Proposal for a Regulation of the European Parliament and of the Council on Detergents
Date: 2002-09-04
Institutions: European Commission
Subjects: analytical chemistry, biodegradability, environmental protection, environmental standard, free movement of goods, labelling, marketing restriction, polishing and scouring preparations, testing

COMMISSION OF THE EUROPEAN COMMUNITIES

Brussels, 4.9.2002
COM(2002) 485 final

2002/0216 (COD)

Proposal for a

REGULATION OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

on Detergents

(presented by the Commission)

EXPLANATORY MEMORANDUM

Article 1. – Objectives

issue. The proposed new biodegradability tests ensure a higher

The fundamental objective of this Regulation is the free movement of detergents in the
Internal Market. In particular it modernises the existing detergent directives, regarding the
in relation to this
biodegradability of surfactants and the protection of the environment
fundamental
level of
environmental protection and at the same time are applicable to all types of surfactants in
detergents. Furthermore, the requirements specified in Commission Recommendation 89/542,
on labelling of detergents and cleaning products, and specific information to the consumers
related to the presence in detergents of fragrance substances are made binding for the products
covered by this Regulation.

Article 2 and Annex I. – Definitions

The definition proposed for “detergent” enlarges the scope of the existing legislation to cover
other similar uses, which come within the objectives of this legislation in line with relevant
experiences in implementation in Member States.

It introduces a definition for surfactants, which was lacking in existing legislation.

Definitions are provided for the biodegradation concepts involved in the Regulation, as these
are useful for a correct implementation of its provisions.

Finally, other definitions (i.e.: “cleaning”, “washing”, “substance”, “preparation”, “placing on
the market”, etc.) that may be useful for the application of this Regulation are also considered.

Articles 3 to 7. – Limitations to placing on the market

These articles refer explicitly to the requirements for the prohibition of substances on the
market and to the conditions for the granting of derogations.

It is considered appropriate to establish a transition period of two years, counting from the
date of implementation of the Regulation, to allow manufacturers (a term which in this text
extends to include importers) of those substances concerned to apply for derogations.

The hierarchy of tests is based on environmental concerns and at the same time tries to
minimise the expenses of economic operators as only a fraction of the substances concerned
will have to be submitted to the whole array of relevant tests. This would be needed just for
those substances.

The granting of derogations for those substances failing the “ultimate biodegradability” type
tests as established in Annex III, are to be allowed following explicit application by
manufacturers and case by case Commission Decisions adopted by Committee procedure.

The granting of derogations needs as a pre-requisite the compliance with the primary
biodegradability requirements in Annex II, and depends on the assessment of the additional
information to be provided under Annex IV.

It has been considered appropriate to refer in this article to other legislation, in particular
Directive 76/769/EEC, by which substances covered in this Regulation might be the object of

2

marketing restrictions, as for example those in connection with Parcom Decisions or
Recommendations.

It is intended that there should be a shift of emphasis of responsibility towards manufacturers
who would have to ensure that all pertinent tests are carried out, instead of the present
situation that depends much on Member States initiatives.

Article 8. – Duties of the Member States

It is considered fundamental for the objectives of the Regulation to establish with precision
the main actions involving direct responsibility of the appointed competent authorities in
Member States in addition to those stipulated in Article 3 concerning the limitations to the
placing on the market.

As in the preceding legislation, Member States should notify the list of Laboratories
authorised to carry out the reference tests as established in Annexes II and III.

Article 9. – Duties of Manufacturers

Manufacturers of detergents, and/or of surfactants for detergents, should have at the disposal
of the national authorities the corresponding technical files for all substances concerned.
Member states should take all appropriate measures including active actions in order to ensure
this provision is complied with.

Manufacturers of detergents remain responsible for not marketing detergent preparations
containing non-complying surfactants and for ensuring that all
the required technical
documentation is available.

Article 10. – Control measures

The competent authorities of Member States should have the possibility of applying control
measures to ensure that manufacturers comply with this Regulation.

Article 11 and Annex VIII. – Labelling and ingredient datasheet

This article together with the corresponding Annex keep the existing provisions on labelling
as they are to be continued. At the same time and in order to take account of the development
introduced by Commission Recommendation 89/542/EEC for the labelling of detergents and
cleaning products, its provisions as established in Articles 2 and 3 are made binding.

The Recommendation has worked well in the sense that there has been a high level of
compliance in most Member States. However, the present proposal is a useful opportunity to
combine the labelling rules with other rules on the marketing of detergents.

This transition should be considered as a success of the Recommendation and it is by no
means to be interpreted as an approach against voluntary agreements. The Commission
Recommendation 98/480/EC, concerning good environmental practice for household laundry
detergents, will remain separate as it concerns areas not covered by this Regulation.

In the light of the increasing importance of fragrances and preservation agents, they are
included as a new element in relation to Recommendation 89/542/EEC.

3

A new provision is added obliging manufacturers of detergents to have at the disposal of
health care professionals a full listing of the ingredients of the detergents to assist clinicians in
investigating whether a causal link exists between the development of an allergic response
and exposure to a particular chemical substance.

Article 12. – Committee procedure

The Committee procedure proposed is a regulatory one, as established under the new
Decision 1999/468/EC.

Article 13. – Adaptation of the annexes

It is proposed that the revision of Annexes I to IX should follow the Committee procedure, as
these relate to scientific and technical matters and do not touch the fundamental hierarchy
established in the body of the Regulation.

The Committee procedure should also apply to Articles 4, 5, 7, 8 and 13 which are linked to
the placing on the market of substances and preparations.

Article 14. – Free movement clause

This is the explicit complement to the clauses on limitations to marketing and covers those
substances and preparations that are complying with the provisions of the Regulation.

Article 15. – Safeguard clause

The fact that a substance is found to be readily biodegradable does not preclude the possibility
of concern for the degradation products and biodegradation rates in relation to certain types of
uses, in particular, in cases of high influx into ecosystems.

Article 16. – Legislation to be replaced

This establishes which directives are to be superseded by the present Regulation that covers
their relevant provisions.

Article 17. – Sanctions for non-compliance

This requires the Member States to establish sanctions for non-compliance with this
Regulation.

Annex I. – Products covered within the meaning of detergent

This lists the products containing soap or other surfactants that are covered by the new
definition of detergent as set out in Article 2 and gives also a definition of them.

Annex II. – Primary biodegradability test methods

This establishes the test systems and analytical methods for assessing the primary
biodegradability of surfactants: anionic, non-ionic, cationic, and amphoteric.

The main changes in relation to the methods in the existing legislation are intended to cover
for the first time cationic and amphoteric surfactants and also those anionic and non-ionics not
reacting to the tests included in present legislation. The use of instrumental analysis for those

4

surfactants not reacting to semi-specific methods is required so that all surfactants are
covered.

These tests will be relevant
in cases of non-compliance with those on “ultimate”
biodegradability in Annex III, and they will be examined by the Committee on a case by case
basis. It has been considered better to keep the present choice of options on primary
biodegradability tests, but the reference methods for the cases of conflicting results in
different Member States are stipulated. These tests will also be necessary for calculating the
predicted environmental concentrations of the parent substance for risk assessment.

Annex III. – “Ultimate biodegradability” test methods

The approach presented is based on Annex V part C.4 (Determination of “ready”
biodegradability) of Directive 67/548/EEC.

However, account is taken of the need to adapt to scientific progress the test chosen for
reference purposes as developed by ISO.

The use of some tests not considered well suited, in general, for surfactants is made dependent
of specific authorisation by Committee procedure.

The study “Surfactant Ring Test-I” of May 1999 (WRC) concluded that pre-exposing sludge
to a surfactant for seven days in a SCAS unit before testing the surfactant in the headspace
method did not have uniform effects on the biodegradation achieved or on its variability,
although in general the degree of biodegradation was increased. Taking results from all
laboratories it is not worthwhile using this rather mild pre-exposure since it involves a fair
amount of effort for little advantage.

The proposed Annex III is also fully in line with the recommendations included in the opinion
of the CSTEE, which may be summarised as follows:

1.

2.

3.

4.

5.

The proposed “ultimate biodegradability” type tests are an improvement in relation
to primary biodegradability;

The methods ISO headspace, OECD 301 B 1 and OECD 301 D 2 are suitable but the
two OECD methods had some limitations of applicability;

The methods OECD 301 A 3, OECD 301 C 4, OECD 301 E 5 and OECD 301 F 6
were less suitable than the above mentioned;

Pre-adaptation is not deemed desirable;

The ten days window is not deemed desirable.

The test methods of Annex III are therefore the best of the available standardised test methods
for ‘ultimate biodegradability’. They are also more demanding than those for primary

1

2

3

4

5

6

Method Directive 67/548/EEC, Annex V.C.4.C.
Method Directive 67/548/EEC, Annex V.C.4.E.
Method Directive 67/548/EEC, Annex V.C.4.A.
Method Directive 67/548/EEC, Annex V.C.4.F.
Method Directive 67/548/EEC, Annex V.C.4.B.
Method Directive 67/548/EEC, Annex V.C.4.D.

5

biodegradability that are used in the current EU legislation. It is estimated that 3 % of the
surfactants that are capable of passing the test for primary biodegradability under current EU
legislation would not pass the test specified for the ‘ultimate biodegradability’ in Annex III.
Besides being stricter than the existing test, the new test also covers a significant market
segment composed of cationic and amphoteric surfactants, representing about 10 % of all
detergent surfactants, that were not previously covered by the existing tests.

Annex IV. – Complementary Risk Assessment

This establishes the additional information needed for substances failing Annex III tests but
passing Annex II tests and being submitted for derogation under Article 3(3).

Council Regulation (EEC) No 793/93 on the evaluation and control of the risks of existing
substances laid down detailed rules concerning the collection, circulation and accessibility of
information on existing substances, as well as concerning the evaluation of the risks of
existing substances to man and to the environment in order to ensure better management of
those risks within the framework of Community provisions.

Evaluation of risks before the placing on the market of new substances according to agreed
procedures is another type of programmed assessment. Such an evaluation and an appropriate
notification to a competent authority before the placing on the market are required for
chemicals by Directive 92/32/EEC amending for the seventh time Directive 67/548/EEC on
the approximation of
regulations and administrative provisions relating to
classification, packaging and labelling of dangerous substances. Plant protection products and
other biocides also have to pass thorough risk evaluation before they can receive an
authorisation to be commercialised.

the laws,

The approach envisaged here is to establish an ad-hoc complementary assessment not
intended to be closely parallel to the risk assessment procedure in the two above mentioned
pieces of legislation. Instead, the intention of the complementary assessment step is to assess
the reasons for failing the first level stage and the opportunity to allow marketing (provided
that primary biodegradability is complied with).

It is to be considered that in any event these would apply to the substances covered by the
future detergent Regulation when so stipulated.

It is to be considered that detergents and their ingredients are also covered by all the
horizontal legislation on substances and preparations and the corresponding risk assessments.

Following this line, the chosen approach is to concentrate on the elements helping to judge
whether a negative result on “ready biodegradability” type tests is a false negative and to
provide also a number of other elements considered essential to judge the environmental
impact of the surfactant in question and of its biodegradation products.

