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Differences between DSD and CLP

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GHS<br />

New legislation on classification <strong>and</strong><br />

labelling


Preface<br />

2


Table of contents<br />

Preface ................................................................................................................................. 2<br />

Table of contents ................................................................................................................. 3<br />

Introduction/Background .................................................................................................... 6<br />

Building blocks ............................................................................................................... 6<br />

Difference <strong>between</strong> UN <strong>and</strong> EU ................................................................................. 7<br />

Part of UN but not part of EU ..................................................................................... 7<br />

Part of EU but not part of UN ..................................................................................... 8<br />

Downstream legislation .................................................................................................. 8<br />

Classification criteria .......................................................................................................... 9<br />

Physical hazards .............................................................................................................. 9<br />

Explosives ................................................................................................................. 11<br />

Flammable gases ....................................................................................................... 11<br />

Flammable aerosols .................................................................................................. 11<br />

Oxidizing gases ......................................................................................................... 11<br />

Gases under pressure ................................................................................................. 11<br />

Flammable liquids ..................................................................................................... 11<br />

Flammable solids ...................................................................................................... 12<br />

Self-reactive substances <strong>and</strong> mixtures ...................................................................... 12<br />

Pyrophoric liquids ..................................................................................................... 12<br />

Pyrophoric solids ...................................................................................................... 12<br />

Self-heating substances <strong>and</strong> mixtures ....................................................................... 12<br />

Substances <strong>and</strong> mixtures which in contact with water emit flammable gases .......... 12<br />

Oxidizing liquids ....................................................................................................... 12<br />

Oxidizing solids ........................................................................................................ 12<br />

Organic peroxides ..................................................................................................... 13<br />

Corrosive to metals ................................................................................................... 13<br />

Health hazards ............................................................................................................... 14<br />

Acute toxicity ............................................................................................................ 15<br />

Skin corrosion/irritation ............................................................................................ 15<br />

Serious eye damage/eye irritation ............................................................................. 15<br />

Respiratory or skin sensitisation ............................................................................... 15<br />

Germ cell mutagenicity ............................................................................................. 15<br />

Carcinogenicity ......................................................................................................... 15<br />

Reproductive toxicity ................................................................................................ 15<br />

Specific target organ toxicity (STOT) – single exposure ......................................... 15<br />

Specific target organ toxicity (STOT) – repeated exposure ..................................... 15<br />

Aspiration hazard ...................................................................................................... 16<br />

Environmental hazards. ................................................................................................. 17<br />

Hazardous for the ozone layer. ................................................................................. 17<br />

<strong>Differences</strong> <strong>between</strong> <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> ................................................................................. 18<br />

Physical hazards ............................................................................................................ 18<br />

Flammable liquids ..................................................................................................... 18<br />

Health hazards ............................................................................................................... 20<br />

Acute toxicity – inhalation ........................................................................................ 20<br />

3


Acute toxicity – dermal ............................................................................................. 20<br />

Acute toxicity – oral .................................................................................................. 20<br />

Skin corrosion/irritation ............................................................................................ 20<br />

Eye damage/Eye irritation ......................................................................................... 21<br />

Sensitisation .............................................................................................................. 21<br />

Mutagenicity ............................................................................................................. 21<br />

Carcinogenicity ......................................................................................................... 21<br />

Reproductive toxicity ................................................................................................ 22<br />

STOT, single exposure .............................................................................................. 22<br />

STOT, repeated exposure .......................................................................................... 22<br />

Environmental hazards .................................................................................................. 23<br />

Classification of substances .............................................................................................. 24<br />

Classification of mixtures ................................................................................................. 24<br />

Bridging Principles ....................................................................................................... 24<br />

Dilution ..................................................................................................................... 25<br />

Batching .................................................................................................................... 25<br />

Concentration of highly hazardous mixtures ............................................................ 25<br />

Similar mixtures ........................................................................................................ 26<br />

Changes in compositions .......................................................................................... 27<br />

Aerosols .................................................................................................................... 27<br />

Calculation principles ................................................................................................... 28<br />

Cut-off values ............................................................................................................ 28<br />

Acute toxicity ............................................................................................................ 28<br />

Classification based on concentration thresholds ..................................................... 31<br />

Labelling ........................................................................................................................... 38<br />

Labelling of unclassified mixtures ................................................................................ 38<br />

Content of the label ....................................................................................................... 39<br />

Hazard Pictograms ........................................................................................................ 39<br />

Principles of precedence for hazard pictograms ....................................................... 41<br />

Signal words .................................................................................................................. 41<br />

Hazard statements ......................................................................................................... 42<br />

Additional EU-statements ......................................................................................... 42<br />

Precautionary statements .............................................................................................. 43<br />

Product identifiers ..................................................................................................... 45<br />

Supplemental information ......................................................................................... 45<br />

Special rules for packaging not exceeding 125 ml ................................................... 45<br />

Language ....................................................................................................................... 47<br />

Format of a label ........................................................................................................... 47<br />

Outer <strong>and</strong> inner packaging ............................................................................................ 47<br />

Transport regulation <strong>and</strong> <strong>CLP</strong> ....................................................................................... 48<br />

Example of a label ........................................................................................................ 48<br />

Update of label information .......................................................................................... 49<br />

Who is affected by <strong>CLP</strong> <strong>and</strong> how? ................................................................................... 50<br />

Importers <strong>and</strong> manufacturers of substances .................................................................. 50<br />

Classification <strong>and</strong> labelling inventory ...................................................................... 50<br />

Formulators ................................................................................................................... 50<br />

4


Distributors ................................................................................................................... 50<br />

End-users of chemicals ................................................................................................. 50<br />

Preparation for <strong>CLP</strong> in the organisation ........................................................................... 51<br />

<strong>CLP</strong> / GHS in the future .................................................................................................... 51<br />

Transitional period ............................................................................................................ 52<br />

Transitional period for substances ............................................................................ 52<br />

Transitional period for mixtures ............................................................................... 52<br />

Conversion tables .......................................................................................................... 53<br />

Links ................................................................................................................................. 54<br />

GHS/<strong>CLP</strong> Vocabulary ...................................................................................................... 55<br />

Exercises ........................................................................................................................... 57<br />

Exercise 1. Classification of substances – translation table .......................................... 57<br />

Exercise 2. Classification of mixtures – calculation ..................................................... 57<br />

Exercise 3. Labelling – label for previous classified mixture ....................................... 57<br />

Product identifier(s) .................................................................................................. 57<br />

Signal Words ............................................................................................................. 58<br />

Hazard pictograms .................................................................................................... 58<br />

Hazard Statements .................................................................................................... 58<br />

Supplemental information ......................................................................................... 58<br />

Exercise 4. Principles of Precedence – Choosing hazard pictograms ......................... 58<br />

Solutions ........................................................................................................................... 59<br />

Exercise 1 ...................................................................................................................... 59<br />

Exercise 2 ...................................................................................................................... 59<br />

Exercise 3 ...................................................................................................................... 62<br />

Exercise 4 ...................................................................................................................... 64<br />

Final labels .................................................................................................................... 65<br />

5


Introduction/Background<br />

GHS was adopted by UN in 2002. The intention was to introduce a global system for<br />

classification <strong>and</strong> labelling of chemical substances <strong>and</strong> mixtures. Without a global system<br />

a chemical substance may have quite different classifications from country to country <strong>and</strong><br />

from region to region. Some substances may be considered toxic in one country <strong>and</strong><br />

harmless in another country. Harmonised criteria for evaluating the hazardous properties<br />

of chemicals will, by time, ensure uniform classifications all over the world. This will<br />

make it easier for companies to import <strong>and</strong> export chemicals <strong>and</strong> hopefully it will lead to<br />

a better protection of man <strong>and</strong> environment.<br />

GHS should by time be implemented worldwide. However, the timeline for<br />

implementation varies. Some countries have already implemented GHS while others are<br />

still in the process of analyzing how to do it.<br />

In EU GHS entered into force in January 2009. GHS is implemented as “Regulation of<br />

the European Parliament <strong>and</strong> of the council on classification, labelling <strong>and</strong> packaging of<br />

substances <strong>and</strong> mixtures”, in short: <strong>CLP</strong> system or just: <strong>CLP</strong>.<br />

<strong>CLP</strong> is in many ways similar to the current EU system for classification <strong>and</strong> labelling,<br />

<strong>and</strong> EU has implemented most of the building blocks from GHS. The global GHS text<br />

also states criteria for preparation of safety data sheets. The GHS safety data sheets are<br />

almost similar to the EU safety data sheets, however in EU safety data sheets will not be<br />

regulated under <strong>CLP</strong> as they are already regulated under REACH.<br />

In this course the current EU-system for classification <strong>and</strong> labelling of substances<br />

(directive 67/548/EEC) will be referred to as “Dangerous Substance Directive”, <strong>DSD</strong>,<br />

while the current EU-criteria for classification <strong>and</strong> labelling of mixtures (directive<br />

1999/45/EC ) will be referred to as “Dangerous Preparations Directive”, DPD.<br />

Building blocks<br />

GHS introduces the term “Building block approach”. GHS is build up by a large number<br />

of blocks, <strong>and</strong> each country or region (e.g. EU) is free to pick the building blocks they<br />

want, so even if the intention is a globally harmonized system there may still be<br />

differences in the implementation from country to country or region to region. However,<br />

if a country or region chooses to implement a building block they have to implement the<br />

building block as a whole without any changes. If two countries have chosen to<br />

implement the same building block (for example the classification for acute toxicity<br />

category 4) both countries will use the same criteria when classifying chemicals as toxic.<br />

See criteria for Acute toxicity, page 28<br />

6


Difference <strong>between</strong> UN <strong>and</strong> EU<br />

When implementing the UN GHS, EU has left out some hazard classes <strong>and</strong> –categories<br />

<strong>and</strong> introduced some not represented in the UN GHS. An overview of the main<br />

differences <strong>between</strong> <strong>CLP</strong> <strong>and</strong> the GHS proposal from UN is found in Table 1.<br />

UN EU<br />

Flammable liquid, category 4 Not part of <strong>CLP</strong><br />

Acute toxicity, category 5 Not part of <strong>CLP</strong><br />

Skin irritation, category 3 Not part of <strong>CLP</strong><br />

Aspiration Hazard, category 2 Not part of <strong>CLP</strong><br />

Hazardous to the aquatic environment, Nor part of <strong>CLP</strong><br />

Acute category 2 <strong>and</strong> 3<br />

Not part of the UN GHS Hazardous for the ozone layer<br />

Safety data sheets Not part of <strong>CLP</strong>. Safety data sheets are<br />

regulated under REACH. However, the<br />

format <strong>and</strong> contents of a GHS safety data<br />

sheet <strong>and</strong> an EU safety data sheet are<br />

almost similar.<br />

Table 1. UN-GHS versus EU-<strong>CLP</strong><br />

Furthermore <strong>CLP</strong> covers some hazards that lead to additional labelling which is not part<br />

of GHS. These additional hazards are described further under Additional EU statements.<br />

Part of UN but not part of EU<br />

In EU a flammable liquid is a liquid with a flashpoint of not more than 60 °C. In UN a<br />

flammable liquid is a liquid having a flashpoint of not more than 93 °C. In EU the<br />

flammable liquids are divided into category 1, 2 <strong>and</strong> 3 while in UN there is also a<br />

category 4 covering liquids with a flashpoint <strong>between</strong> 60 °C <strong>and</strong> 93 °C.<br />

In EU an acute toxic substance is a substance having an LD50-value of not more than<br />

2000 mg/kg. The hazard class “Acute Toxic” is divided into four categories with category<br />

4 presenting the lowest level of hazard. UN introduces an Acute Toxic category 5 for<br />

chemicals having an LD50-value <strong>between</strong> 2000 <strong>and</strong> 5000 mg/kg. This category 5 is not a<br />

part of <strong>CLP</strong>.<br />

In EU there are two categories for skin corrosion/irritation, namely category 1 <strong>and</strong> 2. In<br />

UN there is a category 3 for mild skin irritation which is not a part of <strong>CLP</strong>.<br />

