CLP CHEMICAL AND PHYSICAL HAZARDS

Transcription

1 31 March 2015 CLP CHEMICAL AND PHYSICAL HAZARDS CLP mengseldag Wim Mak RELEVANT DOCUMENTS Globally Harmonised System of Classification and Labelling of Chemicals, 5 th revised edition, 2013 = UN GHS (the purple book) Regulation (EC) No 1272/2008 = EU GHS = CLP. Guidance on the application of the CLP criteria echa.europa.eu/web/guest/guidance-documents/guidance-on-clp United Nations Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, 5 th revised edition, Wim Mak 1

2 31 March 2015 SCOPE OF THE CLP REGULATION (1) Potentially all substances and mixtures placed on the market fall within the scope of classification under CLP and should be evaluated in order to reach a decision as to whether they should be classified or not. All substances subject to REACH are also subject to classification, even those not placed on the market if they are subject to registration or notification. SCOPE OF THE CLP REGULATION (2) Although CLP does not apply to the transport of dangerous goods, the criteria for classification are intended to be the same in the two systems. A substance or mixture classified in a hazard class which is common to both CLP and the transport legislation will normally be classified the same in both systems. However, the transport classifications do not include all of the GHS categories, so the absence of a transport classification does not mean the substance or mixture should not be classified under CLP. Wim Mak 2

3 31 March 2015 MIXTURES Mixture sum of individual components. Calculation not possible for phys-chem. Strong oxidizer + flammable à explosive or self-reactive. Mixture of organic peroxides may become less thermally stable. Flammable + inert à less flammable. STEPS TO PROPER C&L 1. Identification 2. Old data (from DSD/DPD) 3. External data 4. Desk study 5. Screening tests 6. Classification testing 7. Expert advice Wim Mak 3

4 31 March 2015 EXTERNAL SOURCES OF PHYS-CHEM DATA Books and data: Merck, Beilstein, Lyman, Bretherick, Handbook of Chemistry and Physics. Reviewed literature. Internet data (only use reviewed data!). Do not trust just any Safety Data Sheet on the internet! Software for phys-chem property estimation/calculation (QSPR): Check what the test guideline says about calculation. Check guidance documents. Verify outcome with known data. DESK STUDY / SCREENING TESTS United Nations Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, Appendix 6 Screening procedures. Evaluation on basis of molecular structure and composition. Small-scale tests. Wim Mak 4

5 31 March 2015 CLASSIFICATION TESTING For phys-chem testing, CLP refers to the United Nations Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria. Part I : Explosives. Part II : Self-reactive substances and organic peroxides. Part III : Miscellaneous. UN TEST METHODS (1) Test series 1 to 7: tests for explosive substances and articles. About 40 different methods. Classification of substances and articles into transport class 1 or GHS hazard class explosives. Test series A to H: classification of self-reactive substances and organic peroxides. About 20 different methods. Classification of substances and mixtures into transport class 4.1 or 5.2, or GHS hazard classes self-heating substances and organic peroxides. Wim Mak 5

6 31 March 2015 UN TEST METHODS (2) Test series L: tests for flammable liquids. Classification of substances and mixtures into transport class 3 or GHS hazard class flammable liquids. Test series N: tests for flammable substances etc. Five test methods. Classification of substances and mixtures into transport classes 4.1, 4.2 or 4.3; or GHS hazard classes flammable solids, self-heating substances and mixtures or substances and mixtures which, in contact with water, emit flammable gases. UN TEST METHODS (3) Test series O: tests for oxidizing substances. Classification of substances and mixtures into transport class 5.1 or GHS hazard classes oxidizing solids and oxidizing liquids. Test series C: test for corrosive substances. Classification of substances and mixtures into transport class 8 or GHS hazard classes corrosive substances. UN does not provide test methods for toxicity and eco-toxicity, but refers to general methods and criteria. Wim Mak 6

7 31 March 2015 GENERAL STRUCTURE OF CLP Part 2 comprises criteria etc. for physical hazards. Sixteen hazard classes are included (chapters ). For each chapter: 2.x.1 2.x.2 2.x.3 2.x.4 Definition Classification criteria Hazard communication Decision logic and guidance (Note: decision logic and guidance are formally not part of the harmonized system, but are provided as additional guidance.) HAZARD CLASSES (1) 1. Explosives 2. Flammable gases (including chemically unstable gases) 3. Flammable aerosols 4. Oxidizing gases 5. Gases under pressure 6. Flammable liquids 7. Flammable solids 8. Self-reactives substances and mixtures Wim Mak 7