Account is taken of the Recommendations in the opinion of the CSTEE, so that the risk
assessment should put emphasis on possible metabolites and that information on the toxicity
of these metabolites is needed together with their bioconcentration potential, as well as their
partition to the sediment phase. It is emphasised that if recalcitrant metabolites are produced,
a risk assessment should be performed, according to the relevant EU legislation on dangerous
substances and to the related Technical Guidance Documents. Moreover, if some metabolites
are suspected for endocrine disrupting activity, it
is recommended to have data on this
particular hazard, as soon as validated protocols to assess this kind of effect will be available.

6

Annex V. – List of derogations

This lists all the surfactants obtaining derogations.

Annex VI. – List of banned or restricted surfactants under this Regulation

This lists all the surfactants identified as not complying with the provisions of this Regulation
or restricted in use as a result of this Regulation.

Annex VII. – List of banned surfactants in implementation of other Community
legislation

This lists surfactants covered by this Regulation and banned or restricted by other Community
legislation, in particular Directive 76/769/EEC.

Annex VIII. – Labelling and ingredient datasheet

This describes how detergent packaging shall be labelled for certain ingredients, for the
recommended quantities of detergent appropriate for a standard washing machine load, and
for the number of standard washing machine loads that can be washed with the contents of the
package. It also prescribes the format to be used for the listing of ingredients on the datasheet
intended for health care professionals.

Annex IX. – List of test methods and analytical methods

This lists the test methods and analytical methods that apply to control procedures of
detergents on the market by Member States, which were annexed to the existing detergent
legislation.

7

2002/0216 (COD)

Proposal for a

REGULATION OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

on Detergents

(Text with EEA relevance)

THE EUROPEAN PARLIAMENT AND THE COUNCIL OF THE EUROPEAN UNION,

Having regard to the Treaty establishing the European Community, and in particular
Article 95 thereof,

Having regard to the proposal from the Commission 7,

Having regard to the opinion of the Economic and Social Committee 8,

Acting in accordance with the procedure laid down in Article 251 of the Treaty 9,

Whereas:

(1)

of

anionic

surfactants 12

Council Directive 73/404/EEC of 22 November 1973 on the approximation of the laws
the Member States relating to detergents 10 as last amended by Council
of
Directive 86/94/EEC 11, Council Directive 73/405/EEC of 22 November 1973 on the
approximation of the laws of the Member States relating to methods of testing the
by Council
biodegradability
Directive 82/243/EEC 13, and Council Directive 82/242/EEC of 31 March 1982 on the
approximation of the laws of the Member States relating to methods of testing the
biodegradability
Council
Directive 73/404/EEC 14, for reasons of clarity and efficiency, should be modernised
and replaced by a single text; and labelling provisions concerning detergents and
of
cleaning
13 September 1989 for the labelling of detergents and cleaning products 15 are to be
included;

Recommendation 89/542/EEC

Commission

surfactants

amending

non-ionic

amended

products

and

last

of

of

as

(2)

In accordance with the principles of subsidiarity and of proportionality, as stated in
Article 5 of the Treaty, the objectives of the envisaged action to ensure the internal
market in detergents cannot be achieved individually by Member States if there are no
common technical criteria throughout the Community, and can therefore be better

7

8

9

10

11

12

13

14

15

OJ C , .., p. .
OJ C , .., p. .
Opinion of the European Parliament of .
OJ L 347, 17.12.1973, p. 51.
OJ L 80, 25.3.1986, p. 51.
OJ L 347, 17.12.1973, p. 53.
OJ L 109, 22.4.1982, p. 18.
OJ L 109, 22.4.1982, p. 1.
OJ L 291, 10.10.1989, p. 55.

8

achieved by Community action; this action should be limited to the minimum required
to achieve these objectives and should not exceed what is necessary to this end; a
Regulation is the appropriate legal instrument as it imposes directly on manufacturers
precise requirements to be implemented at the same time and in the same manner
legislation, uniformity of
throughout
application in the Member States is needed, and this can only be guaranteed by a
Regulation;

in the area of technical

the Community;

(3)

(4)

(5)

(6)

(7)

(8)

(9)

A new definition for detergents is needed to cover equivalent uses and be in line with
developments at Member State level;

It is necessary to introduce a surfactant definition, which was lacking in the existing
legislation;

It
is important
biodegradability;

to give a clear and precise description of the relevant

types of

Measures concerning detergents should be adopted to ensure the functioning of the
internal market and avoid restricting the competition in the Community;

As confirmed by the Commission White Paper on the strategy for a future Chemical
Policy 16 these measures should ensure a high level of environmental protection,
especially of the aquatic environment;

Recommendation 89/542/EEC

Detergents are already subject
to certain Community provisions concerning the
manufacture, proper handling, usage and labelling, in particular with reference to
Commission
Commission
Recommendation 98/480/EC of 22 July 1998 concerning good environmental practice
for household laundry detergents 17; Directive 1999/45/EC of the European Parliament
and of the Council of 31 May 1999 concerning the approximation of the laws,
regulations and administrative provisions of the Member States relating to the
classification, packaging and labelling of dangerous preparations 18 applies to
detergents;

and

(including
Ditallow-dimethyl-ammonium-chloride (DTDMAC) and Nonylphenol
ethoxylates derivatives-APEs) are priority substances undergoing at Community level
Risk Assessment activities, in accordance with Council Regulation (EEC) No 793/93
of 23 March 1993 on the evaluation and control of the risks of existing substances 19,
and if necessary adequate strategies to limit the risks of exposure to these substances
will be recommended and implemented in the framework of other
relevant
EC instruments;

(10)

The existing legislation on biodegradability of surfactants in detergents only covers
primary biodegradability 20 and it is only applicable to anionic 21 and non-ionic 22

16

17

18

19

20

21

Document COM(2001) 88 final.
OJ L 215, 1.8.1998, p. 73.
OJ L 200, 30.7.1999, p. 1.
OJ L 84, 5.4.1993, p. 1.
Council Directive 73/404/EEC (OJ L 347, 17.12.1973, p. 51) and Council Directive 86/94/EEC
(OJ L 80, 25.3.1986, p. 51).
Council Directive 73/405/EEC (OJ L 347, 17.12.1973, p. 53) and Council Directive 82/243/EEC
(OJ L 109, 22.4.1982, p. 18).

9

surfactants; therefore it needs to be replaced by new legislation, which lays the main
emphasis on ultimate biodegradability and meets the important concerns related to the
potential toxicity of persistent metabolites;

(11)

This requires the introduction of a new set of tests based on EN ISO standards and
OECD guidelines, which governs the granting of direct permission for placing
detergents on the market;

(12)

To provide a high level of protection of the environment, detergents not fulfilling
requirements laid down by this Regulation, shall not be placed on the market;

(13) On 25 November 1999 the Scientific Committee on Toxicity, Ecotoxicity and the
Environment has issued an opinion on biodegradability of surfactants in detergents
and relevance of test-methods for regulatory control in this area;

(14)

(15)

(16)

(17)

(18)

(19)

(20)

The existing requirements regarding primary biodegradability are to be maintained on
a second hierarchy level for those surfactants failing “ultimate biodegradability” tests;
furthermore surfactants failing primary biodegradability tests cannot obtain marketing
authorisation by way of derogation;

The primary biodegradability requirements need to be extended to all surfactants, in
particular cationic and amphoteric, whilst allowing the possibility of applying
instrumental analyses in those cases in which semi-specific analytical methods are not
suitable;

The determination of biodegradability test-methods, setting criteria for derogations,
and the record-keeping of lists of derogations are technical matters, which need to be
revised taking into account technical and scientific developments as well as regulatory
developments;

Test-methods
biodegradability of surfactants in detergents;

should produce data that give sufficient assurance of aerobic

Test-methods to test biodegradability of surfactants in detergents may produce
variable results and may need to be complemented by additional assessments in order
to determine the risks of continued use;

Provisions should also be set out
in exceptional cases
surfactants in detergents failing “ultimate biodegradability” tests and this should take
place on the basis of all relevant information to ensure environmental protection and
on a case by case basis;.

to place on the market

Since the measures necessary for the implementation of this Regulation are measures
of general scope within the meaning of Article 2 of Council Decision 1999/468/EC of
28 June 1999 laying down the procedures for the exercise of implementing powers
conferred on the Commission23, they should be adopted by use of the regulatory
procedure provided for in Article 5 of that Decision;

22

23

Council Directive 82/242/EEC (OJ L 109, 22.4.1982, p. 1).
OJ L 184, 17.7.1999, p.23.

10

(21)

(22)

is appropriate to refer to other horizontal

It
legislation applicable to detergent
surfactants, in particular Council Directive 76/769/EEC of 27 July 1976 by which the
marketing and use of dangerous substances covered by this Regulation might be
restricted 24, Council Directive 67/548/EEC of 27 June 1967 on the
banned or
approximation of laws, regulations and administrative provisions relating to the
classification, packaging and labelling of dangerous substances 25, Commission
Directive 93/67/EEC of 20 July 1993 on assessment of
risks to man and the
environment of new substances 26 or Regulation (EEC) No 793/93; and Commission
Regulation (EC) No 1488/94 of 28 June 1994 laying down the principles for the
assessment of risks to man and the environment of existing substances 27;

It should be the responsibility of manufacturers to refrain from marketing detergents
not complying with the provisions of this Regulation and to have at the disposal of the
national authorities
substances and
preparations covered by this Regulation; this should also apply to surfactants that have
failed to pass the tests mentioned in Annex III;

the corresponding technical

for all

files

(23) Manufacturers should be able to request a derogation and the Commission should have
the possibility to grant such derogation in accordance with the Committee procedure
of this Regulation;

(24) Members State competent authorities should be able to apply control measures to
detergents on the market, but should avoid repeating tests made by the competent
laboratories;

(25)

be

should

including

provisions

continued,

Labelling
in
Recommendation 89/542/EEC, for the labelling of detergents and cleaning products,
which is included in order to fulfil the objective of modernising the rules on detergent
products. Specific labelling is introduced to inform consumers about fragrance
substances and preservation agents that are present
in detergents. Health care
professionals should be able to obtain from the manufacturer upon request a full listing
of all ingredients of a detergent to assist them investigate whether a causal link exists
between the development of an allergic response and exposure to a particular chemical
substance;

those

(26) All

the above points call for new legislation replacing the existing legislation;
however, for a period not exceeding eighteen months, Member States can continue to
apply their existing laws;

(27)

The technical Annexes to this Regulation are to be adapted by Committee procedure;

(28) Detergents complying with this Regulation should be allowed to be placed on the

market without prejudice to other relevant Community provisions;

(29)

In order to ensure the protection of man and the environment from unforeseen risks of
detergents, a safeguard clause is needed;

24

25

26

27

OJ L 262, 27.9.1976, p. 201.
OJ L 196, 16.8.1967, p. 1.
OJ L 227, 8.9.1993, p. 9.
OJ L 161, 29.6.1994, p. 3.

