REGULATION
LISA D. M. ALLEN
REACHReady Ltd, Kings Buildings, Smith Square, London SW1P 3JJ, United Kingdom.
Lisa D. M. Allen
CLP: the mixtures challenge
KEYWORDS: CLP, mixtures, chemicals, classification, labelling
Abstract
Now that hazardous substances are classified and labelled in accordance with CLP throughout the EU,
attention turns to the supply of mixtures. From 1st June 2015, the CLP Regulation applies to all mixtures, from
simple blends of a substance in a solvent through to complex, multi-stage formulations of mixtures within mixtures alike. Companies
supplying formulated products should consider the most appropriate method to classify their mixtures; when compared to previous
classification and labelling practices, suppliers of mixtures may have to rely on expert judgement more than simple calculations, and
they may find that CLP requires significant label re-design and investment to achieve compliance.
INTRODUCTION
The EU Regulation on the Classification, Labelling and Packaging
of substances and mixtures (CLP) (1) entered into force in
January 2009. In the five years since, it has transformed the
way in which the intrinsic properties of hazardous substances
are identified and categorised, and how that information is
communicated on packaging. Over the next three years the
provisions of CLP will also be applied to mixtures. These changes
bring such ‘classification’ and ‘labelling’ in the EU in line with
the UN’s Globally Harmonised System (GHS) (2), which seeks
to promote a high level of protection of both human health
and the environment. This article aims
to review the CLP Regulation and how it
applies to substances and mixtures in the
EU.
TRANSITION TO CLP
Through its transitional period from 2010 to
2017, CLP repeals the existing provisions
on classification, packaging and labelling
for supply, namely the Dangerous
Substances Directive (DSD) (3) and the
Dangerous Preparations Directive (DPD)
(4). In doing so, the legislative framework
shifts from national laws which implement
these EU Directives, to a direct-acting,
EU-wide Regulation based on a global
scheme to harmonise classification and
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labelling across the world. Despite the significant amount of
work involved to achieve compliance, it is important that such
clear and harmonised rules are not seen as a burden but as a
guarantee for workers and consumers of their protection (5).
NEW LABELS
To ease the burden of implementation of CLP on industry,
different transitional deadlines apply to substances (i.e.
chemical elements and their compounds in the natural state
or obtained by any manufacturing process) and mixtures (i.e.
mixtures or solutions composed of two
or more substances). The first – and most
striking – change that CLP has brought
about is that, since 1st December 2010,
substances being placed on the EU
market must be labelled according to
CLP rather than DSD. Under CLP, the
familiar orange and black square danger
symbols first introduced by DSD in 1967
have been replaced with red-framed
square-on-a-point (diamond) hazard
pictograms containing black symbols
against a white background.
While most of the imagery is familiar, CLP
has introduced three new black symbols
in its pictograms: the ‘exclamation mark’,
which indicates lower acute toxicity
and irritation effects; the ‘silhouette’
Figure 1. The nine CLP pictograms
(sometimes referred to as the ‘exploding
Chimica Oggi - Chemistry Today - vol. 32(3) May/June 2014
Figure 2. Health effects indicated by the silhouette and exclamation
mark pictograms, together with the equivalent DSD/DPD danger
symbols they replace
with the requirements for the transport of dangerous goods.
Although these increased numbers may at first suggest an
increase in scope for classification, the new hazard classes
generally represent the division of the same hazard under more
specific descriptions. For example, under DSD/DPD, the term
‘oxidising’ applied to substances and mixtures which give rise to
a highly exothermic reaction in contact with other (particularly
flammable) substances (6). In CLP, such substances and mixtures
which cause or contribute to the combustion of other materials
are further classified according to their physical state: solid, liquid
or gas (7), yielding three hazard classes in the place of one.
man’), which indicates serious, chronic health effects; and the
‘gas cylinder’ for gases under pressure.
As part of the transitional measures, substances which were
already in the EU supply chain on 1st December 2010 and
labelled to DSD had a grace period of two years to reach
the final user without the need to re-classify and re-label in
accordance with CLP. For all other substances that were first
placed on the EU market after that date, CLP applied. From
1st December 2012, all substances on the EU market had to
be labelled according to CLP; substances still labelled to DSD
are no longer in compliance.
DEADLINE TO CLASSIFY AND LABEL MIXTURES
From 1st June 2015, mixtures being placed on the EU market
must be classified and labelled in accordance with CLP.