In EU there is one category for the hazard class Aspiration Hazard while in UN there is<br />

both category 1 <strong>and</strong> 2.<br />

Regarding Environmental hazards, EU has chosen to implement one category for acute<br />

toxicity, but the UN system introduces three categories.<br />

7


Part of EU but not part of UN<br />

In EU there is an additional hazard class, which is not part of the UN system, namely the<br />

classification as Hazardous for the ozone layer<br />

Downstream legislation<br />

<strong>CLP</strong> will affect most chemical legislation including REACH. REACH <strong>and</strong> other<br />

legislations often refer to specific classifications <strong>and</strong> specific R-phrases. With <strong>CLP</strong> these<br />

R-phrases will no longer exist <strong>and</strong> therefore, in time, downstream legislation has to be<br />

updated.<br />

8


Classification criteria<br />

Classification of chemical substances <strong>and</strong> mixtures means that the physical hazards, the<br />

health hazards <strong>and</strong> the environmental hazards of the substance/mixture are determined.<br />

A classification consists of a hazard class <strong>and</strong> a hazard category. Table 2, Table 3 <strong>and</strong><br />

Table 4 lists the <strong>CLP</strong> hazard classes <strong>and</strong> hazard categories implemented in EU.<br />

This course will briefly go through the definitions <strong>and</strong> some of the criteria for each<br />

hazard class. Furthermore you will find a short description of the differences <strong>between</strong> the<br />

<strong>CLP</strong> criteria <strong>and</strong> the criteria from the <strong>DSD</strong>.<br />

Physical hazards<br />

To decide whether a substance or mixture is classified with one or more physical hazards<br />

specific tests must always be performed. Most of the physical tests required according to<br />

the <strong>CLP</strong> regulation are identical to the tests described in the UN Recommendations on the<br />

transport of Dangerous Goods, Manual of Tests <strong>and</strong> Criteria.<br />

An overview of the physical hazard classes <strong>and</strong> hazard categories is found in Table 2. In<br />

addition to the table you will find a brief description of each hazard class.<br />

9


Hazard Class Hazard category<br />

Explosives Unstable explosives<br />

Division 1.1<br />

Division 1.2<br />

Division 1.3<br />

Division 1.4<br />

Division 1.5<br />

Division 1.6<br />

Flammable gasses 1<br />

2<br />

Flammable aerosols 1<br />

2<br />

Oxidizing gases 1<br />

Gases under pressure Compresses gas<br />

Liquefied gas<br />

Refrigerated liquefied gas<br />

Dissolved gas<br />

Flammable liquids 1<br />

2<br />

3<br />

Flammable solids 1<br />

2<br />

Self-reactive substances <strong>and</strong> mixtures Type A<br />

Type B<br />

Type C&D<br />

Type E&F<br />

Type G<br />

Pyrophoric liquids 1<br />

Phyrophoric solids 1<br />

Self-heating substances <strong>and</strong> mixtures 1<br />

2<br />

Substances <strong>and</strong> mixtures which in 1<br />

contact with water emit flammable gases<br />

2<br />

3<br />

Oxidizing liquids 1<br />

2<br />

3<br />

Oxidizing solids 1<br />

2<br />

3<br />

Organic peroxides Type A<br />

Type B<br />

10


Type C&D<br />

Type E&F<br />

Type G<br />

Corrosive to metals 1<br />

Table 2. Physical hazards<br />

Explosives<br />

The class of explosives comprises solid <strong>and</strong> liquid substances <strong>and</strong> mixtures as well as<br />

articles. To classify a substance, a mixture or an article as explosive, tests needs to be<br />

performed. This hazard class is found under <strong>DSD</strong>. However, <strong>DSD</strong> does not contain as<br />

many hazard categories for explosives as <strong>CLP</strong>.<br />

Flammable gases<br />

A flammable gas is a gas or a gas mixture having a flammable range with air at 20 °C <strong>and</strong><br />

a pressure of 101.3 kPa. The gas or the gas mixture must be tested to decide whether it<br />

meets the criteria. In <strong>DSD</strong> gasses are classified as flammable, but <strong>DSD</strong> only operate with<br />

one term “Flammable”, which is used for both liquids <strong>and</strong> gasses.<br />

Flammable aerosols<br />

An aerosol dispenser containing compressed gas under pressure shall be classified as<br />

flammable if it contains components classified as flammable liquids, flammable gases or<br />

flammable solids. This hazard class is not a part of <strong>DSD</strong>.<br />

Oxidizing gases<br />

An oxidizing gas is a gas or a gas mixture which may provide oxygen <strong>and</strong> thereby<br />

contribute to the combustion of other material more than air does. In <strong>DSD</strong> oxidising<br />

gasses are classified but they are classified together with other oxidising substances.<br />

Gases under pressure<br />

The gases under pressure comprise compressed gases, liquefied gases, dissolved gases<br />

<strong>and</strong> refrigerated liquefied gases. This hazard class is not a part of <strong>DSD</strong>.<br />

Flammable liquids<br />

A flammable liquid is a liquid having a flash point of 60 °C or less. Flammable liquids<br />

are classified under <strong>DSD</strong>, but the criteria are different.<br />

11


Flammable solids<br />

A flammable solid is a powdered, granular or pasty substance or mixture which can be<br />

easily ignited by brief contact with an ignition source. This hazard class is not a part of<br />

<strong>DSD</strong>.<br />

Self-reactive substances <strong>and</strong> mixtures<br />

A self-reactive substance or mixture is a thermally unstable liquid or solid. The liquid or<br />

solid is liable to undergo a strongly, exothermic decomposition even without the presence<br />

of air. This hazard class is not a part of <strong>DSD</strong>.<br />

Pyrophoric liquids<br />

A pyrophoric liquid is a liquid which, even in small amounts, within 5 minutes of coming<br />

into contact with air is liable to ignite. This hazard class is not a part of <strong>DSD</strong>.<br />

Pyrophoric solids<br />

A pyrophoric solid is a solid which, even in small amounts, within 5 minutes of coming<br />

into contact with air is liable to ignite. This hazard class is not a part of <strong>DSD</strong>.<br />

Self-heating substances <strong>and</strong> mixtures<br />

A self-heating substance or mixture differs from a pyrophoric liquid or solid in that it will<br />

ignite only in large amounts (kilograms) <strong>and</strong> after a long period of time (hours or days).<br />

This hazard class is not a part of <strong>DSD</strong>.<br />

Substances <strong>and</strong> mixtures which in contact with water emit flammable<br />

gases<br />

Hereby means solid or liquid substances or mixtures which in contact with water become<br />

spontaneously flammable or give off flammable gases in dangerous quantities. The<br />

hazard class is also found in <strong>DSD</strong>.<br />

Oxidizing liquids<br />

An oxidizing liquid is a liquid substance or a liquid mixture which may provide oxygen<br />

<strong>and</strong> thereby contribute to the combustion of other material. The oxidizing liquid is not<br />

necessarily combustible itself. Part of <strong>DSD</strong>.<br />

Oxidizing solids<br />

An oxidizing solid is a solid substance or a solid mixture which may provide oxygen <strong>and</strong><br />

thereby contribute to the combustion of other material. The oxidizing solid is not<br />

necessarily combustible itself. Part of <strong>DSD</strong>.<br />

12


Organic peroxides<br />

Organic peroxides are liquid or solid organic substances containing the –O-O– structure.<br />

Whether an organic peroxide is classified or not, depends on the amount of available<br />

oxygen. Organic peroxides are classified under <strong>DSD</strong>, but they do not have a separate<br />

hazard category. In <strong>DSD</strong> organic peroxides are classified together with other oxidising<br />

substances.<br />

Corrosive to metals<br />

A substance or mixture is corrosive to metals if it materially damage or destroy metals.<br />

Whether it is classified or not depend on the corrosion rate on either steel or aluminium.<br />

Not a part of <strong>DSD</strong>.<br />

13


Health hazards<br />

The criteria for classifying a substance or a mixture for one or more health hazards are<br />

very close to the criteria known from the EU system described in <strong>DSD</strong>.<br />

An overview of the health hazard classes <strong>and</strong> hazard categories is found in Table 3. In<br />

addition to the table you will find a brief description of each hazard class.<br />

Hazard Class Hazard category<br />

Acute toxicity 1<br />

2<br />

3<br />

4<br />

Skin corrosion/irritation 1A<br />

1B<br />

1C<br />

2<br />

Serious eye damage/eye irritation 1<br />

2<br />

Respiratory or skin sensitisation Skin sensitiser<br />

Respiratory sensitiser<br />

Germ cell mutagenicity 1A<br />

1B<br />

2<br />

Carcinogenicity 1A<br />

1B<br />

2<br />

Reproductive toxicity 1A<br />

1B<br />

2<br />

Additional category for effects<br />

on or via lactation<br />

Specific target organ toxicity – 1<br />

single exposure<br />

2<br />

3<br />

Specific target organ toxicity – 1<br />

repeated exposure<br />

2<br />

Aspiration hazard 1<br />

Table 3. Health hazards<br />

14


Acute toxicity<br />

Acute toxicity differs <strong>between</strong> oral, dermal <strong>and</strong> inhalation exposure. Acute toxicity takes<br />

into consideration effects occurring after a single dose of a substance or mixture. The<br />

criteria in <strong>CLP</strong> are different from the criteria described in <strong>DSD</strong>.<br />

Skin corrosion/irritation<br />

A corrosive substance or mixture is capable of producing irreversible damage to the skin,<br />

while irritating substances <strong>and</strong> mixtures produce reversible damage to the skin. The<br />

criteria in <strong>CLP</strong> differ from the criteria in <strong>DSD</strong>.<br />

Serious eye damage/eye irritation<br />

Chemicals irritating to eyes or chemicals causing serious eye damage are able to damage<br />

the tissue in the eye or to cause a physical decay of vision. Serious eye damage is not<br />

fully reversible while the eye irritation is fully reversible.<br />

Respiratory or skin sensitisation<br />

A respiratory sensitiser will cause hypersensitivity of the airways if inhaled. A skin<br />

sensitiser will cause an allergic response following skin contact.<br />

Germ cell mutagenicity<br />

To meet the criteria for germ cell mutagenicity, a chemical is able to permanently change<br />

the structure or amount of the genetic material in a cell (DNA). The chemical meeting<br />

these criteria will be called a “mutagen”.<br />

Carcinogenicity<br />

A chemical classified as carcinogen may either cause cancer or increase the incidence of<br />

cancer. The classification does not differ <strong>between</strong> different types of cancer.<br />

Reproductive toxicity<br />

Reproductive toxicity is the ability to affect the sexual function <strong>and</strong> the fertility of adult<br />

male <strong>and</strong> female. Furthermore a chemical toxic to reproduction may be able to affect the<br />

development of the offspring.<br />

Specific target organ toxicity (STOT) – single exposure<br />

Specific target organ toxicity – single exposure is defined as non lethal target organ<br />

toxicity. The effects are significant <strong>and</strong> specific <strong>and</strong> they occur after only one exposure to<br />

the chemical. Both reversible <strong>and</strong> irreversible effects are included in this definition.<br />

Specific target organ toxicity (STOT) – repeated exposure<br />

The definition of specific target organ toxicity – repeated exposure is similar to the<br />

Specific target organ toxicity – single exposure except that for the repeated exposure the<br />

effects will only appear after two or more exposures.<br />

15


Aspiration hazard<br />

Chemicals that pose an aspiration hazard are liquids or solids able to enter the lungs e.g.<br />

following vomiting. The chemicals may cause chemical pneumonia or other severe<br />

injuries.<br />

16


Environmental hazards.<br />

When classifying for environmental hazards only the effects to the aquatic environment<br />

are considered. To classify a chemical you will need to know the acute <strong>and</strong> chronic<br />

toxicity to aquatic organisms as well as the potential to bioaccumulate <strong>and</strong> the ability of<br />

biodegradation.<br />

An overview of the environmental hazard classes <strong>and</strong> hazard categories is found in Table<br />

4.<br />

Hazard Class Hazard category<br />

Hazardous to the aquatic 1<br />

environment - Acute<br />

Hazardous to the aquatic 1<br />

environment - Chronic<br />

2<br />

3<br />

4<br />

Hazardous for the ozone layer<br />

Table 4. Environmental hazards<br />

Hazardous for the ozone layer.<br />

EU has chosen to use an additional hazard class <strong>and</strong> enable the classification of a<br />

chemical as hazardous for the ozone layer.<br />

17


<strong>Differences</strong> <strong>between</strong> <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong><br />