8 31 March 2015 HAZARD CLASSES (2) 9. Pyrophoric liquids 10. Pyrophoric solids 11. Self-heating substances and mixtures 12. Substances which, in contact with water, emit flammable gases 13. Oxidizing liquids 14. Oxidizing solids 15. Organic peroxides 16. Corrosive to metals HAZARD CATEGORIES Each class is divided into hazard categories (between 1 and 7) Each hazard category has: one symbol one signal word one hazard statement (Hxxx) one or more precautionary statements (Pxxx) Wim Mak 8

9 31 March 2015 EXAMPLE Ethanol Flashpoint = 12 C; boiling point = 76 C Hazard class: flammable liquids Hazard category: 2 Symbol: flame Signal word: danger Hazard statement: H225 (highly flammable liquid and vapour) Fifteen precautionary statements 1. EXPLOSIVES (SUBSTANCES AND ARTICLES) Seven hazard categories. Classification criteria: very complex procedure. Screening on basis of chemical structure, oxygen balance and energy content. UN test series 1 to 8. Difference CLP DSD/DPD: complete. Examples: TNT, munitions, pharmaceuticals. N N N OH CH 2 CH 2 COOC 8 H 17 Wim Mak 9

10 31 March FLAMMABLE GASES Two hazard categories. Classification criteria: flammability range (ISO 10156:2010) Cat 1: LEL<13% or UEL-LEL>12%) Cat 2: any range Examples: methane, hydrogen. 2. CHEMICALLY UNSTABLE GASES Two hazard categories. Classification criteria: chemical instability (able to react explosively even in the absence of air or oxygen). Example: acetylene. Wim Mak 10

11 31 March FLAMMABLE AEROSOLS Two hazard categories. Screening: >1% flammable gas, solid, liquid or >20 kj/g. Classification criteria: ignition tests and heat of combustion. Difference CLP DSD/DPD: new class. Examples: cosmetics. 4. OXIDIZING GASES One hazard category. Classification criteria: oxidizing capability (calculation on basis of ISO 10156:2010), more oxidizing than air. Difference CLP DSD/DPD: new class. Examples: fluorine. Wim Mak 11

12 31 March GASES UNDER PRESSURE Four hazard categories. Classification criteria: definitions on basis of vapour pressure, physical state and critical temperature. Difference CLP DSD/DPD: new class. Examples: nitrogen, carbon dioxide, helium. 6. FLAMMABLE LIQUIDS Four hazard categories. Classification criteria: boiling point, flash point, sustained combustibility. Self-ignition temperature is not relevant. Difference CLP DSD/DPD: no. Examples: acetone, toluene, diesel, alcohols. Flammable = inflammable non-flammable. Example: flashpoint for ethanol/water 100/0 12 C 50/50 24 C 20/80 36 C 10/90 49 C 5/95 62 C Wim Mak 12

13 31 March FLAMMABLE SOLIDS Two hazard categories. Classification criteria: burning rate. Depends on physical state! UN test N.1. Difference CLP DSD/DPD: no. Examples: metal powders. 8. SELF-REACTIVE SUBSTANCES AND MIXTURES Five hazard categories. Classification criteria: very complex procedure. Screening on basis of energy content, etc. UN test series A to H. Difference CLP DSD/DPD: new class. Examples: many organic azo compounds (e.g. dyes). Wim Mak 13

14 31 March PYROPHORIC LIQUIDS One hazard category. Classification criteria: spontaneous ignition in contact with air. Screening on basis of chemical structure. UN test N.2. Difference CLP DSD/DPD: no. Examples: organometallics. 10. PYROPHORIC SOLIDS Two hazard categories. Classification criteria: spontaneous ignition in contact with air. Screening on basis of chemical structure. UN test N.3. Difference CLP DSD/DPD: no. Examples: organometallics. Wim Mak 14

15 31 March SELF-HEATING SUBSTANCES AND MIXTURES Two hazard categories. Classification criteria: self-heating properties according to modified Bowes- Cameron cage test. Depends on ability to react with ambient oxygen. UN test N.4. Difference CLP DSD/DPD: new class. Examples: activated carbon, bone meal, sewage sludge. 12. SUBSTANCES WHICH IN CONTACT WITH WATER, EMIT FLAMMABLE GASES Three hazard categories. Classification criteria: rate of evolution of flammable gases in contact with air. Screening on basis of chemical structure. UN test N.5. Difference CLP DSD/DPD: no. Examples: finely divided metal powders (zinc, magnesium). Wim Mak 15