The same set of hazard classes and categories will apply;
the same nine pictograms will pertain to the labelling of
mixtures, heralding the demise of the traditional orange and
black symbols. As with substances, there will be a two-year
grace period for mixtures which are already ‘on the shelves’
and labelled to DPD to reach the final user – for example,
formulated products already received by a retailer from an
EU supplier which are held in the former’s warehouse – but for
goods being first placed on the market on or after 1st June
2015 CLP must be applied.
This deadline applies to all mixtures that are in scope of the
Regulation, from the simplest dissolution of one substance
in one solvent, through to complex formulations comprising
multiple levels of mixtures within mixtures.
CLASSIFICATION
In order to label appropriately, suppliers must first classify their
chemical according to its intrinsic properties. With CLP’s new
hazard pictograms came new hazard classes; which are subdivided into categories with different criteria for classification.
When labelling under CLP, suppliers apply:
• up to six of the nine pictograms;
• one or more hazard class and category;
• one or more associated hazard (H) statements,
• one signal word, either ‘danger’ or ‘warning’, and
• up to six precauationary (P) statements.
Under the old regime there were fifteen danger classes, but CLP
comprises some twenty-nine hazard classes. For the physical
hazards, for example, CLP sees a move from five to sixteen hazard
classes and introduces classes such as ‘corrosive to metals’. In
doing so, the new regime brings the classification for supply in line
Chimica Oggi - Chemistry Today - vol. 32(3) May/June 2014
Table 1. Physical hazards: a comparison of DSD/DPD and CLP
For health effects, changes in terminology result in a significant
change to the hazard classes. Under the former legislative
system, a chemical which causes ‘acute or chronic damage to
health’ is classified as ‘harmful’; under CLP, that same chemical
may instead be classified according to its acute toxicity,
aspiration toxicity, specific target organ toxicity – single exposure
(‘STOT SE’), or specific target organ toxicity – repeated exposure
(‘STOT RE). Furthermore, for some health effects, notably acute
toxicity and irritation, there may be an apparent increase
in hazard when transitioning to CLP. Of course, the intrinsic
properties of the substance or mixture have not changed, but
when compared with the criteria of the two regulatory schemes
those same data indicate different classifications. In the case of
acute oral toxicity, for example, a substance with an LD50 value
of 250 mg/kg was classified as harmful under DSD; under CLP,
the substance is considered toxic (8).
DIFFERENT APPROACHES TO CLASSIFICATION OF MIXTURES
Compared with DPD, when classifying mixtures under CLP there
is less emphasis on making simple calculations and more on
expert judgement. There are, however, four main approaches to
classifying mixtures:
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Table 2. Health and environmental hazard classes under CLP
Classify from raw test data;
Use ‘bridging’ principles to read across from similar
formulations;
• Use an ingredient-based approach;
• Convert existing DPD classifications using the translation
tables in CLP.
While no one approach works for all, each of these methods
comes with its own benefits and limitations and may be useful in
preparing for the 1st June 2015 deadline.
Classifying from test data obtained on the mixture itself is
perhaps the most accurate, but time-consuming, approach.
However, it is not always possible as the required information
may not exist. Mixtures are not normally tested for health effects
in the EU, and national measures may restrict or prohibit the
testing of mixtures, for example the UK coalition’s pledge to ‘end
the testing of household products on animals’ (9).
Bridging principles also rely on data on mixtures, using information
on one tested mixture to allow read-across to another, similar,
mixture. It is a common-sense approach for many new
formulations and can be useful in dilution and concentration,
and interpolation amongst groups of similar mixtures. In the case
of dilution, where a tested mixture is diluted with a substance of
an equivalent or lower hazard category than the least hazardous
ingredient substance, the classifier can assume, as a worst case,
that the respective hazard of the new mixture is equivalent to
that of the original, tested mixture (10). However, not all bridging
principles apply to each hazard class; those planning to use
such approaches must check the relevant sections of CLP to see
which rules apply to the hazard class of interest.
The third approach, which is perhaps most commonly used by
formulators and classification software systems, is an ingredientbased approach. This method relies on combining data for
each of the component substances, which may not exist if
the substance has not been registered under REACH (11) or
a similar regulatory regime. It also requires full knowledge of
the formulation, which is sometimes a significant challenge for
importers. As such, the value of this method depends heavily
on the availability, adequacy and quality of the component
data used. A variety of sources of information exist which the
classifier may need to consult; noteworthy are the registered
substances dissemination portal (12), the harmonised (minimum)
classifications of Annex VI to CLP found in the Classification and
•
•
70
Labelling Inventory (13), and supplier self-classifications which
may be also found in the Classification and Labelling Inventory
and in safety data sheets and catalogues.