Even though the principles for classification are the same in <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> some criteria<br />

are different. The tables below give an overview of the main differences <strong>between</strong> the<br />

classification criteria according to <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> for health hazards <strong>and</strong> environmental<br />

hazards.<br />

Physical hazards<br />

There are major changes <strong>between</strong> <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> when it comes to physical hazards.<br />

Some criteria for existing hazard classes have changed, but the main difference is the<br />

addition of a number of hazard classes, which are not part of <strong>DSD</strong>. The differences<br />

<strong>between</strong> <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> for flammable liquid are shown in Table 5, while Table 6 <strong>and</strong><br />

Table 7 give an overview of the additional hazard classes under <strong>CLP</strong>.<br />

Describing all criteria for classification will be much too comprehensive for this course.<br />

Please see the <strong>CLP</strong>-legislation for details.<br />

Flammable liquids<br />

<strong>DSD</strong> <strong>CLP</strong><br />

Extremely Flash point < 0 °C <strong>and</strong> boiling Category 1 Flash point < 23 ° C <strong>and</strong><br />

flammable point ≤ 35 °C<br />

boiling point ≤ 35 °C<br />

Highly Flash point < 21 ° but not Category 2 Flash point < 23 °C <strong>and</strong><br />

flammable extremely flammable<br />

boiling point > 35 °C<br />

Flammable 21 °C ≤ flash point ≤ 55 °C Category 3 23 ≤ flash point ≤ 60 °C<br />

Table 5. Comparison <strong>between</strong> <strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> for flammable liquids<br />

Hazard classes R-phrases<br />

Explosives E;R2 E;R3<br />

Oxidizing substances O;R7 O;R8 O;R9<br />

Flammable substances F+;R12 F;R11 F;R15 F;R17 R10<br />

Table 6. Physical hazard classes under <strong>DSD</strong><br />

18


Hazard classes Hazard categories<br />

Explosives Unstable Div 1.1 Div 1.2 Div 1.3 Div 1.4 Div 1.5 Div 1.6<br />

Flammable gases 1 2<br />

Flammable aerosols 1 2<br />

Oxidizing gases 1<br />

Gases under pressure<br />

Compressed gas 1<br />

Liquified gas 1<br />

Refrigerated liquefied<br />

gas 1<br />

Dissolved gas 1<br />

Flammable liquids 1 2 3<br />

Flammable solids 1 2<br />

Self-reactive substances <strong>and</strong><br />

mixtures Type A Type B Type C Type D Type E Type F Type G<br />

Pyrophoric liquids 1<br />

Pyrophoric solids 1<br />

Self-heating substances <strong>and</strong><br />

mixtures 1 2<br />

Substances <strong>and</strong> mixtures<br />

which in contact with water<br />

emit flammable gases 1 2 3<br />

Oxidizing liquids 1 2 3<br />

Oxidizing solids 1 2 3<br />

Organic peroxides Type A Type B Type C Type D Type E Type F Type G<br />

Corrosive to metals 1<br />

Table 7. Hazard classes under <strong>CLP</strong><br />

19


Health hazards<br />

Acute toxicity – inhalation<br />

<strong>DSD</strong> R26 R23 R20<br />

LC50 (mg/l/4 hours) ≤ 0,5 0,5 -2 2 - 10 10 -20<br />

<strong>CLP</strong> Category 1 Category 2 Category 3 Category 4<br />

Acute toxicity – dermal<br />

<strong>DSD</strong> R27 R24 R21<br />

LD50 (mg/kg) ≤ 50 50-200 200-400 400-1000 1000-2000<br />

<strong>CLP</strong> Category 1 Category 2 Category 3 Category 4<br />

Acute toxicity – oral<br />

<strong>DSD</strong> R28 R25 R22<br />

LD50 (mg/kg) ≤ 5 5-25 25-50 50-200 200-300 300-2000<br />

<strong>CLP</strong> Category 1 Category 2 Category 3 Category 4<br />

Skin corrosion/irritation<br />

<strong>DSD</strong> R35 R34 R38<br />

Exposure ≤ 3 min 3 min – 1 hour 1 hour – 4 hours See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

<strong>CLP</strong> Category 1A Category 1B Category 1C Category 2<br />

20


Eye damage/Eye irritation<br />

<strong>DSD</strong> R41 R36<br />

See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

<strong>CLP</strong> Category 1 Category 2<br />

Sensitisation<br />

<strong>DSD</strong> R42 R43<br />

<strong>CLP</strong> Respiratory sensitiser,<br />

Category 1<br />

Mutagenicity<br />

Skin sensitiser,<br />

Category 1<br />

<strong>DSD</strong> Mut, cat 1;R46 Mut, cat 2;R46 Mut, cat 3;R68<br />

See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

<strong>CLP</strong> Category 1A Category 1B Category 2<br />

Carcinogenicity<br />

<strong>DSD</strong> Carc, cat 1;R45<br />

<strong>and</strong> R49<br />

Carc, cat 2;R45 <strong>and</strong><br />

R49<br />

See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

Carc, cat 3;R40<br />

<strong>CLP</strong> Category 1A Category 1B Category 2<br />

21


Reproductive toxicity<br />

<strong>DSD</strong> Rep, cat 1;R60<br />

<strong>and</strong> R61<br />

Rep, cat 2;R60 <strong>and</strong><br />

R61<br />

See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

Rep, cat 3;R62 <strong>and</strong> R63<br />

<strong>CLP</strong> Category 1A Category 1B Category 2<br />

STOT, single exposure<br />

<strong>DSD</strong> Tx;R39 T;R39 R68 R37, R67<br />

See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

<strong>CLP</strong> Category 1 Category 2 Category 3<br />

STOT, repeated exposure<br />

<strong>DSD</strong> T;R48 Xn;R48<br />

See <strong>DSD</strong> for criteria<br />

See <strong>CLP</strong> for criteria<br />

<strong>CLP</strong> Category 1 Category 2<br />

22


Environmental hazards<br />

<strong>DSD</strong> R50 R52<br />

L(E)C50 ≤ 1 mg/l See <strong>DSD</strong> for criteria<br />

<strong>CLP</strong> Acute, Category 1<br />

<strong>DSD</strong> R50/53 R51/53 R52/53 R53<br />

L(E)C50 ≤ 1 mg/l


Classification of substances<br />

Classification of a substance is based on test data (in vitro tests <strong>and</strong> animal data), QSARresults<br />

<strong>and</strong> human experience. For each hazard class <strong>and</strong> hazards category criteria are set<br />

up which enable the manufacturer of a substance to classify the substance based on<br />

available data.<br />

Classification of mixtures<br />

To classify a mixture the same tests as for substances can be performed <strong>and</strong> the mixture<br />

can be classified based on data for the mixture. However, test data are normally not<br />

available for mixtures. As it is desirable to avoid animal testing <strong>and</strong> since testing may be<br />

very expensive, it is possible to classify a mixture if sufficient data for the ingredient<br />

substances are available. Classification of a mixture based on substance data can only be<br />

done for health <strong>and</strong> environmental hazards.<br />

The physical hazards of a mixture cannot be calculated based on classification on ingoing<br />

substances. Therefore tests always have to be performed for the mixture itself to<br />

determine the physical hazards.<br />

Bridging Principles<br />

If test data are not available for a mixture but there are available test data for a similar<br />

mixture, it is possible to classify the untested mixture using bridging principles. There are<br />

different types of bridging principles.<br />

24


Dilution<br />

If a mixture is diluted with a substance with an equivalent or lower hazard category<br />

classification than the least hazardous original substance <strong>and</strong> the diluent is not expected<br />

to affect the hazard classification of any other substances in the mixture, one of the<br />

following shall be applied:<br />

Mixture A<br />

Tested<br />

Mixture A<br />

Tested<br />

Diluent<br />

Equivalent or lower<br />

hazard than original<br />

substance<br />

Diluent<br />

Water or other nonhazardous<br />

substance<br />

Mixture B<br />

Same classification<br />

as mixture A<br />

Mixture B<br />

Calculation based<br />

on dilution<br />

Batching<br />

When producing a batch of a hazardous substance or mixture under controlled conditions<br />

the hazards of each new batch can be assumed to be equivalent to the previous batch. If<br />

there is reason to believe the composition may vary significantly, a new evaluation is<br />

required.<br />

Concentration of highly hazardous mixtures<br />

When a mixture is already classified in the highest hazard category increasing the<br />

concentration of ingredients in that category shall lead to classification in the same<br />

hazard category without additional testing.<br />

25


Interpolation<br />

For three mixtures which contain the same hazardous substances, where mixtures A <strong>and</strong><br />

B are in the same hazard category <strong>and</strong> mixture C contains the same active hazardous<br />

substances with concentrations intermediate to the concentrations of those hazardous<br />

substances in mixtures A <strong>and</strong> B, then mixture C is assumed to be in the same hazard<br />

category as A <strong>and</strong> B.<br />

80% 20%<br />

30%<br />

70%<br />

Mixture A<br />

STOT Kat. 1<br />

Similar mixtures<br />

Two mixtures both contain two substances, where the concentration of substance B is<br />

essentially the same in both mixtures<br />

Mixture 1: A + B (tested)<br />

Mixture 2: B + C (not tested)<br />

50% 50%<br />

Mixture B<br />

STOT Kat. 1<br />

30% to 80% 20% to 70%<br />

Mixture C<br />

Interpolate STOT Kat. 1<br />

If the hazard category of substance A <strong>and</strong> C is the same <strong>and</strong> the concentration of A equals<br />

that of C then mixture 2 can be assigned the same hazard category as mixture 1.<br />

26


Changes in compositions<br />

Applying bridging principles the following variations in composition is allowed:<br />

Initial concentration range Permitted variation in initial<br />

concentration<br />

≤ 2.5 % ± 30 %<br />

2.5 % < C ≤ 10 % ± 20 %<br />

10 % < C ≤ 25 % ± 10 %<br />

25 % < C ≤ 100 % ± 5 %<br />

Be aware of substance specific concentration limits <strong>and</strong> the M-factor for substances<br />

classified for environmental hazards.<br />

Aerosols<br />

An aerosol form of a mixture shall be classified in the same hazard category as the nonaerosolized<br />

mixture unless it is assumed that the propellant will affect the hazards upon<br />

spraying.<br />

27


Calculation principles<br />

If the hazardous properties of a mixture is unknown but the hazard properties of some or<br />

every ingoing substances are known it is possible to classify the mixture using<br />

calculation.<br />

Cut-off values<br />

Depending on the classification of a substance there are so-called “cut-off” values to take<br />

into consideration when calculating the classification of a mixture. If a substance is<br />

present in a mixture in a concentration below the cut-off value the hazardous properties<br />

of the substance should not be taken into consideration when calculating. <strong>CLP</strong> lays down<br />

a table containing generic cut-off values for substances. For substances present on the list<br />

of harmonised substances there may be individual concentration limits lower than the<br />

generic cut-off values. In this case, the lowest value must be used. The same goes for<br />

substances present on the Agency’s “Classification <strong>and</strong> labelling inventory”.<br />

For substances hazardous to the aquatic environment where an M-factor has been set the<br />

generic cut-off value must be adjusted accordingly.<br />

The generic cut-off values for solid <strong>and</strong> liquid substances are found in Table 8.<br />

Hazard Class Cut-off value (weight percentage)<br />

Acute toxicity, category 1-3 0.1 %<br />

Acute toxicity, category 4 1 %<br />

Skin corrosion / irritation 1 %<br />

Serious damage to eyes / eye irritation 1 %<br />

Hazardous to aquatic environment – Acute<br />

category 1<br />

0.1 %<br />

Hazardous to aquatic environment –<br />

Chronic category 1<br />

0.1 %<br />

Hazardous to aquatic environment –<br />

Chronic category 2-4<br />

1 %<br />

Table 8. Cut-off values<br />

Acute toxicity<br />

The acute toxicity estimate, ATE, equals the LD50/LC50-values for a substance or<br />

mixture.<br />

To decide whether a mixture should be classified as acute toxic, the ATE for the mixture<br />

must be calculated. Every ingoing substance classified as acute toxic <strong>and</strong> present in<br />

concentrations above the cut-off limit must be taken into consideration when calculating<br />

the ATE for a mixture. When using the formula substances classified for both dermal,<br />

oral <strong>and</strong> inhalation toxicity must be included.<br />

The formula for calculating the ATE for a mixture where information for all ingoing<br />

substances is available is:<br />

28


100<br />

ATE<br />

Where:<br />

∑<br />

C<br />

i<br />

=<br />

mix n ATEi<br />

Ci = concentration of ingredient i (% w/w or v/v)<br />

i = the individual ingredient from 1 to n<br />

n = the number of ingredients<br />

ATEi = acute toxicity estimate for ingredient i.<br />

The formula may also be used even if data are not available for all substances as long as<br />

the concentration of unknown substances does not exceed 10 %.<br />

In some cases actual LD50/LC50-values for a substance are not available, but as long as<br />

the classification of the substance is known it is possible to find a converted ATE using<br />