11

(30)

meeting

The tests specified for the biodegradability of surfactants should be carried out in
namely
laboratories
EN/ISO/IEC/17025; it would not be justified to ask for the application of this latter
requirement to existing surfactants to the extent that the available tests on them had
been performed before the entering into force of the above standard and still provide a
comparable level of scientific quality;

internationally

recognised

standard,

an

(31)

The issues relating to anaerobic biodegradation, the biodegradation of the main non-
surfactant organic detergent ingredients, and phosphate content should be reviewed by
the Commission and, where this is justified, a proposal should be presented to the
European Parliament and the Council;

(32)

The five Directives and the Commission Recommendation mentioned in recital 1
which are replaced by this Regulation should be repealed;

HAVE ADOPTED THIS REGULATION:

1.

2.

Article 1
Objectives and scope

This Regulation establishes rules designed to achieve the free movement of
detergents and surfactants for detergents in the internal market while, at the same
time, ensuring a high degree of protection of the environment.

For this purpose, this Regulation lays down rules for:

–

–

the biodegradability of surfactants in detergents and

the labelling of detergents.

For the purpose of this Regulation:

Article 2
Definitions

1.

2.

3.

4.

“Detergent” means any substance or preparation containing soaps or other
surfactants intended for water-based washing processes. Detergents may be in any
form (liquid, powder, paste, bar, cake, moulded piece, shape, etc.) and used for
household, and/or institutional and/or industrial purposes. Other products to be
considered as covered within the meaning of this definition are listed in Annex I.A;

“Washing” means the cleaning of laundry, fabrics, dishes or kitchen utensils;

“Cleaning” has the meaning defined by EN ISO 862;

“Substance” means chemical elements and their compounds in the natural state or
obtained by any production process, including any additive necessary to preserve the
stability of the products and any impurity deriving from the process used, but
excluding any solvent which may be separated without affecting the stability of the
substance or changing its composition;

12

5.

6.

7.

8.

9.

“Preparation” means mixture or solution composed of two or more substances;

“Surfactant” means any organic substance and/or preparation used in detergents
which is intentionally added to achieve cleaning, rinsing, fabric softening and/or any
other purpose due to its surface-active properties, and which consists of one or more
hydrophilic and one or more hydrophobic groups of such a nature and size that it is
capable of forming micelles;

“Primary biodegradation” means the structural change (transformation) of a
surfactant by micro-organisms resulting in the loss of its surface-active properties
due to the degradation of the parent substance and consequential loss of the surface-
active property as measured in test-methods listed in Annex II;

“Ultimate aerobic biodegradation” means the level of biodegradation achieved when
the surfactant is totally used by micro-organisms in the presence of oxygen resulting
in its breakdown to carbon dioxide, water and mineral salts of any other elements
present (mineralisation) , as measured in tests methods listed in Annex III, and new
microbial cellular constituents (biomass) ;

“Placing on the market” means introducing onto the Community market, thereby
making available to third parties, whether
in exchange for payment or not.
Importation into the Community customs territory shall be deemed to be placing on
the market;

10.

“Manufacturer” means the natural or legal person (including importers) placing a
detergent and/or a surfactant for detergents on the market.

Article 3
The placing on the market

1.

2.

3.

1.

2.

Detergents and surfactants for detergents referred to in Article 1 shall conform with
the conditions, characteristics and limits laid down in this Regulation and its
Annexes when placed on the Community market.

Manufacturers of detergents and/or of surfactants for detergents shall be established
within the Community.

Manufacturers shall be responsible for
surfactants for detergents with the provisions of this Regulation and its Annexes.

the conformity of detergents and of

Article 4
Limitations to the placing on the market

If a detergent contains surfactants for which the level of “ultimate aerobic
biodegradation” is less than that stipulated in Annex III, manufacturers of detergents
containing surfactants, and/or of surfactants for detergents may ask for derogation.
Requests for derogation shall be made in accordance with the provisions of Articles 5
and 9.

The level of “primary biodegradability” shall be measured for all surfactants in
detergents failing “ultimate aerobic biodegradation” tests. Detergent surfactants, for

13

which the level of “primary biodegradability” is less than that stipulated in Annex II,
shall not be granted derogation.

Article 5
Granting of derogation

The request by a manufacturer for derogation shall be made by sending an
application to the competent authorities of the Member State concerned, referred to
in Article 8(1), and to the Commission, providing evidence relating to the criteria
mentioned under Article 6(1).

include a technical file supplying all

the information and
Applications shall
justifications necessary for evaluating the safety aspects related to the specific use of
surfactants in detergents failing to comply with the biodegradability limits, as set out
in Annexes II and III.

In addition to the results of tests stipulated in Annex III, the technical file shall
include results of tests, as stipulated in Annexes II and IV.

receiving applications for
The competent authorities of
derogation according to paragraphs 1 and 2 above, shall examine the requests,
evaluate their compliance with the conditions for derogation and inform the
Commission about the results without delay.

the Member States,

If the competent authority of the Member State deems it necessary, for the evaluation
of the risk which may be caused by a substance and/or a preparation, it may ask for
information, verification and/or confirmatory tests concerning these
further
substances and/or preparations or their transformation products, of which they have
been notified or have received information under this Regulation.

The Commission may grant derogation in accordance with the procedure set out in
Article 12(2). If necessary before granting derogation the Commission may evaluate
further the matters indicated in paragraph 3 above.

Such derogations may allow, limit or severely restrict the placing on the market and
the use of surfactants in detergents, depending on the results of the complementary
risk assessment, as defined in Annex IV of this Regulation. They may include a
phase-out period for placing on the market and the use of surfactants in detergents.

The Commission shall publish the list of surfactants that have obtained derogation,
with the corresponding conditions or limitations of use, as provided in Annex V.

Article 6
Refusal of derogation

Where the Commission intends to refuse to grant a derogation it may do so on the
basis of the following criteria:

–

use in high volumes;

1.

2.

3.

4.

5.

6.

1.

14

–

–

use in wide-dispersive applications, such as use by the general public, rather
than in low-dispersive applications, such as specialized industrial and/or
institutional cleaning;

socio-economic benefits do not outweigh the impact on human health and the
environment.

As long as the Commission has not decided on a request for derogation, the use of
the surfactant in question may be maintained, provided the manufacturer can show
that the surfactant was already in use on the Community market at the date of entry
into force of this Regulation and that the request for derogation was made within two
years from that date. If the Commission refuses to grant a derogation for a surfactant,
it may set a transitional period during which the use of the surfactant in question
shall be phased-out. This transitional period shall not exceed two years.

Article 7
Testing of surfactants and listing of those that are banned or restricted for use

All tests referred to in Articles 3 and 4 and in Annexes II, III, IV and IX shall be
conducted in compliance with the standard mentioned in Annex I.B.1. In cases where
surfactants are used in detergents which were marketed before the entry into force of
the above standard, existing tests that were performed using the best scientific
knowledge available, and that were performed to a standard comparable to that of the
standard mentioned in Annex I.B.1, may be accepted on a case-by-case basis. The
manufacturer or the Member State may submit to the Commission any case over
which there is doubt or dispute. A decision will then be taken in accordance with the
procedure laid down in Article 12(2).

Surfactants, which are banned or restricted for use for not complying with this
Regulation, are listed in Annex VI.

Surfactants listed in Annex VII are also banned or restricted for use in detergents,
independently of the results of the tests under Annexes II, III, and IV, as a result of
other Community legislation and in particular Directive 76/769/EEC.

Article 8
Duties of the Member States

Member States shall appoint the competent authority or authorities responsible for
communicating and exchanging information relating to the management of this
Regulation and inform the Commission of the name and full address of these
authorities.

Each Member State shall notify the other Member States and the Commission the list
that are competent and
of approved laboratories, with full name and address,
authorised to carry out the tests required by this Regulation and its Annexes. Member
States shall demonstrate the competence of the above laboratories according to the
standards mentioned in Annex I.B.

Where a Member State competent authority has grounds for believing that an
approved laboratory does not possess the competence referred to in paragraph 2

15

2.

1.

2.

3.

1.

2.

3.

4.

1.

2.

3.

1.

2.

above, it shall raise the matter in the Committee referred to in Article 12. If the
Commission decides that the laboratory does not possess the required competence
referred to in paragraph 2, the name of the approved laboratory shall be removed
from the list referred to in paragraph 4. Article 15(2) shall apply.

The Commission shall publish the lists of competent authorities, mentioned in
paragraph 1, and of approved laboratories, mentioned in paragraph 2, in the Official
Journal of the European Communities.

Article 9
Duties of Manufacturers

Manufacturers placing on the market the preparations and/or the substances covered
by this Regulation shall hold at the disposal of the competent authorities of the
Member States:

–

–

information on one or more results of the tests mentioned in Annex III;

for those surfactants failing to pass tests stipulated in Annex III, and for which
a request for derogation was made as referred to in Article 5:

i)

ii)

a technical file on results of tests as stipulated in Annex II,

a technical file on results of tests as stipulated in Annex IV.

Whenever substances and preparations covered by this Regulation are placed on the
market, the manufacturer shall be responsible for the correct performance of the
relevant tests mentioned above. He shall also have available - documentation on the
testing carried out to demonstrate compliance with the Regulation, and to show that
he is allowed to benefit from the property rights concerning the test results, other
than for those test results already in the public domain.

Manufacturers placing on the market the preparations covered by this Regulation
shall, upon request, make available without delay and free of charge, to any health
care professional, a datasheet listing all ingredients as stipulated in Annex VIII.C.

Article 10
Control measures

Member State competent authorities may apply, as appropriate, control measures to
detergents on the market by using the test and analytical methods referred to in
Annex IX. These control measures shall not oblige manufacturers to repeat tests
made by laboratories fulfilling the conditions indicated in Article 8(2), or to pay for
any repeat or additional test, provided the initial test has shown compliance of
detergents, or surfactants used in detergents, with this Regulation.

In cases of concern that the test-methods in Annex II, III, IV or IX have produced
false positive results,
the Member State competent authorities shall notify the
Commission and the Commission may, in accordance with the procedure laid down
in Article 12(2), verify those results and take the necessary measures.

16

1.

2.

3.

4.

5.

1.

2.

3.

4.

Article 11
Labelling

The provisions of this Article are without prejudice to the provisions relating to the
classification, packaging and labelling of dangerous substances and preparations in
Directive 67/548/EEC and Directive 1999/45/EC on the approximation of the laws,
regulations and administrative provisions of the Member States relating to the
classification, packaging and labelling of dangerous preparations .

The following information must appear in legible, visible and indelible characters on
the packaging in which the detergents are put up for sale to the consumer:

a)

b)

c)

the name of the product;

the name or trade name and address or trademark of the party responsible for
placing the product on the market;

the address from which the datasheet referred to in Article 9(3) can be
obtained.

The same information must appear on all documents accompanying detergents
transported in bulk.

The packaging of detergents
specifications provided for in Annex VIII.A.

shall

indicate the content, according to the

Additionally, the packaging of detergents sold to the general public intended to be
used as laundry detergents shall bear the information provided for in Annex VIII.B.

In cases where a Member State has a national requirement to label in the national
language(s), it shall notify the Commission thereof, and the manufacturer shall
comply with that requirement for the information specified in paragraphs 3 and 4
above.

Article 12
Committee procedure

The Commission shall be assisted by a committee, composed of representatives of
the Member States and chaired by the representative of the Commission.

Where
to
Decision 1999/468/EC shall apply in compliance with Article 8 thereof.

paragraph, Articles 5

is made

reference

this

and

7

of

The period provided for in Article 5(6) of Decision 1999/468/EC shall be three
months.