When classifying a mixture in this manner, the principle of
additivity may be used for some effects such as acute toxicity,
whereas fixed concentration limits must be used for effects such
as STOT, sensitisation, and carcinogenicity since these hazards
tend to be molecule-specific. The nature of the product being
placed on the market must also be considered: although the
formulation lists the ingredients added to the mixing vessel,
these substances do not necessarily correspond to the species
present in the final mixture. Changing physical form, for example
dissolving solids into liquids or liquefying gases, may also impact
the hazard profile of the final mixture.
Under CLP, calculation methods offer more flexibility to deviate
from criteria than was permitted under DPD. However, to do so
requires expert judgement, normally involving significant training,
or the use of consultants proficient in the field of classification.
In the fourth approach, CLP’s translation tables (14) may assist reclassification for endpoints where the mixture is classified under
DPD and where there is reasonable coherence between the
criteria of DPD and CLP, such as carcinogenicity. Few physical
hazards can be translated, however, and for some health
effects, such as acute toxicity, the method gives only a minimum
classification. In addition, particular care is required with mixtures
which have been classified under DPD on the basis of expert
judgement rather than calculation alone, and those which were
not classified as dangerous under DPD but contain corrosive or
irritant components or reproductive toxicants. Note that the use
of this approach is limited to where there are no further data
available for the considered hazard class (15); whenever data
for the mixture are available, an evaluation and classification
must be carried out in accordance with Articles 9 to13 of CLP
(14), rather than relying on the translation tables in Annex VII.
For physical hazards, where insufficient data are available to
classify for a particular endpoint, companies must carry out
testing to generate the data required for classification. Such
testing either needs to be carried out to a recognised quality
system such as Good Laboratory Practice (‘GLP’) (16) or by
laboratories complying with a relevant recognised standard
such as ISO 17025 (17) or a national accreditation body such
as UKAS in the UK (18). For hazards to human health and the
environment, there is no obligation to carry out new testing;
however, companies are required to exhaust all other means
of generating data. Furthermore, for acute toxicity and
environmental effects, where a mixture contains components
for which there are no useable data the mixture may be
classified on the basis of the known components alone, with the
additional statement, ‘contains x percent of component(s) with
unknown toxicity’(19) or ‘contains x percent of component(s)
with unknown hazards to the aquatic environment’ (20) as
appropriate.
PRACTICAL ASPECTS OF LABELLING
For many years, under DSD and DPD, common practice
across industry was for suppliers to use generic format labels
pre-printed with blank orange squares for overprinting with
the black symbols relevant to the contents of the packaging.
To do the same for CLP would mean that the templates are
pre-printed with empty red diamond frames. Although not a
new issue, this practice raises concerns in the EU and beyond
that some information may have been excluded by mistake or
Chimica Oggi - Chemistry Today - vol. 32(3) May/June 2014
may desensitise the user to the impact of warnings placed on
labels (21). Although CLP does not expressly forbid the use of
pre-printed blank diamonds, suppliers must ensure any which
are surplus to requirements do not cause confusion. Article
19(1) of CLP requires suppliers to ‘include the relevant hazard
pictogram(s), intended to convey specific information on
the hazard concerned’. Moreover, Article 25(3) requires that
any supplemental information shown does not make it more
difficult to identify the mandatory label elements and does not
contradict or cast doubt on the validity of that information.
After much discussion on the subject, the European Chemicals
Agency (ECHA) recommends that, if blank diamonds are
unavoidable, suppliers cover them completely with a solid
overprint to avoid the impression that relevant symbols have
been accidentally omitted (22).
For many suppliers, CLP poses much more of a challenge to
practical labelling than DPD. Under DSD and DPD there were
sixty-six individual risk (R) phrases (23) and fifty-five individual safety
(S) phrases (24); CLP replaces these phrases with 99 individual
hazard (H) statements and 137 (including combinations)
precautionary (P) statements, respectively, increasing the
amount of information a label potentially needs to show. For
example, for a category 3 flammable liquid with no other hazard
classes, the CLP Regulation indicates one hazard statement and
eleven precautionary statements (25). For a mixture with several
hazards, therefore, it is not uncommon for more than thirty P
statements to apply. However, suppliers are normally expected
to use no more than six P statements on the label.