Table 9.<br />

Exposure routes Classification Category or<br />

experimentally obtained<br />

acute toxicity range<br />

Oral<br />

(mg/kg<br />

bodyweight)<br />

Dermal<br />

(mg/kg<br />

bodyweight)<br />

Gases<br />

(ppmV)<br />

Vapours<br />

(mg/l)<br />

Dust/mist<br />

(mg/l)<br />

Table 9. Converted ATE for substances<br />

estimate<br />

0 < Category 1 ≤ 5<br />

5 < Category 2 ≤ 50<br />

50 < Category 3 ≤ 300<br />

300 < Category 4 ≤ 2000<br />

0 < Category 1 ≤ 50<br />

50 < Category 2 ≤ 200<br />

200 < Category 3 ≤ 1000<br />

1000 < Category 4 ≤ 2000<br />

0 < Category 1 ≤ 100<br />

100 < Category 2 ≤ 500<br />

500 < Category 3 ≤ 2500<br />

2500 < Category 4 ≤ 20000<br />

0 < Category 1 ≤ 0.5<br />

0.5 < Category 2 ≤ 2.0<br />

2.0 < Category 3 ≤ 10.0<br />

10.0 < Category 4 ≤ 20.0<br />

0< Category 1 ≤ 0.05<br />

0.05 < Category 2 ≤ 0.5<br />

0.5 < Category 3 ≤ 1.0<br />

1.0 < Category 4 ≤ 5.0<br />

Converted Acute Toxicity<br />

point estimate 1<br />

0.5<br />

5<br />

100<br />

500<br />

5<br />

50<br />

300<br />

1100<br />

10<br />

100<br />

700<br />

4500<br />

0.05<br />

0.5<br />

3<br />

11<br />

0.005<br />

0.05<br />

0.5<br />

1.5<br />

1 These values are designed to be used in the calculation of the ATE for classification of a mixture based on<br />

its components <strong>and</strong> do not represent test results.<br />

29


Using either actual ATE-values for each substance or converted ATE-values, the ATE for<br />

the mixture is determined. Once the ATE for the mixture is known, the classification is<br />

found using Table 10.<br />

Exposure Route Category 1 Category 2 Category 3 Category 4<br />

Oral (mg/kg<br />

ATE ≤ 5 5 < ATE ≤ 50 50 < ATE ≤ 300 300 < ATE ≤<br />

bodyweight)<br />

2000<br />

Dermal (mg/kg ATE ≤ 50 50 < ATE ≤ 200 200 < ATE ≤ 1000 1000 < ATE ≤<br />

bodyweight)<br />

2000<br />

Gases (ppmV) ATE ≤ 100 100 < ATE ≤ 500 500 < ATE ≤ 2500 2500 < ATE ≤<br />

20000<br />

Vapours (mg/l) ATE ≤ 0.5 0.5 < ATE ≤ 2.0 2.0 < ATE ≤ 10.0 10.0 < ATE ≤<br />

20.0<br />

Dusts <strong>and</strong> Mists<br />

(mg/l)<br />

Table 10. Hazard categories <strong>and</strong> ATE<br />

ATE ≤ 0.05 0.05 < ATE ≤ 0.5 0.5 < ATE ≤ 1.0 1.0 < ATE ≤ 5.0<br />

Example:<br />

If a mixture A contains 10 % of substance 1 classified as acute toxic category 3, oral <strong>and</strong><br />

5 % of substance 2 classified as acute toxic, category 2, oral, <strong>and</strong> the rest of the<br />

substances are known to be not hazardous, then the calculations will be as follow:<br />

The converted ATE-values for each substance are found using Table 9.<br />

ATEoral for substance 1: = 100<br />

ATEoral for substance 2 = 5<br />

The converted ATE-values are inserted in the formula.<br />

100 10 5<br />

= + ⇒ ATEmix, oral = 91<br />

ATEmix,<br />

oral 100 5<br />

Using Table 10 we find that an ATE for oral exposure of 91 gives a classification as<br />

acute toxic, category 3<br />

Therefore the classification of mixture A will be acute toxicity, category 3, oral<br />

It is not yet clear how a mixture containing substances classified for acute toxicity but<br />

with different routes of exposure should be h<strong>and</strong>led. Guidance from ECHA is foreseen in<br />

summer 2009.<br />

More than 10 % unknown.<br />

If data are missing for more than 10 % of the ingoing substances, it is still possible to<br />

classify the mixture using calculation. In this case the formula is:<br />

30


100 − ( ∑ C unknown)<br />

=<br />

ATEmix<br />

∑<br />

n<br />

Ci<br />

ATEi<br />

Where Cunknown is the concentration of each substance where hazard data are not<br />

available.<br />

Classification based on concentration thresholds<br />

Additive concentration limits<br />

Additive concentration limits are used for some hazard classes. Each substance in these<br />

hazard classes contributes to the overall classification of the mixture. The following<br />

hazard classes use additive concentration limits.<br />

• Skin corrosion/irritation<br />

• Serious eye damage/eye irritation<br />

• Hazardous to the aquatic environment<br />

Skin corrosion/irritation<br />

When using the additivity approach to calculate the classification of a mixture each<br />

ingredient classified as skin corrosive or skin irritant should be taken into account. A<br />

weighing factor of 10 is used for a corrosive substance present at a concentration below<br />

the generic cut-off value, if manufacturers or importers find it relevant to take this<br />

substance into consideration when classifying. Table 11 shows the generic concentration<br />

limits using the additivity approach. Below is given examples of calculations based on<br />

the additivity approach.<br />

Sum of ingredients classified as: Concentration limits for classification as:<br />

Skin corrosive, category 1 Skin irritant, category 2<br />

Skin corrosive, categories 1A,<br />

1B, 1C<br />

≥ 5 % 2<br />

≥ 1 % but < 5 %<br />

Skin irritant, category 2 ≥ 10 %<br />

(10 x skin corrosive, category 1A,<br />

1B, 1C) + skin irritant, category 2<br />

≥ 10 %<br />

Table 11. Generic concentration limits of ingredients classified for skin corrosive/irritant hazards<br />

2 If the sum of the Skin Corrosive Category 1A ingredients is ≥ 5 %, the mixture shall be classified as Skin<br />

Corrosive Category 1A. If the sum of the Skin Corrosive Category 1A ingredients is < 5 % but the sum of<br />

Category 1A+1B ingredients is ≥ 5 %, the mixture shall be classified as Skin Corrosive Category 1B.<br />

Similarly, if the sum of Skin Corrosive Category 1A+1B ingredients is < 5 % but the sum of Category<br />

1A+1B+1C ingredients is ≥ 5 % the mixture shall be classified as Skin Corrosive Category 1C.<br />

31


Examples of classification using the additivity approach. It is assumed that substance<br />

classified in category 1A should be taken into consideration when present in amounts<br />

below 1 %:<br />

4% Category<br />

1A<br />

3% Category<br />

1A<br />

0.5% Category<br />

1A<br />

+ +<br />

1% Category<br />

1B<br />

+ +<br />

1% Category<br />

1B<br />

1% Category<br />

1C<br />

1% Category<br />

1C<br />

⇒<br />

⇒<br />

+ ⇒<br />

6% Category 2<br />

Mixture classified as<br />

skin corrosive,<br />

category 1B<br />

Mixture classified as<br />

skin corrosive,<br />

category 1C<br />

Mixture classified as<br />

skin irritant,<br />

category 2<br />

32


Care must be taken when classifying mixtures containing ingredients such as strong acids<br />

<strong>and</strong> bases, inorganic salts, aldehydes, phenols, surfactants etc. as the additivity approach<br />

may not be applicable for many of these ingredients. For mixtures containing strong acids<br />

or strong bases the pH shall be used as classification criteria since pH is a better indicator<br />

than concentration limits. Mixtures that cannot be classified using the additivity approach<br />

shall be classified using the approach shown in Table 12.<br />

Ingredient Concentration Classification<br />

Acid with pH ≤ 2 ≥ 1 % Skin corrosive, category 1<br />

Base with pH ≥ 11.5 ≥ 1 % Skin corrosive, category 1<br />

Other skin corrosive,<br />

≥ 1 % Skin corrosive, category 1<br />

categories 1A, 1B, 1C<br />

Other skin irritant, category 2 ≥ 3 % Skin irritant, category 2<br />

Table 12. Generic concentration limits of ingredients for which the additivity approach does not apply<br />

Serious eye damage/eye irritation<br />

When using the additivity approach to calculate the classification of a mixture each<br />

ingredient classified as corrosive or irritant should be taken into account. A weighing<br />

factor of 10 is used for a corrosive substance present at a concentration below the generic<br />

cut-off value, if manufacturers or importers find it relevant to take this substance into<br />

consideration when classifying. Table 13 shows the generic concentration limits using the<br />

additivity approach. Below is given examples of calculations based on the additivity<br />

approach.<br />

Sum of ingredients classified as: Concentration limits for classification as:<br />

Eye damage, category 1 Eye irritation, category<br />

2<br />

Eye damage, category 1 or Skin<br />

corrosive, categories 1A, 1B, 1C<br />

≥ 3 % ≥ 1 % but < 3 %<br />

Eye irritation, category 2 ≥ 10 %<br />

(10 * eye damage, category 1) +<br />

eye irritation, category 2<br />

≥ 10 %<br />

Skin corrosive, categories 1A,<br />

≥ 3 % ≥ 1 % but < 3 %<br />

1B, 1C + eye damage, category 1<br />

10 * (skin corrosive, category 1A,<br />

1B, 1C + eye damage, category 1)<br />

+ eye irritation, category 2<br />

Table 13. Generic concentration limits of ingredients classified for corrosive/irritant hazards<br />

≥ 10 %<br />

Care must be taken when classifying mixtures containing ingredients such as strong acids<br />

<strong>and</strong> bases, inorganic salts, aldehydes, phenols, surfactants etc. as the additivity approach<br />

may not be applicable for many of these ingredients. For mixtures containing strong acids<br />

or strong bases the pH shall be used as classification criteria since pH is a better indicator<br />

than concentration limits. Mixtures that cannot be classified using the additivity approach<br />

shall be classified using the approach shown in Table 14.<br />

33


Ingredient Concentration Classification<br />

Acid with pH ≤ 2 ≥ 1 % Eye damage, category 1<br />

Base with pH ≥ 11.5 ≥ 1 % Eye damage, category 1<br />

Other corrosive, category 1 ≥ 1 % Eye damage, category 1<br />

Other irritant, category 2 ≥ 3 % Eye irritation, category 2<br />

Table 14. Generic concentration limits of ingredients for which the additivity approach does not apply<br />

Non-additive concentration limits<br />

For some hazard classes the concentration limits are non-additive. If any ingredient in the<br />

mixture exceeds the limit the mixture shall be classified in the respective hazard class.<br />

The following hazard classes use non-additive concentration limits:<br />

• Sensitisers (respiratory <strong>and</strong> skin)<br />

• CMR-substances<br />

• STOT<br />

• Aspiration hazard<br />

• Hazardous to the ozone layer<br />

Sensitisation<br />

The mixture shall be classified as a respiratory or skin sensitiser when at lease one<br />

ingredient has been classified as a respiratory or skin sensitiser <strong>and</strong> is present at or above<br />

the concentration limits shown in Table 15.<br />

Ingredient classified<br />

as:<br />

Concentration limits for classification as:<br />

Skin sensitiser Respiratory sensitiser<br />

Solid / liquid gas<br />

-<br />

Skin sensitiser ≥ 0.1 % 3 -<br />

≥ 1 % - -<br />

Respiratory<br />

- ≥ 0.1 %<br />

sensitiser<br />

3 ≥ 0.1 % 3<br />

- ≥ 1 % ≥ 0.2 %<br />

Table 15. Generic concentration limits of ingredients classified for sensitising hazards<br />