The committee shall adopt its rules of procedure.

17

Article 13
Adaptation of the annexes

The amendments necessary for adapting Annexes I, II, III, IV, V, VI, VII, VIII and IX shall
be adopted in accordance with the procedure laid down in Article 12(2), and shall, wherever
possible, use European Standards.

Article 14
Free movement clause

Members States shall not prohibit, restrict or impede the placing on the market of detergents,
and/or of surfactants for detergents, which comply with the requirements of this Regulation.

1.

2.

1.

2.

3.

Article 15
Safeguard clause

Where a Member State has justifiable grounds for believing that a specific detergent,
although satisfying the requirements of this Regulation, constitutes a risk to safety or
health of humans or of animals or a risk to the environment, it may temporarily
prohibit the placing on the market of that detergent
in its territory or make it
temporarily subject to special conditions.

It shall immediately inform the other Member States and the Commission thereof,
giving the reasons for its decision.

After consultation of the Member States, or if appropriate of the relevant technical or
scientific committee of the Commission, a decision shall be taken on the matter
within ninety days in accordance with the procedure referred to in Article 12(2).

Article 16
Legislation to be replaced

The following Directives are hereby repealed with effect from the date of entry into
force of this Regulation:

–

–

–

–

–

Directive 73/404/EEC;

Directive 73/405/EEC;

Directive 82/242/EEC;

Directive 82/243/EEC and

Directive 86/94/EEC.

References to the above Directives shall be construed as being references to the
present Regulation.

Recommendation 89/542/EEC for the labelling of detergents falling under the scope
of this Regulation is hereby repealed.

18

Article 17
Sanctions for non-compliance

1.

No later than the day of the entry into force of this Regulation, Member States shall
establish:

–

–

appropriate legal or administrative measures in order to deal with any non-
compliance with the provisions of this Regulation and

dissuasive, effective and proportionate sanctions for any such non-compliance.

2.

They shall immediately inform the Commission thereof.

Article 18
Entry into force

This Regulation shall enter into force 18 months after its publication in the Official Journal of
the European Communities.

This Regulation shall be binding in its entirety and directly applicable in all Member States.

Done at,

For the European Parliament
The President

For the Council
The President

19

ANNEX I

A.

List of products that are covered within the meaning of detergent

The following products containing soap or other surfactants are also covered within the
meaning of the detergent definition as set out in Article 2(1):

–

–

–

–

B.

“Auxiliary washing preparation”, as intended for soaking (pre-washing), rinsing or
bleaching clothes, household linen, etc.;

“Laundry fabric-softener”, as intended to modify the feel of fabrics in processes
which are to complement the washing of fabrics;

“Cleaning preparation”, as intended for domestic all purposes cleaners and/or other
water based cleaning of surfaces (e.g.: materials, products, machinery, mechanical
appliances, means of transport and associated equipment, instruments, apparatus,
etc.);

“Other cleaning and washing preparations”, as intended for any other water-based
processes.

Standards of accreditation concerning the laboratories that are competent and
authorised to provide the necessary service for checking compliance of
EC detergents with the requirements of this regulation and its annexes

1.

Standards applicable at the level of the laboratories:

EN ISO/IEC 17025, General
calibration laboratories.

requirements for

the competence of

testing and

2.

Standards applicable at the level of the accreditation bodies:

EN 45003, Calibration and testing laboratory accreditation system, general
requirements for operation and recognition.

20

ANNEX II
“Primary biodegradability” test methods for surfactants in detergents

Primary biodegradability is measured by the determination in biodegraded liquors of the
remaining level of parent surfactants. This Annex begins with a list of the test-methods
common to all classes of surfactants, and then lists under headings A to D the analytical test
procedures specific to each class of surfactant.

The pass criterion for primary biodegradability shall be a level of at least 80 %, as measured
according to the tests below.

The reference method for the laboratory testing of surfactants in this Regulation is based on
the “Confirmatory test procedure” in the OECD method, described in Annex IX.1. Changes to
the Confirmatory test procedure are permissible provided that
they comply with
EN ISO 11733.

1.

2.

3.

4.

5.

TEST METHODS

The OECD method published in the OECD's technical report of 11 June 1976 on the
“Proposed Method for the Determination of the Biodegradability of Surfactants in
Synthetic Detergents”.

The method in use in France, approved by the “arrêté du 24 décembre 1987”
published in the Journal officiel de la République française of 30 December 1987,
p. 15385, and by standard NF 73-260 of June 1981, published by the Association
française de normalisation (AFNOR);

The method in use in Germany, established by the “Verordnung über die
Abbaubarkeit anionischer und nichtionischer grenzflächenaktiver Stoffe in Wasch-
und Reinigungsmitteln„ of 30 January 1977, published in the Bundesgesetzblatt,
Part I, p. 244, as set out in the Regulation amending that Regulation of 18 June 1980,
published in the Bundesgesetzblatt, Part I, p. 706

The method in use in the United Kingdom called the “Porous Pot Test” and
described in Technical Report No 70 (1978) of the Water Research Centre.

The “Confirmatory test procedure” in the OECD method, described in Annex IX.1
(including possible changes in operating conditions as proposed in EN ISO 11733).
This is also the reference method used for the settlement of litigation.

A.

Analytical Methods for Anionic Surfactants

The determination of anionic surfactants in the tests shall be done by the Methylene Blue
Active Substance (MBAS) analysis according to the criteria established in Annex IX.2

For those anionic surfactants not reacting to the above-mentioned MBAS method, or if it
seems more appropriate for reasons of efficiency or precision (this must be justified)
appropriate instrumental analyses specific for the surfactant under study are to be applied.
Samples of the pure surfactant of interest shall be provided by the manufacturer to the
competent national authorities of the Member States upon request.

21

B.

Analytical Methods for Non-ionic Surfactants

The determination of non-ionic surfactants in the tests shall be done by the Bismuth Active
Substance (BiAS) method, according to the analytical procedure established in Annex IX.3.

For those non-ionic surfactants not reacting to the above-mentioned BiAS method, or if it
seems more appropriate for reasons of efficiency or precision (this must be justified)
appropriate instrumental analyses specific for the surfactant under study are to be applied.
Samples of the pure surfactant of interest shall be provided by the manufacturer to the
competent national authorities of the Member States upon request.

C.

Analytical Methods for Cationic Surfactants

The determination of cationic surfactants in the tests shall be done by the Disulfine Blue
Active Substance (DBAS) analysis according to the following DBAS procedures:

The method in use in the Federal Republic of Germany,
Ausgabe: 1989-07.

(1989) DIN 38 409 –

For those cationic surfactants not reacting to the above-mentioned test method, or if it seems
more appropriate for reasons of efficiency or precision (this must be justified) appropriate
instrumental analyses specific for the surfactant under study are to be applied. Samples of the
pure surfactant of interest shall be provided by the manufacturer to the competent national
authorities of the Member States upon request.

D.

Analytical Methods for Amphoteric Surfactants

The determination of amphoteric surfactants in the tests shall be done by analysis following
the procedures listed below:

1.

2.

If cationics absent:

The method in use in the Federal Republic of Germany, (1989) DIN 38 409-Teil 20.

Otherwise:

Orange II method (Boiteux, 1984).

For those amphoteric surfactants not reacting to the above-mentioned tests, or if it seems
more appropriate for reasons of efficiency or precision (this must be justified) appropriate
instrumental analyses specific for the surfactant under study are to be applied. Samples of the
pure surfactant of interest shall be provided by the manufacturer to the competent authorities
of the Member States upon request.

22

ANNEX III
“Ultimate biodegradability” (mineralisation) test methods for surfactants in detergents

A.

reference method for

surfactant ultimate
The
biodegradability in this Regulation is based on the EN ISO Standard 14593:
1999 (CO2 headspace test).

laboratory

testing

of

Surfactants in detergents shall be considered as biodegradable if the level of biodegradability
(mineralisation) measured according to one of the five following tests 28 is at least 60 %
within twenty-eight days:

1.

2.

3.

4.

5.

B.

1.

2.

28

29

EN ISO Standard 14593: 1999. Water quality. – Evaluation of ultimate aerobic
biodegradability of organic compounds in aqueous medium. – Method by analysis of
inorganic carbon in sealed vessels (CO2 headspace test). Pre-adaptation is not to be
used. The ten days window principle is not applied. (Reference method.)

Method Directive 67/548/EEC Annex V.C.4.C [Carbon dioxide (CO2) Evolution
Modified Sturm Test]: Pre-adaptation is not to be used. The ten days window
principle is not applied.

Method Directive 67/548/EEC Annex V.C.4.E (Closed Bottle): Pre-adaptation is not
to be used. The ten days window principle is not applied.

Method Directive 67/548/EEC Annex V.C.4.D (Manometric Respirometry): Pre-
adaptation is not to be used. The ten days window principle is not applied.

Method Directive 67/548/EEC Annex V.C.4.F (MITI: Ministry of International Trade
and Industry-Japan): Pre-adaptation is not to be used. The ten days window principle
is not applied.

Depending on the physical characteristics of the surfactant, one of the methods
listed below might be used if appropriately justified 29. It should be noted that the
pass criterion of at least 70 % of these methods is to be considered as equivalent to
the pass criterion of at least 60 % referred to in methods listed in point A above. The
adequacy of the choice of the methods listed below shall be decided on a case by
case confirmation, in accordance with Article 5 of this Regulation.

Method Directive 67/548/EEC Annex V.C.4.A (Dissolved Organic Carbon DOC
Die-Away): Pre-adaptation is not to be used. The ten days window principle is not
applied. The pass criteria for biodegradability measured according to the test shall be
at least 70 % within twenty-eight days.

Method Directive 67/548/EEC Annex V.C.4.B (Modified OECD Screening-DOC
Die-Away): Pre-adaptation is not to be used. The ten days window principle is not

These five tests are identified as the most suitable for surfactants.
The DOC methods could give results on the removal and not on the ultimate biodegradation. The
Manometric Respirometry and the MITI would not be appropriate in some cases because the high initial
test concentration could be inhibitory.

23

applied. The pass criteria for biodegradability measured according to the test shall be
at least 70 % within twenty-eight days.

N.B. – All the above-mentioned methods from Council Directive 67/548/EEC can also be
found in the publication Classification, Packaging and Labelling of Dangerous Substances in
the European Union. Part 2: “Testing Methods”. European Commission 1997. ISBN 92-828-
0076-8.

24

ANNEX IV
Complementary risk assessment for surfactants in detergents

For those surfactants for which environmental risk assessment is available in the context of
Directive 93/67/EEC, or Regulation (EEC) No 793/93 and Regulation (EC) No 1488/94, and
Technical Guidance Documents, this risk assessment shall be considered together with the
complementary risk assessment run in the scope of this Regulation.

The complementary risk assessment run in the scope of this Regulation, in case it is likely that
recalcitrant metabolites are produced, shall be considered in the context of assessments made
on the basis of Directive 93/67/EEC and Regulation (EEC) No 793/93. This is to be assessed
case by case and in particular on the basis of the results of the tests referred to in part 3 of this
Annex.

