration of national framework and subsequent legislation • 2002 – Environmental Protection Act • Classification of hazardous activities is a duty of the operator • 2000 – Chemicals Act • Gives classification criteria • Elaboration of inventory of possible hazardous activities • Based on inspection results, lists of controlled sites, feedback from industry • Exclusion of establishments and activities out of the scope of the Convention

  39. Bulgarian Experience in the Identification of Dangerous Substances • 2000 - 2002 • Seminars and workshops with the Industry • Result – Classification manual

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