3 This concentration limit is used for application of specific label requirements. Safety Data Sheet is<br />

required for mixtures containing ingredients above this limit.<br />

34


CMR-effects<br />

The mixture shall be classified as a carcinogen when at least one ingredient has been<br />

classified as a category 1A, 1B or 2 carcinogen <strong>and</strong> is present at or above the<br />

concentration limits shown in Table 16.<br />

Concentration limits for classification as:<br />

Ingredient classified as:<br />

Category 1A Category 1B Category 2<br />

carcinogen carcinogen carcinogen<br />

Category 1A carcinogen ≥ 0.1 %<br />

Category 1B carcinogen ≥ 0.1 %<br />

Category 2 carcinogen ≥ 1 % 4<br />

Table 16. Generic concentration limits of ingredients classified for carcinogenic hazards<br />

The mixture shall be classified as a mutagen when at least one ingredient has been<br />

classified as a category 1A, 1B or 2 mutagen <strong>and</strong> is present at or above the concentration<br />

limits shown in Table 17<br />

Concentration limits for classification as:<br />

Ingredient classified as:<br />

Category 1A Category 1B Category 2<br />

mutagen mutagen mutagen<br />

Category 1A mutagen ≥ 0.1 %<br />

Category 1B mutagen ≥ 0.1 %<br />

Category 2 mutagen ≥ 1 %<br />

Table 17. Generic concentration limits of ingredients classified for germ cell mutagenic hazards<br />

The mixture shall be classified as a reproductive toxicant when at least one ingredient has<br />

been classified as a category 1A, 1B or 2 reproductive toxicant <strong>and</strong> is present at or above<br />

the concentration limits shown in Table 18.<br />

The mixture shall be classified for effects on or via lactation when at lease one ingredient<br />

has been classified for effects on or via lactation <strong>and</strong> is present at or above the<br />

concentration limits shown in Table 18.<br />

Ingredient classified as:<br />

Category 1A<br />

reproductive<br />

toxicant<br />

Concentration limits for classification as:<br />

Category 1B<br />

reproductive<br />

toxicant<br />

Category 2<br />

reproductive<br />

toxicant<br />

Effects on<br />

or via<br />

lactation<br />

Category 1A reproductive toxicant ≥ 0.3 % 5<br />

Category 1B reproductive toxicant ≥ 0.3 % 5<br />

Category 2 reproductive toxicant ≥ 3 % 5<br />

Effects on or via lactation ≥ 0.3 % 5<br />

Table 18. Generic concentration limits of ingredients classified for reproductive toxic hazards<br />

4<br />

If a category 2 carcinogen is present in the mixture at a concentration ≥ 0,1% a safety data sheet shall be<br />

available on request.<br />

5<br />

If the concentration is ≥ 0,1% a safety data sheet shall be available on request.<br />

35


STOT – single exposure<br />

The mixture shall be classified as a specific target organ toxicant (specific organ<br />

specified), following single exposure when at least one ingredient has been classified as a<br />

category 1 or 2 specific target organ toxicant <strong>and</strong> is present at or above the concentration<br />

limits shown in Table 19.<br />

Ingredient classified as:<br />

Category 1, Specific Target Organ<br />

Toxicant<br />

Category 2, Specific Target Organ<br />

Toxicant<br />

Category 3, Specific Target Organ<br />

Toxicant<br />

Concentration limits for classification as:<br />

Category 1 Category 2<br />

≥ 10 % 1 % ≤ conc. < 10 %<br />

≥ 10 % 6<br />

Concentration limit depends on the<br />

hazard(s) of the category 3 substance(s).<br />

However, a generic concentration limit of<br />

20 % is normally appropriate.<br />

Table 19. Generic concentration limits of ingredients classified for specific target organ toxic hazards<br />

STOT – repeated exposure<br />

The mixture shall be classified as a specific target organ toxicant (specific organ<br />

specified), following single exposure, repeat exposure, or both when at least one<br />

ingredient has been classified as a category 1 or 2 specific target organ toxicant <strong>and</strong> is<br />

present at or above the concentration limits shown in Table 20<br />

Ingredient classified as:<br />

Category 1, Specific Target Organ<br />

Toxicant<br />

Category 2, Specific Target Organ<br />

Toxicant<br />

Concentration limits for classification as:<br />

Category 1 Category 2<br />

≥ 10 % 1 % ≤ conc. < 10 %<br />

≥ 10 % 7<br />

Table 20. Generic concentration limits of ingredients classified for specific target organ toxic hazards<br />

Aspiration hazard<br />

Ingredient classified as: Classification of mixture<br />

Category 1, aspiration hazard<br />

Category 1, aspiration hazard ≥ 10 % 8,9<br />

Table 21. Classification for Aspiration hazard<br />

6<br />

If the concentration is ≥ 1% a safety data sheet shall be available on request<br />

7<br />

If the concentration is ≥ 1% a safety data sheet shall be available on request<br />

8 2 0<br />

Kinematic viscosity of mixture is ≤ 20.5 mm /s at 40 C<br />

9<br />

Mixtures with two or more distinct layers one of which classified Caterory 1, aspiration hazard <strong>and</strong> with a<br />

kinematic viscosity of mixture is ≤ 20.5 mm 2 /s at 40 0 C<br />

36


Environmental effects<br />

All ingredients classified as Acute category 1 must be considered. The effects are<br />

additive. If the sum of the ingredients is ≥ 25 % the mixture shall be classified as Acute<br />

Category 1. The classification is summarised in Table 22<br />

Sum of ingredients classified as: Classification of mixture<br />

Acute Category 1 * M 10 ≥ 25 %<br />

Acute Category 1<br />

Table 22. Classification for Acute hazards based on summation<br />

The classification of mixtures for Chronic (long term) hazards based on summation of<br />

classified ingredients is shown in Table 23. These effects are additive.<br />

Sum of ingredients classified as: Classification of mixture<br />

Chronic Category 1 x M 9 ≥ 25 % Chronic Category 1<br />

(M x 10 x Chronic Category 1) + Chronic Category 2 ≥<br />

25 %<br />

Chronic Category 2<br />

(M x 100 x Chronic Category 1) + (10 x Chronic<br />

Category 2) + Chronic Category 3 ≥ 25 %<br />

Chronic Category 3<br />

Chronic Category 1 + Chronic Category 2 + Chronic<br />

Category 3 + Chronic Category 4 ≥ 25 %<br />

Chronic Category 4<br />

Table 23. Classification for Chronic hazards based on summation<br />

Highly toxic components<br />

Acute category 1 <strong>and</strong> Chronic category 1 with toxicities below 1 mg/l contributes to the<br />

toxicity of the mixture even at low concentration <strong>and</strong> should therefore be multiplied by a<br />

factor instead of just adding up the percentages. Table 24 shows the corresponding<br />

L(E)C50 value <strong>and</strong> multiplying factor M.<br />

L(E)C50 value Multiplying factor (M)<br />

0.1 < L(E)C50 ≤ 1 1<br />

0.01 < L(E)C50 ≤ 0.1 10<br />

0.001 < L(E)C50 ≤ 0.01 100<br />

0.0001 < L(E)C50 ≤ 0.001 1000<br />

0.00001 < L(E)C50 ≤ 0.0001 10000<br />

continue in factor 10 intervals<br />

Table 24. Multiplying factor (M)<br />

Hazardous for the ozone layer<br />

Mixtures shall be classified as hazardous for the ozone layer on the basis of the individual<br />

concentration of the substance(s). This hazard is not an additive effect.<br />

Ingredient classified as: Classification of mixture<br />

Hazardous for the ozone layer ≥ 0.1 %<br />

Table 25. Classification as hazardous for the ozone layer<br />

10 See Table 24 for explanation of the M-factor<br />

37


Labelling<br />

The supplier of a substance or mixture shall ensure that any substance or mixture<br />

classified as hazardous according to the criteria described in <strong>CLP</strong> carries a label.<br />

Unclassified mixtures must, in some cases, be labelled as well.<br />

Labelling of unclassified mixtures<br />

Mixtures not classified as hazardous must be labelled if they fulfil the criteria described<br />

in Table 26. They should be labelled with one or more of the supplemental statements<br />

described in the chapter: Supplemental information. Please note that the criteria in some<br />

cases also apply for classified mixtures.<br />

Unclassified mixture containing:<br />

Lead ≥ 0.15 %<br />

Cyanoacrylate<br />

Cement containing > 0.0002 % Chromium (VI)<br />

Isocyanates<br />

Epoxy constituents, MW ≤ 700<br />

> 1 % active chlorine <strong>and</strong> sold to the general public<br />

Cadmium <strong>and</strong> intended to be used for soldering or brazing<br />

Halogenated hydrocarbon <strong>and</strong> > 5 % flammable or highly<br />

flammable substances<br />

≥ 0.1 % of a substance classified as skin or respiratory sensitiser,<br />

category 1<br />

≥ 0.1 % of a substance classified as carcinogenic, category 2<br />

≥ 0.1 % of a substance classified as toxic to reproduction, category<br />

1A, 1B or 2 or with effects via lactation<br />

≥ 1 % (0.2 % for gaseous mixtures) of a substance classified with<br />

other health or environmental hazards than mentioned above<br />

≥ 1 % (0.2 % for gaseous mixtures) of a substance with an EU<br />

exposure limit value<br />

Table 26. Unclassified mixtures with dem<strong>and</strong> for a label<br />

38


Content of the label<br />

A label must contain the following information:<br />

1. Name, address <strong>and</strong> telephone number of the supplier of the substance or mixture<br />

2. For chemicals sold to the general public: The nominal quantity<br />

3. Product identifiers (see page 45)<br />

4. Hazard pictogram(s), if required<br />

5. Signal word, if required<br />

6. Hazard statement(s), if required<br />

7. Precautionary statement(s), if required<br />

8. Supplemental information, if required (see page 45)<br />

For placement of the above information on the label please see Example of a label, page<br />

48.<br />

Hazard Pictograms<br />

With <strong>CLP</strong> new hazard pictograms are introduced. The EU symbols which are black on an<br />

orange background will no longer be used. The new hazard pictograms for<br />

physical/chemical hazards are found in Table 27.<br />

Pictogram Name Number<br />

Exploding bomb GHS01<br />

Flame GHS02<br />

Flame over circle GHS03<br />

Gas cylinder GHS04<br />

Corrosion GHS05<br />

Table 27. Pictograms for physical/chemical hazards<br />

39


The hazard pictograms for health hazards <strong>and</strong> environmental hazards are found in Table<br />

28.<br />

Pictogram Name Number<br />

Skull <strong>and</strong><br />

crossbones<br />

GHS06<br />

Table 28. Pictograms for health hazards<br />

Corrosion GHS05<br />

Exclamation mark GHS07<br />

Health hazard GHS08<br />

Environment GHS09<br />

40


Principles of precedence for hazard pictograms<br />

Labels for substances <strong>and</strong> mixtures labelled according to <strong>DSD</strong> <strong>and</strong> DPD will contain<br />

three hazard symbols as a maximum. This is due to the fact that only one hazard symbol<br />

for health hazards, one for physical/chemical hazards <strong>and</strong> one for environmental hazards<br />

must be stated on the label.<br />

With <strong>CLP</strong> there is no upper limit for the number of hazard pictograms. Therefore more<br />

than three pictograms on the label are possible. However, <strong>CLP</strong> introduces principles of<br />

precedence for hazard pictograms which will, in some cases, reduce the number of<br />

pictograms on the label. An overview of the principles of precedence is found in Table<br />