The study shall cover the aquatic environmental compartment. Additional
information
relating to specific risk assessment concerns might be required by the Committee on a case by
case basis. Additional information might include other environmental compartments such as
sewage sludge and soil.

As noted in Articles 12(2) and 13 the guidelines included in this Annex for the Decisions on
derogation may be adapted as appropriate on the basis of the accumulated experience.

The technical file referred to in Articles 5 and 9 shall contain at
described here below.

least

the information

1.

Identity of the surfactant (in accordance with the provisions laid down by
Annex VII.A of Directive 67/548/EEC.)

1.1.

Name

1.1.1. Names in the IUPAC nomenclature

1.1.2. Other names

1.1.3. CAS number and CAS name (if available)

1.1.4.

EINECS

30 or ELINCS

31 numbers (if available)

1.2.

1.3.

Molecular and structural formula

Composition of the surfactant

30

31

European Inventory of Existing Chemical Substances.
European List of Notified Chemical Substances.

25

2.

2.1.

2.2.

Information on the surfactant

Quantities of the surfactant used in detergents

The information on use patterns given in this section shall be sufficient to allow an
approximate but realistic estimate of function and environmental exposure to the
surfactant as associated with its use in detergents. It shall include the following:

–

–

–

–

–

importance of the application (societal value);

use conditions (release scenario);

use volume;

availability and suitability of alternatives
considerations);

(performance and economic

assessment of relevant environmental information.

3.

Information on the potential recalcitrant metabolite

Toxicity information on test liquors shall be provided. If no data are available on
residue identity, the information referred to in point 4.2.1 below may be requested,
depending on the potential risk, the importance and the quantity of the surfactant
used in detergents. In conflicting cases concerning this information, a Decision may
be taken in accordance with Article 12(2).

4.

Additional studies

4.1.

Biodegradability tests

4.1.1.

Pre-adapted inoculum

Any of the preferred tests described in Annex III, may be run with pre adapted
inoculum in order to provide evidence of the relevance of pre-adaptation for the
surfactant.

4.1.2.

Inherent Biodegradability Tests

At least one of the tests referred to below shall be included:

–

–

method Directive 67/548/EEC Annex V.C.12 (Modified SCAS test);

method Directive 67/548/EEC Annex V.C.9 (Zahn-Wellens).

Failure to pass the inherent biodegradability test would indicate potential for
persistency which may be considered, in general terms, as sufficient to prohibit the
placing on the market of such a surfactant unless, as stated in Article 5, there are
other justifiable reasons for granting a derogation.

26

4.1.3. Activated Sludge Simulation Biodegradability Tests

The following tests referred below shall be included:

–

method Directive 67/548/EEC Annex V.C.10;

(including possible changes in operating conditions as proposed in EN ISO 11733).

Failure to pass the activated sludge simulation biodegradability test, would indicate
potential for the release of the metabolites by sewage treatment, which may be
considered,
terms, as evidence of need for a more complete risk
assessment.

in general

4.2.

Toxicity testing of biodegradation test liquors

Toxicity information on test liquors is to be provided on:

4.2.1. Chemical and physical information, such as:

–

–

identity of the metabolite (and analytical means by which it was obtained);

key physical chemical properties (water solubility, Octanol: Water partition
coefficient (Log Po/w, etc.).

4.2.2.

Effects on organisms

Fish: The test recommended is that in Annex V.C.1 of Directive 67/548/EEC

Daphnia: The test recommended is that in Annex V.C.2 of Directive 67/548/EEC

Algae: The test recommended is that in Annex V.C.3 of Directive 67/548/EEC

Bacteria: The test recommended is that in Annex V.C.11 of Directive 67/548/EEC

4.2.3. Degradation

Biotic: The test recommended is that in Annex V.C.5 of Directive 67/548/EEC

Abiotic: The test recommended is that in Annex V.C.7 of Directive 67/548/EEC. The
information to be provided will consider as well the potential of metabolites for bio-
concentration and their partitioning to the sediment phase.

Moreover, if some metabolites are suspected for endocrine disrupting activity, it is
recommended to determine if these have potential to result in adverse affects as soon
as validated testing schemes to assess such adverse effects are available.

N.B. – All the above mentioned methods from Directive 67/548/EEC can also be consulted in
the publication Classification, Packaging and Labelling of Dangerous Substances in the
European Union; Part 2: “Testing Methods”. European Commission 1997. ISBN 92-828-
0076-8.

27

ANNEX V
List of surfactants that have obtained a derogation

The following detergent surfactants passing tests stipulated in Annex II, but not passing tests
stipulated in Annex III, may be placed on the market by means of derogation stipulated in
Article 5 and in accordance with the procedure laid down in Article 12(2) of this Regulation:

NAME
in the IUPAC
NOMENCLATURE

EINECS or ELINCS
NUMBER

CAS NUMBER
and CAS NAME

LIMITATIONS

EINECS means the European Inventory of Existing Commercial Substances. This inventory
contains the definitive list of all substances deemed to be on the Community market on
18 September 1981.

ELINCS means the list of new substances as defined in Council Directive 92/32/EEC of
30 April 1992 amending for the seventh time Directive 67/548/EEC on the approximation of
the laws, regulations and administrative provisions relating to the classification, packaging
and labelling of dangerous substances 32.

32

OJ L 154, 5.6.1992, p. 1.

28

ANNEX VI
List of banned or restricted detergent surfactants

The following detergent surfactants have been identified as not complying with the provisions
of this Regulation:

NAME
in the IUPAC
NOMENCLATURE

EINECS or ELINCS
NUMBER

CAS NUMBER
and CAS NAME

LIMITATIONS

EINECS means the European Inventory of Existing Commercial Substances. This inventory
contains the definitive list of all substances deemed to be on the Community market on
18 September 1981.

ELINCS means the list of new substances as defined in Directive 92/32/EEC.

29

ANNEX VII
List of banned or restricted detergent surfactants
in implementation of other community legislation

The following list of detergent surfactants incorporates surfactants covered by this Regulation
and
particular
Directive 76/769/EEC 33:

Community

legislation,

restricted

banned

other

by

or

in

NAME
in the IUPAC
NOMENCLATURE

LEGISLATION
ENFORCED

EINECS or ELINCS
NUMBER

CAS NUMBER
and CAS NAME

LIMITATIONS

EINECS means the European Inventory of Existing Commercial Substances. This inventory
contains the definitive list of all substances deemed to be on the Community market on
18 September 1981.

ELINCS means the list of new substances as defined in Council Directive 92/32/EEC.

33

It may refer as appropriate to the enforcement of International agreements and/or Organisations.

30

ANNEX VIII
Labelling and ingredient datasheet

A.

Labelling for contents

As prescribed in Article 11(3) of this Regulation, the following provisions on labelling shall
apply to the packaging of detergents sold to the general public.

The following weight percentage ranges:

–

–

–

–

less than 5 %,

5 % or over but less than 15 %,

15 % or over but less than 30 %,

30 % and more,

shall be used to indicate the content of the constituents listed below where they are added in a
concentration above 0,2 weight %:

–

–

–

–

–

–

–

–

–

–

–

–

–

–

–

–

phosphates,

phosphonates,

anionic surfactants,

cationic surfactants,

amphoteric surfactants,

non-ionic surfactants,

oxygen-based bleaching agents,

chlorine-based bleaching agents,

EDTA,

nitrilotriacetic acid,

phenols and halogenated phenols,

paradichlorobenzene,

aromatic hydrocarbons,

aliphatic hydrocarbons,

halogenated hydrocarbons,

soap,

31

–

–

zeolites,

polycarboxylates.

For other constituents, if added, neither the above percentage ranges nor the concentration
threshold of 0,2 % shall be applied.The following classes of constituent, if added, shall be
listed irrespective of their concentration:

–

–

enzymes,

disinfectants.

If added, preservation agents shall be listed, irrespective of their concentration, using where
possible the common nomenclature established under Article 8 of Directive 76/768/EEC.

If added, fragrances that appear on the list of allergenic perfume ingredients, first established
by the Scientific Committee on Cosmetics and Non Food Products in its opinion
SCCNFP/0017/9834, shall be listed using the nomenclature established by that Committee,
irrespective of their concentration.

For detergents intended to be used in the industrial sector, and not made available to members
of the general public, the above-mentioned requirements do not have to be fulfilled if the
equivalent information is provided by means of technical data sheets, safety data sheets, or in
a similar appropriate manner.

B.

Labelling for Dosage information

As prescribed in Article 11(4) of this Regulation, the following provisions on labelling shall
apply to the packaging of detergents sold to the general public. The packaging of detergents
sold to the general public intended to be used as laundry detergents shall bear the following
information:

–

–

–

The recommended quantities and/or dosage instructions expressed in millilitres or
grams appropriate to a standard washing machine load, for specified water hardness
classes and making provision for one or two cycle washing processes.

The number of standard washing machine loads of ‘normally soiled’ fabrics that can
be washed with the contents of the package using water of medium hardness,
corresponding to 2,5 millimoles CaCO3/l.

The capacity of any measuring cup, if provided, shall be indicated in millilitres or
grams.

The standard washing machine loads are 4,5 kg dry fabric for heavy-duty detergents and
2,5 kg dry fabric for low-duty detergents in line with the definitions of Commission
Decision 1999/476/EC establishing the ecological criteria for the award of the Community
eco-label to laundry detergents. A detergent shall be considered to be a heavy-duty detergent
unless the claims of the manufacturer or importer predominantly promotes fabric care i.e. low
temperature wash, delicate fibres and colours.

34

http://europa.eu.int/comm/food/fs/sc/sccp/out98_en.html

32

C.

Ingredient datasheet

The following provisions shall apply to the listing of ingredients on the datasheet referred to
in Article 9(3) of this Regulation.

The datasheet shall list the name of the detergent and of the manufacturer.

All ingredients shall be listed; they shall be listed in order of decreasing abundance by weight,
and the list shall be sub-divided into the following weight percentage ranges:

–

–

–

–

10 % or more,

1 % or over, but less than 10 %,

0,1 % or over, but less than 1 %,

less than 0,1 %.

Impurities shall not be considered to be ingredients.

The common chemical name or IUPAC35 name, the CAS number, and, where available, the
INCI36 name, and the European Pharmacopoeia name, shall be given for each ingredient.

35

36

International Union of Pure and Applied Chemistry
International Nomenclature Cosmetic Ingredient

33

ANNEX IX
Test methods and analytical methods

The following test and analytical methods apply to control procedures of detergents on the
market made by Member States:

1.

REFERENCE METHOD (confirmatory test)

1.1.

Definition

This method describes a laboratory model of the activated sludge + secondary settler which is
designed to simulate municipal sewage treatment. The conditions described are those from
Directives that preceded this Regulation. Improved state-of-the-art operating conditions can
be applied to this test method as described in EN ISO 11733

1.2.

Equipment needed for measurement

The method of measurement employs the small-activated sludge plant shown in Figure 1, and
in greater detail in Figure 2. The equipment consists of a sewage vessel A for synthetic
sewage, dosing pump B, aeration vessel C, settling vessel D, air-lift pump E to recycle the
activated sludge, and vessel F for collecting the treated effluent.