16 31 March OXIDIZING LIQUIDS Two hazard categories. Classification criteria: capability to enhance burning of a flammable substance. Screening on basis of chemical structure. UN test O.2. Difference CLP DSD/DPD: new class. Examples: nitric acid, periodic acid, concentrated hydrogen peroxide, concentrated aqueous solutions of solid oxidizers. 14. OXIDIZING SOLIDS Three hazard categories. Classification criteria: capability to enhance burning of a flammable substance. Screening on basis of chemical structure. UN test O.1 or O.3. Difference CLP DSD/DPD: different method and criteria. Sodium chlorate, potassium nitrate. Properties depend on particle size. Wim Mak 16

17 31 March ORGANIC PEROXIDES Easily identified: -O-O- Five hazard categories. Classification criteria: very complex procedure. UN test series A to H. Screening on basis of chemical structure and active oxygen content. Difference CLP DSD/DPD: new class. Examples: tert-butyl peroxybenzoate, dicumyl peroxide. 16. CORROSIVE TO METALS One hazard category. Classification criteria: corrosion rate on steel or aluminium. Difference CLP DSD/DPD: no. Examples: several acids. Wim Mak 17

18 31 March 2015 MISSING HAZARD CLASSES Ammonium nitrate based fertilizers. Substances having explosive properties. FROM DSD/DPD TO CLP Differences in classification procedures and criteria vary from virtually none to complete. For several hazard classes, tests and criteria have been taken over from transport regulations. Wim Mak 18

19 31 March 2015 DIFFERENCES BETWEEN CLP AND DSD/DPD (1) No hazard classes and categories in DSD/DPD. In several cases, CLP adopts tests from UN Manual of Tests and Criteria (transport). In the same way, criteria were adopted. Some hazard classes were not recognized at all in the DSD/DPD. Hazard (H) statements and precautionary (P) statements instead of risk (R) phrases and safety (S) phrases. DIFFERENCES BETWEEN CLP AND DSD/DPD (2) In Europe, some R phrases were retained and turned into EUH statements, for instance: R44 à EUH044. DSD/DPD C&L related to the substance only, intrinsic properties. CLP C&L sometimes relates to packaged substances. Wim Mak 19

20 31 March 2015 TRANSLATION FROM DSD/DPD TO CLP (1) In some cases, straightforward translation is possible. In a large number of cases, translation is impossible or difficult and requires expert judgement or additional information (e.g. underlying data). Do NOT trust automatic translation programs! TRANSLATION FROM DSD/DPD TO CLP (2) Wim Mak 20

21 31 March 2015 TRANSLATION FROM DSD/DPD TO CLP (3) E;R2 or E;R3 O;R7 O;R8 (g) O;R8 (l/s) O;R9 (l/s) R10 (l) F;R11 (l/s) à no direct translation possible à organic peroxide CD or EF; H241 or H242 à oxidizing gas; H270 à no direct translation possible à oxidizing liquid or solid; H271 à no direct translation possible à no direct translation possible TRANSLATION FROM DSD/DPD TO CLP (4) F+;R12 (g) F+;R12 (l) F;R15 F;R17 à no direct translation possible à flammable liquid cat. 1; H224 à self-reactive CD or EF; H242 à self-reactive G à no direct translation possible à pyrophoric solid or liquid; H250 Self-ignition temperatures determined under DSD/DPD (92/69/EEC methods A.15 and A.16) cannot be translated to hazard categories. Wim Mak 21

22 31 March 2015 DIFFERENCES BETWEEN CLP AND OTHER REGULATIONS The basis of all regulatory systems is supposed to be the same (UN-GHS). Differences will occur where not all classification systems use all hazard categories (for instance flammable liquids cat. 4). Also other differences may occur, for instance between the different implementations of GHS. GENERAL REMARKS Pitfalls of phys-chem properties are often underestimated, even by experts. Consequences of accidents involving flammability and explosivity can be tremendous. Risks of flammability and explosivity often depend on many factors. Wim Mak 22

23 31 March 2015 NOT ONLY FOR C&L! The potential effects to human health shall be assessed for the following physico-chemical properties: Flammability à burns, asphyxiation, death Explosivity à injury, death Oxidizing properties à burns When a hazard exists, steps should be taken to eliminate or control it. If the hazard cannot be eliminated or reasonably controlled through technical means, appropriate risk management measures should be used to avoid human health hazard. POTENTIAL CONSEQUENCES Wim Mak 23

24 31 March 2015 QUESTIONS? 47 Wim Mak 24