29.<br />

If this pictogram is used Do NOT use Comments<br />

Flame <strong>and</strong> Flame over<br />

Circle must be on the<br />

label if both hazard<br />

pictograms are m<strong>and</strong>atory<br />

for respiratory<br />

sensitisation<br />

irritation<br />

Table 29. Principles of precedence for hazard pictograms<br />

for skin or eye<br />

for skin<br />

sensitisation or for skin <strong>and</strong><br />

eye irritation<br />

Signal words<br />

<strong>CLP</strong> introduces two signal words: “Danger” <strong>and</strong> “Warning”. For each hazard class <strong>and</strong><br />

category a signal word is assigned. “Danger” indicates the more severe hazard category<br />

while “Warning” indicates the less severe hazard categories. The signal words are used<br />

on the hazard labels for substances <strong>and</strong> mixtures. Only one signal word is used on a label.<br />

If “Danger” is used on the label, “Warning” shall not appear on the label. See also<br />

Example of a label page 48.<br />

41


Hazard statements<br />

The <strong>CLP</strong> hazard statements correspond to the R-phrases (Risk phrases) known from the<br />

<strong>DSD</strong>/DPD system. There are no principles of precedence for the <strong>CLP</strong> hazard statements.<br />

All hazard statements resulting from the classification of a substance or a mixture must<br />

appear on the label. This includes hazards statements where the corresponding hazard<br />

pictogram has been left out due to precedence principles. However, a hazard statement<br />

may be omitted if there is evident duplication.<br />

Examples of hazard statements are shown in Table 30 <strong>and</strong> also in Example of a label.<br />

H225 Highly flammable liquid <strong>and</strong> vapour<br />

H301 Toxic if swallowed<br />

Table 30 Example of hazard statements<br />

Additional EU-statements<br />

To maintain the present level of protection for human <strong>and</strong> environment, EU has chosen to<br />

add some additional hazard statements <strong>and</strong> labelling elements. These hazard statements<br />

<strong>and</strong> labelling elements are not a part of the global GHS-system. The criteria for use are<br />

given in the Annex II of the <strong>CLP</strong>-regulation.<br />

<strong>CLP</strong> contains 14 additional hazard statements. The additional hazard statements are<br />

found in Table 31.<br />

EUH001 Explosive when dry<br />

EUH006 Explosive with or without contact with air<br />

EUH014 Reacts violently with water<br />

EUH018 In use may form flammable/explosive vapour-air mixture<br />

EUH019 May form explosive peroxides<br />

EUH030 Can become highly flammable in use<br />

EUH044 Risk of explosion if heated under confinement<br />

EUH029 Contact with water liberates toxic gas<br />

EUH031 Contact with acids liberates toxic gas<br />

EUH032 Contact with acids liberates very toxic gas<br />

EUH066 Repeated exposure may cause skin dryness or cracking<br />

EUH070 Toxic by eye contact<br />

EUH071 Corrosive to the respiratory tract<br />

EUH059 Hazardous to the ozone layer<br />

Table 31. Additional EU hazard statements<br />

Furthermore the <strong>CLP</strong> contains additional statements for labelling of certain substances<br />

<strong>and</strong> mixtures. The supplemental label elements are found in Table 32.<br />

42


EUH201 Contains lead. Should not be used on surfaces liable to be chewed or<br />

sucked by children<br />

EUH201A Warning! Contains lead<br />

EUH202 Cyanoacrylate. Danger. Bonds skin <strong>and</strong> eyes in seconds. Keep out of<br />

the reach of children<br />

EUH203 Contains chromium (VI). May produce an allergic reaction<br />

EUH204 Contains isocyanates. May produce an allergic reaction<br />

EUH205 Contains epoxy constituents. May produce an allergic reaction<br />

EUH206 Warning! Do not use together with other products. May release<br />

dangerous gases (chlorine)<br />

EUH207 Warning! Contains cadmium. Dangerous fumes are formed during<br />

use. See information supplied by the manufacturer. Comply with<br />

safety instructions<br />

EUH208 Contains “name”. May produce an allergic reaction<br />

EUH209 Can become highly flammable in use<br />

EUH209A Can become flammable in use<br />

EUH210 Safety data sheet available on request<br />

EUH401 To avoid risk to human health <strong>and</strong> the environment, comply with the<br />

instructions for use<br />

Table 32. Additional EU labelling statements<br />

Precautionary statements<br />

The <strong>CLP</strong> precautionary statements correspond to the S-phrases (Safety phrases) known<br />

from the <strong>DSD</strong>/DPD-system. The precautionary statements are supposed to guide the user<br />

of a substance or a mixture to a safe use of a chemical. Furthermore the precautionary<br />

statements tell about disposal of the chemical <strong>and</strong> first aid measures in case of accidents.<br />

The precautionary statements are divided into five groups: General, prevention, response,<br />

storage <strong>and</strong> disposal. For each hazard class <strong>and</strong> category a number of precautionary<br />

statements are assigned. The general precautionary statements are not assigned for<br />

specific hazard classes <strong>and</strong> they are used for consumer products only. In Table 33 is<br />

shown an example of precautionary statements for hazard class flammable liquid <strong>and</strong><br />

hazard category 3. See also Example of a label, page 48.<br />

43


Hazard statement H226: Flammable liquid <strong>and</strong> vapour<br />

Precautionary statements – Prevention P210: Keep away from heat/sparks/open<br />

flames/hot surfaces. – No smoking.<br />

P233: Keep container tightly closed.<br />

P240: Ground/bond container <strong>and</strong> receiving<br />

equipment.<br />

P241: Use explosion-proof<br />

electrical/ventilating/lighting/…/equipment.<br />

P242: Use only non-sparking tools.<br />

P243: Take precautionary measures against<br />

static discharge.<br />

P280: Wear protective gloves/protective<br />

clothing/eye protection/face protection.<br />

Precautionary statements – Response P303 + P361 +P353: Remove/Take off<br />

immediately all contaminated clothing.<br />

P370 + P378: In case of fire: Use … for<br />

extinction.<br />

Precautionary statements – Storage P403 + P235: Store in a well-ventilated<br />

place. Keep cool.<br />

Precautionary statements – Disposal P501: Dispose of contents/container to<br />

Table 33. Example of precautionary statements for flammable liquid, category 3<br />

The number of precautionary statements on a label should not exceed six. However, EU<br />

still needs to set criteria for choosing precautionary statements.<br />

44


Product identifiers<br />

The product identifier for a substance consists normally of a name <strong>and</strong> an identification<br />

number. If the substance is present on the List of Harmonised Classifications (Annex VI,<br />

part 3) the name <strong>and</strong> an identification number from this list must be used. If the substance<br />

is present in the Classification <strong>and</strong> Labelling Inventory (See page 50) the name <strong>and</strong><br />

identification number from this list must be used. If the substance is not present on any of<br />

the lists mentioned above, the CAS-number together with the IUPAC-name must be<br />

stated.<br />

The product identifier for a mixture consists of the trade name for the mixture (identical<br />

with the name stated in the SDS) <strong>and</strong>, in some cases, the identity of certain ingoing<br />

substances. For certain classifications of the mixture the substance(s) contributing to the<br />

classification must be stated. It is important to notice, that the dem<strong>and</strong> for identity of<br />

substances on the label for a mixture is only relevant if the mixture is classified in one or<br />

more of the categories stated in Table 34.<br />

Classification of mixture which leads to a dem<strong>and</strong> for identity of substance(s) on<br />

mixture label<br />

Acute toxicity, category 1, 2, 3 <strong>and</strong> 4<br />

Skin corrosion, category 1A, 1B <strong>and</strong> 1C<br />

Serious eye damage, category 1<br />

Germ cell mutagenicity, category 1A, 1B <strong>and</strong> 2<br />

Carcinogenicity, category 1A, 1B <strong>and</strong> 2<br />

Reproductive toxicity, category 1A, 1B <strong>and</strong> 2<br />

Respiratory sensitisation<br />

Skin sensitisation<br />

Specific target organ toxicity (STOT), single exposure, category 1, 2 <strong>and</strong> 3<br />

Specific target organ toxicity (STOT), repeated exposure, category 1 <strong>and</strong> 2<br />

Aspiration hazard, category 1<br />

Table 34. Mixture classifications which lead to a dem<strong>and</strong> for identity of substance(s) responsible for mixture<br />

classification<br />

Supplemental information<br />

For the label for a substance or mixture there may be a dem<strong>and</strong> for additional EU<br />

statements as described in Annex II of the <strong>CLP</strong> regulation. The additional EU statements<br />

are given in Table 32<br />

Special rules for packaging not exceeding 125 ml<br />

If the package of a substance or mixture does not exceed 125 ml, the hazard statements<br />

<strong>and</strong> the precautionary statements may be omitted from the label if the substance or<br />

mixture is classified as given in Table 35<br />

45


Oxidising gas, category 1<br />

Gas under pressure<br />

Flammable liquid, category 1, 2 or 3<br />

Flammable solid, category 1 or 2<br />

Self-reactive substance or mixture, type C, D, E or F<br />

Self heating substance or mixture, category 2<br />

Substance which in contact with water emit flammable gases, category 1, 2 or 3<br />

Oxidising Liquid, category 2 or 3<br />

Oxidising solid, category 2 or 3<br />

Organic peroxides, type C, D, E or F<br />

Acute Toxicity, category 4, unless supplied to the general public<br />

Skin irritant, category 2<br />

Eye irritant, category 2<br />

Specific Target Organ Toxicity (STOT), single exposure, category 2 or 3, unless supplied<br />

to the general public<br />

Specific Target Organ Toxicity (STOT), repeated exposure, category 2, unless supplied<br />

to the general public<br />

Hazardous to the aquatic environment, Acute category 1<br />

Hazardous to the aquatic environment, Chronic category 1 or 2<br />

Table 35. Classifications which allow omission of hazard- <strong>and</strong> precautionary statements on label given that<br />

package ≤ 125 ml<br />

If the size of the packaging does not exceed 125 ml then precautionary statements (but<br />

not hazard statements) may be omitted on the label if the substance or mixture is<br />

classified as given in Table 36.<br />

Flammable gas, category 2<br />

Reproductive toxicity, effects on or via lactation<br />

Hazardous to the aquatic environment, chronic category 3 or 4.<br />

Table 36. Classifications which allow omission of precautionary statements on label given that package ≤ 125 ml<br />

The hazard pictogram(s) <strong>and</strong> the signal word related to the classification of a substance or<br />

mixture must be on the label even if the hazard statements <strong>and</strong> precautionary statements<br />

are omitted. If a packaging does not exceed 125 ml but the substance or mixture does not<br />

meet the requirement for certain classifications allowing omission of hazard- <strong>and</strong>/or<br />

precautionary statements, then ALL hazard statements <strong>and</strong> precautionary statements<br />

relevant for the substance or mixture must be stated on the label. It is not allowed to omit<br />

only some of the hazard statements. En example is given in Table 37.<br />

46


Mixture 1<br />

(packaging<br />

< 125 ml)<br />

Mixture 2<br />

(packaging<br />

< 125 ml)<br />

Classification Labelling<br />

Flammable<br />

liquid, category<br />

2<br />

Flammable<br />

liquid, category<br />

2<br />

Acute toxicity,<br />

oral, category 3<br />

Table 37. Label elements of packaging less than 125 ml<br />

Pictogram Signal<br />

word<br />

Hazard<br />

statement(s)<br />

Precautionary<br />

statements<br />

Danger Omitted Omitted<br />

Danger<br />

H225: Highly<br />

flammable<br />

liquid<br />

<strong>and</strong> vapour<br />

H301:<br />

Toxic if<br />

swallowed<br />

To be chosen<br />

according to<br />

Annex I<br />

Language<br />

The language of the label must be in the official language(s) of the member state(s)<br />

where the chemical is marketed. The label may contain information in more than one<br />

language. In that case, all information must appear in all languages. Furthermore groups<br />

of hazards statements <strong>and</strong> groups of precautionary statements must be located together on<br />

the label by language.<br />

Format of a label<br />

The <strong>CLP</strong> regulation sets up requirements for a label format. Those requirements are<br />

similar to the requirements known from the <strong>DSD</strong> <strong>and</strong> DPD.<br />

The dimensions of the label depend of the size of the package. The dimensions shall be as<br />

stated in Table 38.<br />

Size of the package Label dimensions (in millimetres)<br />

3 litres or less At least 52 x 74, if possible<br />

More than 3 litres but not more than 50 litres At least 74 x 105<br />

More than 50 litres but not more than 500 litres At least 105 x 148<br />

More than 500 litres At least 148 x 210<br />

Table 38. Dimension of a label<br />

Each hazard pictogram shall cover at least 1/15 of the surface area of the label. However,<br />

the size of each hazard pictogram shall not be less than 1 cm 2 .<br />

Outer <strong>and</strong> inner packaging<br />

If a package consists of an outer <strong>and</strong> an inner packaging it is sufficient to label the outer<br />

packaging according to the rules on the transport of dangerous goods. The inner<br />

packaging must be labelled according to the <strong>CLP</strong>-regulation. If the chemical does not<br />