Vessels A and F must be of glass or suitable plastic and hold at least twenty-four litres.
Pump B must provide a constant flow of synthetic sewage to the aeration vessel; this vessel,
during normal operation, contains three litres of mixed liquor. A sintered aeration cube G is
suspended in the vessel C at the apex of the cone. The quantity of air blown through the
aerator shall be monitored by means of a flow meter H.

1.3.

Synthetic sewage

A synthetic sewage is employed for the test. Dissolve in each litre of tap water:

–

–

–

–

–

–

–

–

160 mg peptone;

110 mg meat extract;

30 mg urea, CO(NH2)2;

7 mg sodium chloride, NaCl;

4 mg calcium chloride, CaCl2.2H2O;

2 mg magnesium sulphate, MgSO4.7H2O;

28 mg of di-potassium hydrogen phosphate, K2HPO4;

and 10 ± 1 mg of the surfactant.

The synthetic sewage is freshly prepared daily.

34

1.4.

Preparation of samples

Uncompounded surfactants are examined in the original state. Active content of surfactant
samples must be determined in order to prepare the synthetic sewage (1.3).

1.5.

Operation of equipment

Initially, fill aeration vessel C and settling vessel D with synthetic sewage. The height of the
vessel D should be so fixed that the volume contained in the aeration vessel C is three litres.
Inoculation is made by introducing 3 ml of a secondary effluent of good quality, freshly
collected from a treatment plant dealing with a predominantly domestic sewage. The effluent
must be kept under aerobic conditions in the period between sampling and application. Then
set the aerator G, air-lift E and dosing device B in operation. The synthetic sewage must pass
through the aeration vessel C at a rate of one litre per hour; this gives a mean retention time of
three hours.

The rate of aeration should be so regulated that the contents of vessel C are kept constantly in
suspension and the dissolved oxygen content is at least 2 mg/l. Foaming must be prevented by
appropriate means. Anti-foaming agents that inhibit the activated sludge or contain surfactants
must not be used. The air-lift pump E must be set so that the activated sludge from the settling
vessel
is continually and regularly recycled to aeration vessel C. Sludge which bas
accumulated around the top of the aeration vessel C, in the base of the settling vessel D, or in
the circulation circuit must be returned to the circulation at least once each day by brushing or
its settleability may be
some other appropriate means. When the sludge fails to settle,
increased by the addition of 2 ml portions of a 5 % solution of ferric chloride, repeated as
necessary.

The effluent from the settling vessel D is accumulated in vessel F for twenty-four hours,
following which a sample is taken after thorough mixing. Vessel F must then be carefully
cleaned.

1.6.

Checking measuring equipment

The surfactant content (in mg/l) of the synthetic sewage is determined immediately before
use.

The surfactant content (in mg/l) of the effluent collected over twenty-four hours in vessel F
should be determined analytically by the same method,
immediately after collection:
otherwise the samples must be preserved, preferably by freezing. The concentrations must be
determined to the nearest 0,1 mg/l surfactant

As a check on the efficiency of the process, the chemical oxygen demand (COD) or the
dissolved organic carbon (DOC) of the glass fibre filtered effluent accumulated in vessel F
and of the filtered synthetic sewage in vessel A is measured at least twice per week.

The reduction in COD or DOC should level off when a roughly regular daily surfactant
degradation is obtained at the end of the running-in period shown in Figure 3.

The content of dry matter in the activated sludge contained in the aeration vessel should be
determined twice a week in g/l. If it is more than 2,5 g/l, the excess activated sludge must be
discarded.

35

The degradation test is performed at room temperature; this should be steady and kept
between 19-24 °C.

1.7.

Calculation of biodegradability

The percentage degradation of surfactant must be calculated every day on the basis of the
surfactant content
in mg/l of the synthetic sewage and of the corresponding effluent
accumulated in vessel F.

The degradability values thus obtained should be presented graphically as in Figure 3.

The degradability of the surfactant should be calculated as the arithmetic mean of the values
obtained over the twenty-one days that follow the running-in and acclimatisation period,
during which degradation has been regular and the operation of the plant trouble-free. In any
event the duration of the running-in period should not exceed six weeks.

The daily degradation values are calculated to the nearest 0,1 % but the final result is given to
the nearest whole number.

In some cases it may be permissible to reduce the frequency of sampling but at least fourteen
results collected over the twenty-one days which follow the running-in period should be used
in calculating the average.

2.

DETERMINATION OF ANIONIC SURFACTANTS IN BIODEGRADABILITY TESTS

2.1.

Principle

The method is based on the fact that the cationic dye methylene blue forms blue salts with
anionic surfactants [MBAS 37], which can be extracted with chloroform. To eliminate
interference, the extraction is first effected from alkaline solution and the extract is then
shaken with acidic methylene blue solution. The absorbency of the separated organic phase is
measured photometrically at the wavelength of maximum absorption of 650 nm.

2.2.

Reagents and equipment

2.2.1.

Buffer solution pH 10

Dissolve 24 g sodium bicarbonate, NaHCO3 AR, and 27 g anhydrous sodium carbonate
(Na2CO3) AR in deionised water and dilute to 1 000 ml.

2.2.2. Neutral methylene blue solution

Dissolve 0,35 g methylene blue AR in deionised water and dilute to 1 000 ml. Prepare the
solution at least twenty-four hours before use. The absorbency of the blank chloroform phase,
measured against chloroform must not exceed 0,015 per 1 cm of layer thickness at 650 nm.

2.2.3.

Acidic methylene blue solution

Dissolve 0,35 g methylene blue AR in 500 ml deionised water and mix with 6,5 ml H2SO4
(d = 1,84 g/ml). Dilute to 1 000 ml with deionised water. Prepare the solution at least twenty-

37

MBAS means Methylene Blue Active Substances.

36

four hours before use. The absorbency of the blank chloroform phase, measured against
chloroform must not exceed 0,015 per 1 cm of layer thickness at 650 nm.

2.2.4. Chloroform (trichloromethane) AR freshly distilled

2.2.5. Dodecyl benzene sulphonic acid methyl ester

2.2.6.

Ethanolic potassium hydroxide solution, KOH 0,1 M

2.2.7.

Ethanol pure, C2H5OH

2.2.8.

Sulphuric acid, H2SO4 0,5 M

2.2.9.

Phenolphthalein solution

Dissolve 1 g phenolphthalein in 50 ml ethanol and add 50 ml deionised water while stirring
continuously. Filter off any precipitate obtained.

2.2.10. Methanolic hydrochloric acid: 250 ml hydrochloric acid AR and 750 ml methanol

2.2.11. Separating funnel, 250 ml

2.2.12. Graduated flask, 50 ml

2.2.13. Graduated flask, 500 ml

2.2.14. Graduated flask, 1 000 ml

2.2.15. Round-bottomed flask with ground glass stopper and reflux condenser, 250 ml;

boiling granules

2.2.16. pH meter

2.2.17. Photometer for measurements at 650 nm, with 1 to 5 cm cells

2.2.18. Qualitative grade filter paper

2.3.

Procedure

The samples for analysis must not be taken through a layer of foam.

After thorough cleaning with water, the equipment used for the analysis must be thoroughly
rinsed with methanolic hydrochloric acid (2.2.10) and then with deionised water before using.

Filter the activated sludge plant
sampling. Discard the first 100 ml of the filtrates.

influent and effluent

to be examined immediately on

Place a measured volume of the sample, neutralised if necessary, into a 250 ml separating
funnel (2.2.11). The volume of sample should contain between 20 and 150 µg of MBAS. At
the lower MBAS content, up to 100 ml of sample may be used. When using less than 100 ml,
dilute to 100 ml with deionised water. Add to the sample 10 ml of buffer solution (2.2.1), 5 ml
of neutral methylene blue solution (2.2.2) and 15 ml of chloroform (2.2.4). Shake the mixture
uniformly and not too vigorously for one minute. After phase separation, run the chloroform
layer into a second separating funnel, containing 110 ml of deionised water and 5 ml of acidic

37

methylene blue solution (2.2.3). Shake the mixture for one minute. Pass the chloroform layer
through a cotton-wool filter previously cleaned and wetted with chloroform into a graduated
flask (2.2.12).

Extract the alkaline and acid solutions three times, using 10 ml of chloroform for the second
and third extractions. Filter the combined chloroform extracts through the same cotton wool
filter and dilute to the mark in the 50 ml flask (2.2.12) with chloroform used for rewashing the
cotton wool. Measure the absorbency of the chloroform solution with a photometer at 650 nm
in 1 to 5 cm cells against chloroform. Run a blank determination through the whole
procedure.

2.4.

Calibration curve

Prepare a calibration solution from the standard substance dodecylbenzene sulphonic acid
methyl ester (tetrapropylene type mol. wt. 340) after saponification into the potassium salt.
The MBAS is calculated as sodium dodecyl benzene sulphonate (mol. wt. 348).

From a weighing pipette, weigh 400 to 450 mg of dodecyl-benzene-sulphonic-acid-methyl-
ester (2.2.5) to the nearest 0,1 mg in a round-bottomed flask and add 50 ml of ethanolic
potassium hydroxide solution (2.2.6) and some boiling granules. After mounting the reflux
condenser, boil for one hour. After cooling, wash the condenser and ground glass joint with
about 30 ml of ethanol, and add these washings to the contents of the flask. Titrate the
solution with sulphuric acid against phenolphthalein until it becomes colourless. Transfer this
solution to a 1 000 ml graduated flask (2.2.14), dilute to the mark with deionised water and
mix.

Part of this surfactant stock solution is then further diluted. Withdraw 25 ml, transfer to a
500 ml graduated flask (2.2.13), dilute to the mark with deionised water and mix.

This standard solution contains:

E · 1,023
20 000

mg MBAS per ml,

where E is the sample weight in mg.

To establish the calibration curve, withdraw 1, 2, 4, 6, 8 ml portions of the standard solution
and dilute each to 100 ml with deionised water. Then proceed as stated under item 2.3
including a blank determination.

2.5.

Calculation of results

The amount of anionic surfactant (MBAS) in the sample is read from the calibration curve
(2.4). The MBAS content of the sample is given by:

mg MBAS · 1 000
V

= MBAS mg/l

where: V = ml volume of the sample used.

Express the results as sodium dodecylbenzene sulphonate (MW 348).

38

2.6.

Expression of results

Express the results as MBAS mg/l to the nearest 0,1.

3.

3.1

DETERMINATION OF NON-IONIC SURFACTANTS IN BIODEGRADATION TEST LIQUORS

Principle

Surface active agents are concentrated and isolated by gas stripping. In the sample used, the
quantity of non-ionic surfactant should be in the range 250-800 µg.

The stripped surfactant is dissolved in ethyl acetate.

After phase separation and evaporation of the solvent, the non-ionic surfactant is precipitated
in aqueous solution with modified Dragendorff reagent (KBiI4 + BaCl2 + glacial acetic acid).

The

The precipitate is filtered, washed with glacial acetic acid and dissolved in ammonium tartrate
solution.
potentiometrically with
pyrrolidinedithiocarbamate solution at pH 4-5 using a bright platinum indicator electrode and
a calomel or silver/silver chloride reference electrode. The method is applicable to non-ionic
surfactants containing 6-30 alkylene oxide groups.

bismuth

solution

titrated

the

in

is

The titration result is multiplied by the empirical factor of 54 for conversion to the reference
substance nonylphenol condensed with 10 mols ethylene oxide (NP 10).