For a mixture made available to the consumer the six selected
P statements may differ to those most applicable for supply
to industrial or professional users, meaning that a supplier may
need more than one label for a given formulation based
on the type of customer. Furthermore, where the product is
placed on the market in more than one country, the supplier
has two options. Either: produce a multi-language label which
must remain legible and show the same CLP information in all
languages used; or produce a single-language label in the
language of each recipient Member State, resulting in multiple
labels per product.
Carried through from the former legislative system are general
requirements for the legibility of the label (26, 27). The label and
any hazard pictograms must comply with the minimum size
requirements detailed in Annex I, Part 1.2.1; the pictograms must
stand out clearly and the other label elements must be sized
and spaced appropriately so that they are easy to read. The
label must also be fixed such that it is readable horizontally when
the package is set down normally – meaning that labelling on
the underside of a box is not usually compliant.
Although there are some small package exemptions which
allow some H and P statements to be omitted from the label,
suppliers may find they have to reduce the branding and
marketing information in order to make room for the CLP label
elements. For very small packages companies may use fold-out
labels or tie-on tags on which to provide the full information,
and for soluble single-use packaging (such as clothes detergent
capsules), the outer packaging can suffice. However, fold-out
labels and tie-on tags cannot be used only to increase the
number of languages.
CHALLENGES FOR SUPPLIERS OF MIXTURES
1st June 2015 may seem distant but the deadline to implement
the requirements of CLP for mixtures is fast approaching.
Chimica Oggi - Chemistry Today - vol. 32(3) May/June 2014
Moreover, as the deadline applies to simple mixtures (i.e. blends
of substances alone) and mixtures within mixtures alike, end
formulators using mixtures as raw materials will expect – and need
– their suppliers to provide CLP information far in advance of 1st
June 2015. Such customer expectations may compel suppliers to
apply CLP early; where products have short shelf lives suppliers
may choose to implement CLP ‘early’ in order to demonstrate
the sale of ‘fresh’ stocks, or perhaps as a strategy to gain market
share as a visibly responsible and compliant supplier.
Formulators and importers of mixtures should expect the
transition to CLP to be challenging and potentially costly.
Where information is lacking or difficult to obtain, or where the
classification is complicated by multiple formulation stages (i.e.
mixtures within mixtures), companies may find they have to
invest in external expert judgement to collate and assess the
data and classify appropriately under CLP.
To produce CLP-compliant labels on demand, colour printing
facilities are required. Many suppliers may also find they require
significant re-design of artwork in order to incorporate branding,
usage instructions, and the regulatory information required
under CLP and other EU legislation, such as the Biocidal Products
Regulation (28). Under DSD and DPD, symbols were required to
cover a minimum of 1cm2; for CLP, although the minimum size is
the same, the pictograms must be set on a point. Therefore, the
virtual square within which the pictogram sits is larger than the
corresponding symbol size under the former regime, taking up
more space on the label.
CONCLUSIONS ON MANAGING COMPLIANCE
To help companies achieve their classification and labelling
obligations, REACHReady offers some simple, practical advice
on applying CLP to mixtures. When classifying, first review
the type of hazard and refer to the ECHA guidance (29) to
gain a better understanding of the classification criteria in
CLP. For physical hazards, consider testing, or compare with
tested mixtures if any components are hazardous. For health
effects, remember that acute local effects such corrosion and
irritation are generally reduced on dilution, but that additivity
does not normally apply for systemic effects such as STOT and
sensitisation. Ecotoxicity is also generally reduced on dilution and
an additivity approach may be appropriate.
Second, check the type of chemical, including any nonhazardous components. Consider pH (for example, buffering
and neutralising properties), physicochemical properties which
can affect penetration and exposure (such as surface tension,
wetting, solubility, particle size) and reactivity (including any ions
produced).
Remember that most mixtures fit into simple rules and can be
classified using an ingredient-based approach based on the
hazards of the components. For the others, however, expert
judgement may be necessary.
When it comes to labelling, be prepared for a significant
re-design. Logos and marketing information may need to be resized or even removed to make room for mandatory regulatory
information. Consider whether your products are better suited
to single- or multi-language labels, in view of both commercial
implications and regulatory requirements. Such decisions may
have financial and business consequences and should involve
more organisational functions than Regulatory Affairs alone.
Finally, consult an expert for independent advice if you are
unsure. A little spent on getting it right first time may save you a
lot in months to come.
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