47


need labelling according to the rules on the transport of dangerous goods both the inner<br />

<strong>and</strong> the outer packaging must be labelled according to the <strong>CLP</strong>-regulation.<br />

Transport regulation <strong>and</strong> <strong>CLP</strong><br />

A chemical may be classified as dangerous according to the <strong>CLP</strong>-regulation <strong>and</strong><br />

according to the rules on the transport of dangerous goods. If the hazard pictogram(s)<br />

required according to the <strong>CLP</strong>-regulation relate to the same hazard as in rules on the<br />

transport of dangerous goods, the <strong>CLP</strong>-pictograms for this/these hazard(s) are not<br />

required on the label. Only the pictograms assigned according to the rules on the<br />

transportation of dangerous goods are required.<br />

Example of a label<br />

The example below is for a product classified as flammable liquid, category 2 Flammable<br />

liquid <strong>and</strong> category 3 acute toxicity, oral <strong>and</strong> containing 0.5 % of a substance classified as<br />

a skin sensitiser, category 1. The size of the packaging is assumed to be > 125 ml <strong>and</strong> the<br />

product is assumed to be sold to professional users only. In Table 39 an example of a<br />

label is shown.<br />

48


<strong>CLP</strong>-Company <strong>CLP</strong> Test Product Name 11<br />

<strong>CLP</strong>-street 111<br />

1111 <strong>CLP</strong>-city<br />

<strong>CLP</strong>- country<br />

+45 11 11 11 11<br />

Danger 13<br />

Highly flammable liquid <strong>and</strong><br />

vapour 14<br />

Toxic if swallowed<br />

Contains (name of sensitising<br />

substance). May produce an<br />

allergic reaction 16<br />

Table 39. Example of a label<br />

12<br />

Contains:<br />

<strong>CLP</strong>-substance(s) 11<br />

contributing to the<br />

classification as toxic.<br />

Wash h<strong>and</strong>s thoroughly after h<strong>and</strong>ling 15<br />

Do not eat, drink or smoke when using this product<br />

IF SWALLOWED: Immediately call a POISON<br />

CENTER or doctor/physician<br />

Store in a well-ventilated place<br />

Store locked up<br />

Dispose of contents/container in accordance with<br />

national regulation<br />

Update of label information<br />

The supplier of a chemical shall update his label at once if the classification of the<br />

chemical changes <strong>and</strong> the new hazard is more severe. Furthermore the label shall be<br />

updated at once if new supplemental information is required.<br />

If there are changes to the label for other reasons than mentioned above e.g. changes in<br />

classification to a lower hazard or change of product name, the label must be updated<br />

within 18 months.<br />

11 Product identifiers<br />

12 Hazard pictograms<br />

13 Signal word<br />

14 Hazard statements<br />

15 Precautionary statements<br />

16 Additional EU statement<br />

49


Who is affected by <strong>CLP</strong> <strong>and</strong> how?<br />

Importers <strong>and</strong> manufacturers of substances<br />

Manufacturers of substances will have to change classification, labels <strong>and</strong> safety data<br />

sheets for all substances. If a substance has already been classified according to <strong>DSD</strong>, the<br />

manufacturer does not have to re-evaluate the hazardous properties of the substance.<br />

Instead the manufacturer can “translate” the <strong>DSD</strong> classification into a <strong>CLP</strong> classification<br />

by using a conversion table given in the legislation. However, for substances placed on<br />

the market after 1 December 2010 the manufacturer will have to evaluate all hazardous<br />

properties according to <strong>CLP</strong> criteria. For substances already labelled <strong>and</strong> placed on the<br />

market before 1 December 2010 the deadline for re-labelling is 1 December 2012.<br />

Classification <strong>and</strong> labelling inventory<br />

THE GHS/<strong>CLP</strong> system is mainly a system for self-classification of substances <strong>and</strong><br />

mixtures. However, to ensure transparency of classifications of substances The European<br />

Chemicals Agency (ECHA) will establish a classification <strong>and</strong> labelling inventory. Every<br />

manufacturer or importer of substances must report the classification of a substance to<br />

ECHA no later than 1 December 2010 unless the substance has to be registered under<br />

REACH. These classifications will be gathered in the classification <strong>and</strong> labelling<br />

inventory, which will be accessible via internet. It is the hope that manufacturers <strong>and</strong><br />

importers by time will agree upon the same classification for the same substance.<br />

Formulators<br />

Formulators/Manufacturers of mixtures should keep the date 1 June 2015 in mind. From<br />

this date classification of all mixtures must be amended. Both labels <strong>and</strong> safety data<br />

sheets must be changed. If a mixture has already been classified according to criteria<br />

from DPD, the manufacturers may choose simply to translate the existing classification<br />

into the new <strong>CLP</strong> classification. For mixtures already labelled <strong>and</strong> placed on the market<br />

before 1 June 2015 the deadline for re-labelling is 1 June 2017.<br />

Distributors<br />

Distributors of chemicals must keep the dates for re-classification of substances <strong>and</strong><br />

mixtures in mind <strong>and</strong> they should make sure that the labels <strong>and</strong> safety data sheets from<br />

their suppliers are in compliance with the <strong>CLP</strong> legislation.<br />

End-users of chemicals<br />

The end-user of a chemical substance or mixture does not have any obligation under<br />

<strong>CLP</strong>. However, every user of chemicals must get used to the new pictograms, hazard<br />

statements <strong>and</strong> precautionary statements. The users must be properly educated to<br />

50


underst<strong>and</strong> the pictograms <strong>and</strong> phrases in order to work safely with the chemicals.<br />

Internal work place instructions may need a revision due to changed classifications.<br />

Preparation for <strong>CLP</strong> in the organisation<br />

When preparing for <strong>CLP</strong> it is first of all important to underst<strong>and</strong> your role, hence your<br />

obligations under <strong>CLP</strong>. Furthermore you should ask yourself whether you have the<br />

resources within the company to do the work or whether you need additional assistance.<br />

Most companies use IT-systems for Chemicals Management. Furthermore a lot of<br />

companies use IT-systems for classification of mixtures <strong>and</strong> for preparation of safety data<br />

sheets. There are also various IT-systems for labelling of chemicals on the market. It is<br />

important to find out whether the various IT-systems used in the company are ready for<br />

<strong>CLP</strong> or whether updates are required.<br />

Overall you should consider the resources needed for:<br />

- Training<br />

- Update of software / IT-systems (classification, labels, SDS etc.)<br />

- Generating new labels<br />

- Generating new Safety Data Sheets<br />

- Packaging<br />

- Evaluation of currently non-hazardous products – may become classified as hazardous<br />

under <strong>CLP</strong><br />

<strong>CLP</strong> / GHS in the future<br />

Guidance on how to apply the provisions of the new Regulation on classification,<br />

labelling <strong>and</strong> packaging is currently developed at the European Commission's Joint<br />

Research Centre (JRC) within REACH Implementation Project 3.6 (RIP 3.6). Four<br />

working groups have been established, dealing with general aspects, physical, health <strong>and</strong><br />

environmental hazards. They consist largely of Member State experts. The RIP 3.6<br />

guidance document will be finalized in the first half of 2009. In addition to the guidance<br />

given in RIP 3.6, it is planned to provide short <strong>and</strong> industry-oriented guidance on basic<br />

features <strong>and</strong> procedures of the proposed GHS-implementing act in form of a<br />

downloadable print document.<br />

All over the world countries are working on implementing GHS. An overview of the<br />

worldwide GHS-implementation status can be found on UNECE’s website.<br />

The plan is to update <strong>CLP</strong> / GHS biannually.<br />

51


Transitional period<br />

The transitional periods for substances <strong>and</strong> mixtures are found in Table 40 <strong>and</strong> Table 41.<br />

Transitional period for substances<br />

20 January 2009 1 December 2012<br />

1 December 2010 1 June 2015<br />

Classification <strong>DSD</strong> 17<br />

Labelling <strong>DSD</strong> or <strong>CLP</strong> <strong>CLP</strong> 18<br />

Table 40. Transitional period for substances<br />

Transitional period for mixtures<br />

<strong>DSD</strong> <strong>and</strong> <strong>CLP</strong><br />

<strong>DSD</strong> <strong>and</strong> <strong>CLP</strong> <strong>CLP</strong><br />

<strong>CLP</strong><br />

<strong>CLP</strong><br />

20 January 2009 1 June 2015<br />

1 December 2010 1 June 2017<br />

Classification DPD 19<br />

19<br />

DPD<br />

<strong>CLP</strong> <strong>CLP</strong><br />

Labelling DPD or <strong>CLP</strong> DPD or <strong>CLP</strong> <strong>CLP</strong> 20<br />

Table 41. Transitional period for mixtures<br />

<strong>CLP</strong><br />

17 In addition substances may, before 1 December 2010, be classified, labelled <strong>and</strong> packaged in accordance<br />

with <strong>CLP</strong>. In that case the provisions on labelling <strong>and</strong> packaging in <strong>DSD</strong> shall not apply.<br />

18<br />

Substances placed on the market before 1. December 2010 need not to be labelled according to <strong>CLP</strong> until<br />

1 December 2012.<br />

19 In addition mixtures may, before 1 June 2015, be classified, labelled <strong>and</strong> packaged in accordance with<br />

<strong>CLP</strong>. In that case the provisions on labelling <strong>and</strong> packaging in DPD shall not apply.<br />

20<br />

Mixtures placed on the market before 1 June 2015 need not to be labelled according to <strong>CLP</strong> until 1 June<br />

2017.<br />

52


Conversion tables<br />

To facilitate the re-classification of existing substances <strong>and</strong> mixtures a conversion table<br />

has been made. Substances already classified according to <strong>DSD</strong> before 1 December 2010<br />

do not have to be evaluated according to new <strong>CLP</strong> criteria. For these substances it is<br />

possible to use the conversion table <strong>and</strong> simply “translate” every R-phrase into<br />

corresponding <strong>CLP</strong> hazard statements. For mixtures classified according to DPD before 1<br />

June 2015 the same conversion table can be used. It is important to notice, that in some<br />

cases the classification resulting from the conversion table will be different from a<br />

classification resulting from evaluating a chemical according to new <strong>CLP</strong> criteria. One<br />

should also notice that for some physical-chemical properties no direct conversion is<br />

possible. When the transitional period is over, the conversion table is no longer relevant,<br />

as all substances <strong>and</strong> mixtures shall then be evaluated according to <strong>CLP</strong> criteria.<br />

For substances <strong>and</strong> mixtures which are not classified according to <strong>DSD</strong> or DPD, the<br />

conversion table cannot be used. The substance or mixture must be evaluated according<br />

to <strong>CLP</strong> criteria.<br />

The list of harmonised classifications from the <strong>DSD</strong>, Annex 1, has already been<br />

converted into <strong>CLP</strong> classifications. The converted list is now a part of the <strong>CLP</strong>-system.<br />

53


Links<br />

<strong>CLP</strong> Regulation:<br />

http://eurlex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2008:353:0001:1355:EN:PDF<br />

The <strong>CLP</strong> Regulation is published as one, large document containing all Annexes. The<br />

content of the Annexes are:<br />

Annex I – Classification <strong>and</strong> labelling requirements for substances <strong>and</strong> mixtures<br />

Annex II – Special rules for labelling <strong>and</strong> packaging<br />

Annex III – Hazard Statements<br />

Annex IV – Precautionary statements:<br />

Annex V – Hazard Pictograms<br />

Annex VI - Harmonised classification <strong>and</strong> labelling for certain hazardous substances, part<br />

1 <strong>and</strong> 2<br />

Annex VI – List of harmonised classification <strong>and</strong> labelling of hazardous substances, part<br />

3<br />

Annex VII – Conversion table<br />

GHS pictograms: http://www.unece.org/trans/danger/publi/ghs/pictograms.html<br />