3.2.

Reagents and Equipment

Reagents are to be made up in deionised water.

3.2.1.

Pure ethyl acetate, freshly distilled

3.2.2.

Sodium bicarbonate, NaHCO3 AR

3.2.3. Dilute hydrochloric acid [20 ml concentrated acid (HCl) diluted to 1 000 ml with

water]

3.2.4. Methanol AR, freshly distilled, stored in a glass bottle.

3.2.5.

Bromocresol purple, 0,1 g in 100 ml methanol.

3.2.6.

Precipitating agent: the precipitating agent is a mixture of two volumes of solution A
and one volume of solution B. The mixture is stored in a brown bottle and can be
used for up to one week after mixing.

3.2.6.1. Solution A

Dissolve 1,7 g bismuth nitrate, BiONO3.H2O AR, in 20 ml glacial acetic acid, and make up to
100 ml with water. Then dissolve 65 g potassium iodide AR in 200 ml water. Mix these two
solutions in a 1 000 ml measuring flask, add 200 ml glacial acetic acid (3.2.7) and make up to
1 000 ml with water.

39

3.2.6.2. Solution B

Dissolve 290 g barium chloride, BaCl2.2H2O AR, in 1 000 ml of water.

3.2.7. Glacial acetic acid 99-100 % (lower concentrations are unsuitable).

3.2.8.

Ammonium tartrate solution: mix 12,4 g tartaric acid AR and 12,4 ml of ammonia
solution AR (d = 0,910 g/ml) and make up to 1 000 ml with water (or use the
equivalent amount of ammonium tartrate AR).

3.2.9. Dilute ammonia solution: 40 ml ammonia solution AR (d = 0,910 g/ml) diluted to

1 000 ml with water.

3.2.10. Standard acetate buffer: dissolve 40 g solid sodium hydroxide AR, in 500 ml water in
a beaker and allow to cool. Add 120 ml glacial acetic acid (3.2.7). Mix thoroughly,
cool and transfer to a 1 000 ml volumetric flask. Make up to the mark with water.

3.2.11. Pyrrolidinedithiocarbamate solution (known as “carbate solution”): dissolve
103 mg sodium pyrrolidinedithiocarbamate, C5H8NNaS2.2H2O,
in about 500 ml
water, add 10 ml of n-amyl alcohol AR and 0,5 g NaHCO3 AR, and make up to
1 000 ml with water.

3.2.12. Copper sulphate solution (for standardisation of 3.2.11).

S T O C K S O L UT I O N

Mix 1 249 g copper sulphate, CuSO4.5H2O AR, with 50 ml 0,5 M sulphuric acid and make up
to 1 000 ml with water.

S T AN D AR D S O L UT I O N

Mix 50 ml stock solution with 10 ml 0,5 M H2SO4 and make up to 1 000 ml with water.

3.2.13. Sodium chloride AR

3.2.14. Gas-stripping apparatus (see Figure 5).

The diameter of the sintered disc must be the same as the internal diameter of the cylinder.

3.2.15. Separating funnel, 250 ml.

3.2.16. Magnetic stirrer with magnet 25-30 mm.

3.2.17. Gooch crucible, diameter of the perforated base = 25 mm, Type G4.

3.2.18. Circular glass-fibre filter papers, 27 mm diameter with fibre diameter 0,3-1,5 µm.

3.2.19. Two filter flasks with adapters and rubber collars, 500 and 250 ml respectively.

3.2.20. Recording potentiometer fitted with a bright platinum indicator electrode and a
calomel or silver/silver chloride reference electrode with a 250 mV range, with
automatic burette of 20-25 ml capacity, or alternative manual equipment.

40

3.3.

Method

3.3.1. Concentration and separation of the surfactant

Filter the aqueous sample through a qualitative filter paper. Discard the first 100 ml of the
filtrate.

Into the stripping apparatus, previously rinsed with ethyl acetate, place a measured quantity of
the sample, such that it contains between 250-800 µg non-ionic surfactant.

To improve the separation add 100 g sodium chloride and 5 g sodium bicarbonate.

If the volume of the sample exceeds 500 ml, add these salts to the stripping apparatus in solid
form, and dissolve by passing nitrogen or air through.

If a smaller-sized sample is used, dissolve the salts in 400 ml water and then add to the
stripping apparatus.

Add water to bring the level to the upper stopcock.

Cautiously add 100 ml ethyl acetate on top of the mater.

Fill the wash-bottle in the gas-line (nitrogen or air) two-thirds full with ethyl acetate.

Pass a gas stream of 30-60 l/h through the apparatus; the use of a flowmeter is recommended.
The rate of aeration must be increased gradually at the beginning. The gas rate must be so
adjusted that the phases remain noticeably separate to minimise the mixing of the phases and
the solution of the ethyl acetate in the water. Stop the gas flow after five minutes.

If there is a reduction of more than 20 % in the volume of the organic phase through solution
in water, the sublation must be repeated paying special attention to the rate of gas flow.

Run off the organic phase into a separating funnel. Return any water in the separating funnel
from the aqueous phase - it should only be a few ml - to the stripping apparatus. Filter the
ethyl acetate phase through a dry qualitative filter paper into a 250 ml beaker.

Put a further 100 ml ethyl acetate into the stripping apparatus and again pass nitrogen or air
through for five minutes. Draw off the organic phase into the separating funnel used for the
first separation, reject the aqueous phase and run the organic phase through the same filter as
the first ethyl acetate portion. Rinse both the separating funnel and the filter with about 20 ml
ethyl acetate.

Evaporate the ethyl acetate extract to dryness using a water-bath (fume cupboard). Direct a
gentle stream of air over the surface of the solution to accelerate the evaporation.

3.3.2.

Precipitation and filtration

Dissolve the dry residue from 3.3.1 in 5 ml methanol, add 40 ml water and 0,5 ml dilute HCl
(3.2.3) and stir the mixture with a magnetic stirrer.

To this solution add 30 ml of precipitating agent (3.2.6) from a measuring cylinder. The
precipitate forms after repeated stirring. After stirring for ten minutes leave the mixture to
stand for at least five minutes.

41

Filter the mixture through a Gooch crucible, the base of which is covered with a glass-fibre
filter paper. First wash the filter under suction with about 2 ml glacial acetic acid. Then
thoroughly wash the beaker, magnet, and crucible with glacial acetic acid, of which about 40-
50 ml is necessary. It is not necessary to quantitatively transfer the precipitate adhering to the
sides of the beaker, to the filter, because the solution of the precipitate for the titration is
returned to the precipitating beaker, and the remaining precipitate will then be dissolved.

3.3.3. Dissolution of the precipitate

Dissolve the precipitate in the filter crucible by the addition of hot ammonium tartrate
solution (about 80 °C) (3.2.8) in three portions of 10 ml each. Allow each portion to stand in
the crucible for some minutes before being sucked through the filter into the flask.

Put the contents of the filter flask into the beaker used for the precipitation. Rinse the sides of
the beaker with a further 20 ml of tartrate solution to dissolve the rest of the precipitate.

Carefully wash the crucible, adapter and filter flask with 150-200 ml water, and return the
rinsing water to the beaker used for the precipitation.

3.3.4

The titration

Stir the solution using a magnetic stirrer (3.2.16), add a few drops of bromocresol purple
(3.2.5) and add the dilute ammonia solution (3.2.9) until the colour turns violet (the solution is
initially weakly acid from the residue of acetic acid used for rinsing).

Then add 10 ml standard acetate buffer (3.2.10), immerse the electrodes in the solution, and
titrate potentiometrically with standard “carbate solution” (3.2.11), the burette tip being
immersed in the solution.

The titration rate should not exceed 2 ml/min.

The endpoint is the intersection of the tangents to the two branches of the potential curve. It
will be observed occasionally that the inflection in the potential curve becomes flattened; this
can be eliminated by carefully cleaning the platinum electrode (by polishing with emery
paper).

3.3.5.

Blank determinations

At the same time run a blank determination through the whole procedure with 5 ml methanol
and 40 ml water, according to the instructions in 3.3.2. The blank titration should be below
1 ml, otherwise the purity of the reagents (3.2.3, 3.2.7, 3.2.8, 3.2.9, 3.2.10) is suspect,
especially their content of heavy metals, and they must be replaced. The blank must be taken
into account in the calculation of the results.

3.3.6. Control of the factor of the “carbate solution”

Determine the factor for the carbate solution on the day of use. To do this, titrate 10 ml of the
copper sulphate solution (3.2.12) with “carbate solution” after the addition of 100 ml water
and 10 ml standard acetate buffer (3.2.10). If the amount used is a ml, the factor f is:

and all the results of the titration are multiplied by this factor.

f =

10
a

42

3.4.

Calculation of results

Every non-ionic surfactant has its own factor, depending on its composition, particularly on
the length of the alkene oxide chain. The concentration of non-ionic surfactant is expressed in
relation to a standard substance – a nonyl phenol with ten ethylene oxide units (NP 10) – for
which the conversion factor is 0,054.

Using this factor the amount of surfactant present in the sample is found expressed as mg of
NP 10 equivalent, as follows:

(b – c).f.0,054 = mg non-ionic surfactant as NP 10

where:

b = volume of “carbate solution” used by the sample (ml),

c = volume of “carbate solution” used by the blank (ml),

f = factor of the ”carbate solution”.

3.5

Expression of results

Express the results in mg/l as NP 10 to the nearest 0,1.

4.

PRELIMINARY TREATMENT OF ANIONIC SURFACTANTS TO BE TESTED

4.1.

Preliminary notes

4.1.1.

Treatment of samples

The treatment of anionic surface-active agents and formulated detergents prior to the
determination of primary biodegradability in the confirmatory test is:

PRODUCTS

TREATMENT

Anionic surfactants

Formulated detergents

None

Alcoholic extraction followed by separation of
the anionic surfactants by ion exchange

The purpose of the alcoholic extraction is to eliminate the insoluble and inorganic ingredients
of the commercial product, which in some circumstances might upset the biodegradability
test.

4.1.2.

Ion-exchange procedure

Isolation and separation of anionic surface active agents from soap, non-ionic and cationic
surfactants are required for correct biodegradability tests.

This is achieved by an ion-exchange technique using a macro-porous exchange resin and
suitable eluants for fractional elution. Thus soap, anionic and non-ionic surfactants may be
isolated in one procedure.

43

4.1.3.

Analytical control

After homogenising, the concentration of anionic surfactants in the synthetic detergent is
determined according to the MBAS analytical procedure. The soap content is determined by a
suitable analytical method. This analysis of the products is necessary to calculate the
quantities required for preparing fractions for the biodegradability test.

Quantitative extraction is not necessary; however, at least 80 % of the anionic surfactants
should be extracted. Usually, 90 % or more is obtained.

4.2.

Principle

From a homogeneous sample (powders, dried pastes and dried liquids) an ethanol extract is
obtained which contains the surfactants, soap and other alcohol-soluble constituents of the
synthetic detergent sample.