ECHA, European Chemicals Agency: http://echa.europa.eu<br />

UNECE – Overview of GHS-implementation status:<br />

http://www.unece.org/trans/danger/publi/ghs/implementation_e.html<br />

UN GHS text: http://www.unece.org/trans/danger/publi/ghs/ghs_rev02/02files_e.html<br />

European Commission – Enterprise <strong>and</strong> Industry:<br />

http://ec.europa.eu/enterprise/reach/ghs_more_on_com_proposal_en.htm<br />

54


GHS/<strong>CLP</strong> Vocabulary<br />

Term Explanation<br />

Substance Pure chemical substance. May be a liquid,<br />

a gas or a solid substance<br />

Mixture Mixture of two or more chemical<br />

substances. The mixture may be a liquid, a<br />

gas or a solid mixture. A water-based<br />

dilution of a pure substance is also<br />

considered a mixture. The term “mixture”<br />

used in <strong>CLP</strong> is equal to the term<br />

“preparation” used under REACH<br />

Chemical A common term used for both substances<br />

<strong>and</strong> mixtures<br />

Classification Determination of the hazardous properties<br />

of a chemical substance or mixture. It is<br />

important to notice that the classification is<br />

not a risk assessment. The classification<br />

tells about the inherent hazards of a<br />

chemical.<br />

GHS Globally Harmonised System of<br />

classification <strong>and</strong> labelling of chemicals<br />

<strong>DSD</strong> Dangerous Substance Directive<br />

(67/548/EEC)<br />

DPD Dangerous Preparations Directive<br />

(1999/45/EC)<br />

<strong>CLP</strong> Regulation of Classification, Labelling <strong>and</strong><br />

Packaging of substances <strong>and</strong> mixtures<br />

Formulator Any natural or legal person established<br />

within the Community who manufactures a<br />

mixture <strong>and</strong> place it on the market within<br />

the Community<br />

Importer Any natural or legal person established<br />

within the Community who is responsible<br />

for import into the Community.<br />

Manufacturer Any natural or legal person established<br />

within the Community who manufactures a<br />

substance within the Community.<br />

QSAR Quantitative Structure Activity<br />

Relationship. The process by which<br />

chemical structure is quantitatively<br />

correlated with a well defined process, such<br />

as biological activity or chemical reactivity.<br />

ECHA European Chemicals Agency<br />

55


End User Any professional user or consumer who<br />

buys <strong>and</strong> uses chemicals but who do not<br />

market the chemicals.<br />

56


Exercises<br />

Exercise 1. Classification of substances – translation table<br />

Convert the <strong>DSD</strong> classifications of the following substances into <strong>CLP</strong> classifications<br />

using the translation table in Annex VII. In addition, list the relevant hazard statement for<br />

each hazard class <strong>and</strong> category.<br />

Substance A: T;R25 C;R34 Carc3;R40 R43<br />

Substance B: F;R11 Xi;R41 R67 <strong>and</strong> initial boiling point > 35 °C<br />

Substance C: Xn;R22 Xi;R38 N;R50/53 21<br />

Exercise 2. Classification of mixtures – calculation<br />

Classify the following mixtures based on the <strong>CLP</strong> classifications of the ingoing<br />

substances found in exercise 1. Use the calculation principles described in Annex I or in<br />

this compendium.<br />

Mixture 1<br />

Substance Weight %<br />

Substance A 4 %<br />

Substance C 2 %<br />

Rest: Water 94 %<br />

Mixture 2 22<br />

Substance Weight %<br />

Substance A 23<br />

0.5 %<br />

Substance B 9 %<br />

Substance C 7 %<br />

Rest: Water 83.5 %<br />

Exercise 3. Labelling – label for previous classified mixture<br />

Product identifier(s)<br />

State which (if any) substance(s) must be stated on the label for mixture 1 <strong>and</strong> mixture 2.<br />

Use table 31 in this compendium.<br />

21<br />

LC50 = 0,03 mg/l for substance C<br />

22<br />

Flash point of mixture > 60 °C<br />

23<br />

Substance A should be taken into consideration for skin <strong>and</strong> eye irritation even when present in amounts<br />

below the generic cut-off value<br />

57


Signal Words<br />

State the signal word on the label for mixture 1 <strong>and</strong> mixture 2. Use the label elements<br />

tables in Annex 1 to assign the correct signal word.<br />

Hazard pictograms<br />

State the hazard pictograms required on the label for mixture 1 <strong>and</strong> 2. Do not use<br />

principles of precedence yet. Use the label elements tables in Annex 1 to choose the<br />

correct hazard pictograms.<br />

Hazard Statements<br />

State the hazard statements resulting from the classification of mixture 1 <strong>and</strong> 2. Assume<br />

that packaging > 125 ml. Use the label elements tables in Annex 1 to assign the correct<br />

hazard statements.<br />

Supplemental information<br />

State which (if any) supplemental information is required on the label for mixture 1 <strong>and</strong><br />

2. Use table 29 in this compendium.<br />

Exercise 4. Principles of Precedence – Choosing hazard<br />

pictograms<br />

Using principles of precedence, state the hazard pictograms required on the label for<br />

mixture 1 <strong>and</strong> 2. In addition consider whether evident duplication makes it relevant to<br />

omit one or more hazard statements. Use Table 29 in this compendium.<br />

58


Solutions<br />

Exercise 1<br />

The <strong>CLP</strong>-classifications are:<br />

Substance <strong>DSD</strong> <strong>CLP</strong><br />

Hazard Class Hazard<br />

Category<br />

A T;25 Acute toxicity 3 H301<br />

A C;R34 Skin Corrosion 1B H314<br />

A Carc3;R40 Carcinogenicity 2 H351<br />

A R43 Skin Sensitiser 1 H317<br />

B F;R11 Flammable<br />

liquid<br />

2 H225<br />

B Xi;R41 Eye Damage 1 H318<br />

B R67 STOT, single<br />

exposure<br />

3 H336<br />

C Xn;R22 Acute toxicity 4 H302<br />

C Xi;R38 Skin irritation 2 H315<br />

C N;R50/53 Aquatic Acute 1 H400<br />

C N;R50/53 Aquatic<br />

Chronic<br />

1 H410<br />

Exercise 2<br />

Mixture 1<br />

Substance Weight %<br />

Substance A 4 %<br />

Acute toxicity, cat 3, oral<br />

Skin corr., cat 1B<br />

Carc, cat 2<br />

Skin sens., cat 1<br />

Substance C 2 %<br />

Skin irrit., cat 2<br />

Acute toxicity, cat 4, oral<br />

Aquatic Acute, cat 1<br />

Aquatic Chronic, cat 1<br />

Water 94 %<br />

Not classified<br />

Hazard<br />

statement<br />

59


Acute toxicity<br />

Converted ATE-values for substance A <strong>and</strong> C for oral exposure are found using Table 9.<br />

Oral exposure: 100


Mixture 2<br />

Substance Weight %<br />

Substance A 0.5 %<br />

Acute tocixity,cat 3, oral<br />

Skin corr., cat 1<br />

Carc, cat 2<br />

Skin sens., cat 1<br />

Substance B 9 %<br />

Flammable liquid, cat 2<br />

Eye dam., cat 1<br />

STOT, single, cat 3<br />

Substance C 7 %<br />

Skin irrit., cat 2<br />

Acute toxicity, cat 4, oral<br />

Aquatic Acute, cat 1<br />

Aquatic Chronic, cat 1<br />

Water 83.5 %<br />

Not classified<br />

Acute toxicity<br />

Converted ATE-values for substance A <strong>and</strong> C for oral exposure are found using Table 9.<br />

Oral exposure: 100


STOT<br />

Using Table 19 <strong>and</strong> a generic concentration value of 20 % we find that mixture 20 is not<br />

classified for STOT.<br />

Environmental toxicity, acute<br />

The M-factor for substance C is found using Table 24. As the LC50-value for the<br />

substance is 0.03 mg/l the M-factor is 10. Using the formula in Table 22 we find:<br />

10 x 7 % = 70 % → mixture 2 classified as acute, cat. 1<br />

Environmental toxicity, chronic<br />

The M-factor for substance C is 10. Table 23 is used:<br />

10 x 7 % = 70 % → mixture classified as chronic, cat. 1<br />

Classification for mixture 2<br />

Skin irritant, cat. 2, H315<br />

Eye effects, cat. 1, H318<br />

Aquatic acute, cat 1, H400<br />

Aquatic chronic, cat. 1, H410<br />

Exercise 3<br />

62


Hazard pictogram(s) Signal<br />

Word<br />

Mixture 1<br />

Hazard<br />

Statement(s)<br />

Danger H318: Causes<br />

serious eye<br />

damage.<br />

H315: Causes<br />

skin irritation.<br />

H351:<br />

Suspected of<br />

causing<br />

cancer<br />

H317: May<br />

cause an<br />

allergic skin<br />

reaction<br />

H411: Toxic<br />

to aquatic life<br />

with long<br />

lasting effects<br />

Supplemental<br />

hazard<br />

statements<br />

Product<br />

identifier<br />

None Substance<br />

A<br />

63


Hazard<br />

pictogram(s)<br />

Mixture 2<br />

Signal Word Hazard<br />

Statement(s)<br />

Danger H318: Causes<br />

serious eye<br />

damage.<br />

H315: Causes<br />

skin irritation.<br />

H400: Very<br />

toxic to aquatic<br />

life.<br />

H410: Very<br />

toxic to aquatic<br />

life with long<br />

lasting effects.<br />

Supplemental<br />

hazard<br />

statements<br />

Contains<br />

substance A.<br />

May produce<br />

an allergic<br />

reaction<br />

Product<br />

identifier<br />

Substance B<br />

Exercise 4<br />

For mixture 1 no principles of precedence will be relevant. There is no duplication of<br />

hazard statements.<br />

For mixture 2 the hazard pictogram “Exclamation mark” must be omitted, as the<br />

pictogram appears for skin irritation <strong>and</strong> as the pictogram “Corrosive” is m<strong>and</strong>atory.<br />

The hazard statement H400 may be omitted as the exact same statement is found in<br />

H410.<br />

Therefore, the label elements for mixture 2 are:<br />

64


Hazard<br />

pictogram(s)<br />

Final labels<br />

Mixture 2<br />

Signal Word Hazard<br />

Statement(s)<br />

Danger H318: Causes<br />

serious eye<br />

damage.<br />

H315: Causes<br />

skin irritation.<br />

H410: Very<br />

toxic to aquatic<br />

life with long<br />

lasting effects.<br />

The final label for mixture 1 may appear as follows:<br />

Supplemental<br />

hazard<br />

statements<br />

Contains<br />

substance A.<br />

May produce<br />

an allergic<br />

reaction<br />

Company name Mixture 1<br />

Company address<br />

City<br />

Telephone<br />

DANGER<br />

Causes serious eye damage.<br />

Causes skin irritation.<br />

Suspected of causing cancer.<br />

May cause an allergic skin reaction.<br />

Toxic to aquatic life with long lasting<br />

effects.<br />

Product<br />

identifier<br />

Substance B<br />

Contains: Substance A<br />

Obtain special instruction before use.<br />

Wear protective gloves <strong>and</strong> protective<br />

clothing.<br />

IF IN EYES: Rinse cautiously with water<br />

for several minutes. Remove contact<br />

lenses, if present <strong>and</strong> easy to do. Continue<br />

rinsing.<br />

Dispose of contents in according with local<br />

regulation.<br />

Avoid release to the environment.<br />

65


The final label for mixture 2 may appear as follows:<br />

Company name Mixture 2<br />

Company address<br />

City<br />

Telephone<br />

DANGER<br />

Causes serious eye damage.<br />

Causes skin irritation.<br />

Very toxic to aquatic life with long<br />

lasting effects.<br />

Contains substance A. May produce an<br />

allergic reaction<br />

Contains: Substance B<br />

Wear protective gloves <strong>and</strong> protective<br />

clothing.<br />

IF IN EYES: Rinse cautiously with water<br />

for several minutes. Remove contact<br />

lenses, if present <strong>and</strong> easy to do. Continue<br />

rinsing.<br />

IF ON SKIN: Wash with plenty of soap<br />

<strong>and</strong> water.<br />

Dispose of contents in according with local<br />

regulation.<br />

Avoid release to the environment.<br />

66

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