The ethanol extract is evaporated to dryness, dissolved in an isopropanol/water mixture and
the solution obtained is passed through a strongly acidic cation exchange/macro-porous anion
exchange combination heated to 50 °C. This temperature is necessary to prevent
the
precipitation of any fatty acids which may be present in acidic media.

Any non-ionic surfactants remain in the effluent.

Soap fatty acids are separated by extraction with ethanol containing CO2. The anionic
surfactants are then obtained as ammonium salts, by elution with an aqueous isopropanolic
solution of ammonium bicarbonate. These ammonium salts are used for the degradation test.

Cationic surfactants that might upset the biodegradability test and the analytical procedure are
eliminated by the cation exchanger placed above the anion exchanger.

4.3.

Chemicals and equipment

4.3.1. Deionised water

4.3.2.

Ethanol, 95 % (v/v) C2H5OH (permissible denaturant: methyl ethyl ketone or
methanol)

4.3.3.

Isopropanol/water mixture (50/50 v/v):

–

–

4.3.4.

4.3.5.

50 parts by volume isopropanol, CH3CHOH.CH3, and

50 parts by volume water (4.3.1)

Solution of carbon dioxide in ethanol (approximately 0,1 % CO2): using a delivery
tube with a built-in sinter, pass carbon dioxide, CO2, through the ethanol (4.3.2) for
ten minutes . Use fresh solutions only

Ammonium bicarbonate solution (60/40 v/v): 0,3 mol NH4HCO3 in 1 000 ml of an
isopropanol/water mixture consisting of 60 parts by volume isopropanol and
40 parts by volume water (4.3.1)

4.3.6. Cation exchanger (KAT), strongly acidic, resistant to alcohol (50-100 mesh)

44

4.3.7.

Anion exchanger (AAT), macro-porous, Merck Lewatit MP 7080 (70-150 mesh) or
equivalent

4.3.8. Hydrochloric acid, 10 % HCl (w/w)

4.3.9.

2 000 ml round-bottomed flask with ground glass stopper and reflux condenser

4.3.10. 90 mm diameter suction filter (heatable) for filter papers

4.3.11. 2 000 ml filter flask

4.3.12. Exchange columns with heating jacket and tap: inner tube 60 mm in diameter and

450 mm in height (see Figure 4)

4.3.13. Water-bath

4.3.14. Vacuum drying oven

4.3.15. Thermostat

4.3.16. Rotary evaporator

4.4.

Preparation of extract and separation of anionic active agents

4.4.1.

Preparation of extract

The quantity of surfactants necessary for the biodegradation test is about 50 g MBAS.

Normally, the quantity of product to be extracted will not exceed 1 000 g, but it may be
necessary to extract further quantifies of sample. For practical reasons, the quantity of product
used should in most cases be limited to 5 000 g in preparing extracts for the biodegradation
test.

Experience has shown that there are advantages in using a number of small extractions rather
than one large extraction. The exchanger quantifies specified are designed for a working
capacity of 600-700 mmoles of surfactants and soap.

4.4.2.

Isolation of alcohol-soluble constituents

Add 250 g of the synthetic detergent to be analysed to 1 250 ml ethanol, heat the mixture to
boiling point and reflux for one hour with stirring. Pass the hot alcoholic solution through a
coarse-pored suction filter heated to 50 °C and filter rapidly. Wash the flask and suction filter
with approximately 200 ml hot ethanol. Collect the filtrate and filter washings in a filter flask.

In the case of pastes or liquid products to be analysed, make sure that not more than 55 g
anionic surfactants and 35 g soap are contained in the sample. Evaporate this weighed sample
to dryness. Dissolve the residue in 2000 ml ethanol and proceed as described above.

In the case of powders of low apparent density (< 300 g/l) it is recommended to increase the
ethanol ratio in the relation 20:1.Evaporate the ethanolic filtrate to dryness, preferably by
means of a rotary evaporator. Repeat the operation if a greater quantity of extract is required.
Dissolve the residue in 5 000 ml isopropanol/water mixture.

45

4.4.3.

Preparation of ion-exchange columns

C AT I O N - E X C H AN G E

C O L U M N

Place 600 ml cation-exchange resin (4.3.6) in a 3 000 ml beaker and cover by adding 2 000 ml
hydrochloric acid (4.3.8). Allow standing for at least two hours, with occasional stirring.
Decant the acid and transfer the resin into the column (4.3.12) by means of deionised water.
The column should contain a glass-wool plug. Wash the column with deionised water at a rate
of 10-30 ml/min until the eluate is free of chloride. Displace the water with 2 000 ml
isopropanol/water mixture (4.3.3) at a rate of 10-30 ml/min. The exchange column is now
ready for operation.

A N I O N - E XC H AN G E

C O L U M N

Place 600 ml anion-exchange resin (4.3.7) in a 3 000 ml beaker and cover by adding 2 000 ml
deionised water. Allow the resin to swell for at least two hours. Transfer the resin into the
column by means of deionised water. The column should contain a glass-wool plug.

Wash the column with 0,3 M ammonium bicarbonate solution (4.3.5) until free of chloride.
This requires about 5 000 ml solution. Wash again with 2 000 ml deionised water. Displace
the water with 2 000 ml isopropanol/water mixture (4.3.3) at a rate of 10-30 ml/min. The
exchange column is now in the OH-form and ready for operation.

4.4.4.

Ion-exchange procedure

Connect the exchange columns so that the cation-exchange column is placed on top of the
anion-exchange column. Heat the exchange columns to 50 °C using thermostatic control. Heat
5 000 ml of the solution obtained in item 4.4.2 to 60 °C and pass the solution through the
exchanger combination at a rate of 20 ml/min. Wash the columns with 1 000 ml hot
isopropanol/water mixture (4.3.3).

To obtain the anionic surface active agents (MBAS), disconnect the KAT column. Using
5 000 ml ethanol/CO2 solution at 50 °C (4.3.4), elute the soap fatty acids out of the KAT
column. Reject the eluate.

Then elute the MBAS out of the AAT column with 5 000 ml ammonium bicarbonate solution
(4.3.5). Evaporate the eluate to dryness using a steam bath or in a rotary evaporator. The
residue contains the MBAS (as ammonium salt) and possible non-surfactant anionics that
have no detrimental effect on the biodegradation test. Add deionised water to the residue until
a definite volume is obtained and determine the MBAS content in an aliquot. The solution is
used as a standard solution of the anionic synthetic detergents for the biodegradation test. The
solution should be kept at a temperature below 5 °C.

4.4.5.

Regeneration of ion exchange resins

The cation exchanger is rejected after use.

Passing an additional quantity of ammonium bicarbonate solution (4.3.5) down the column at
a flow rate of approximately 10 ml/min until the eluate is free from anionic surfactants
(methylene blue
resin. Then pass 2 000 ml
isopropanol/water mixture (4.3.3) down the anion exchanger to wash. The anion exchanger is
again ready for operation.

anion-exchange

regenerates

test)

the

46

5.

PRELIMINARY TREATMENT OF NON-IONIC SURFACTANTS TO BE TESTED

5.1.

Preliminary notes

5.1.1

Treatment of samples

The treatment of non-ionic surface-active agents and formulated detergents prior to the
determination of primary biodegradability in the confirmatory test is:

PRODUCTS

TREATMENT

Non-ionic surfactants

Formulated detergents

None

Alcoholic extraction followed by separation of
the non-ionic surfactants by ion exchange

The purpose of the alcoholic extraction is to eliminate the insoluble and inorganic ingredients
of the commercial product, which in some circumstances might upset the biodegradability test

5.1.2.

Ion-exchange procedure

Isolation and separation of non-ionic surface active agents from soap, anionic and cationic
surfactants are required for correct biodegradability tests.

This is achieved by an ion exchange technique using a macro-porous exchange resin and
suitable eluants for fractional elution. Thus soap, anionic and non-ionic surfactants may be
isolated in one procedure.

5.1.3.

Analytical control

After homogenising, the concentration of anionic and non-ionic surfactants in the detergent is
determined according to the MBAS and BiAS analytical procedure. The soap content is
determined by a suitable analytical method.

This analysis of the product
fractions for the biodegradability tests.

is necessary to calculate the quantities required preparing

Quantitative extraction is not necessary; however, at least 80 % of the non-ionic surfactants
should be extracted. Usually, 90 % or more is obtained.

5.2.

Principle

From a homogeneous sample (powders, dried paste and dried liquids) an ethanol extract is
obtained which contains the surfactants, soap and other alcohol-soluble constituents of the
detergent sample.

The ethanol extract is evaporated to dryness, dissolved in an isopropanol/water mixture and
the solution obtained is passed through a strongly acidic cation exchange/macro-porous anion
the
exchange combination heated to 50 °C. This temperature is necessary to prevent
precipitation of any fatty acids which may be present
in acidic media. The non-ionic
surfactants are obtained from the effluent by evaporation.

Cationic surfactants, which might upset the degradation test and the analytical procedure, are
eliminated by the cation exchanger placed above the anion exchanger.

47

5.3.

Chemicals and equipment

5.3.1. Deionised water

5.3.2.

Ethanol, C2H5OH 95 % (v/v)
methanol)

(permissible denaturant: methyl-ethyl ketone or

5.3.3.

Isopropanol/water mixture (50/50 v/v):

–

–

50 parts by volume isopropanol, CH3CHOH.CH3, and

50 parts by volume water (5.3.1)

5.3.4.

Ammonium bicarbonate solution (60/40 v/v):

0,3 mol NH4HCO3 in 1 000 ml of an isopropanol/water mixture consisting of 60 parts by
volume isopropanol and 40 parts by volume water (5.3.1)

5.3.5. Cation exchanger (KAT), strongly acidic, resistant to alcohol (50-100 mesh)

5.3.6.

Anion exchanger (AAT), macro-porous, Merck Lewatit MP 7080 (70-150 mesh) or
equivalent

5.3.7. Hydrochloric acid, 10 % HCl w/w

5.3.8.

2 000 ml round-bottomed flask with ground glass stopper and reflux condenser

5.3.9.

90 mm diameter suction Filter (heatable) for filter papers

5.3.10. 2 000 ml filter flask

5.3.11. Exchange columns with heating jacket and tap: inner tube 60 mm in diameter and

450 mm in height (see Figure 4)

5.3.12. Water-bath

5.3.13. Vacuum drying oven

5.3.14. Thermostat

5.3.15. Rotary evaporator

5.4.

Preparation of extract and separation of non-ionic active agents

5.4.1.

Preparation of extract

The quantity of surfactant necessary for the degradation test is about 25 g BiAS.

In preparing extracts for the degradation tests, the quantity of product to be used should be
limited to a maximum of 2 000 g. Therefore it may be necessary to carry out the operation
two or more times in order to obtain sufficient quantity for the degradation tests. Experience
has shown that there are advantages in using a number of small extractions rather than one
large extraction.

48

5.4.2.

Isolation of alcohol-soluble constituents

Add 250 g of the synthetic detergent to be analysed to 1 250 ml ethanol and heat the mixture
to boiling point and reflux for one hour with stirring. Pass the hot alcoholic solution through a
coarse-pored suction filter heated to 50 °C and filter rapidly. Wash the flask and suction filter
with approximately 200 ml hot ethanol. Collect the filtrate and filter washings in a filter flask.

In the case of pastes or liquid products to be analysed, make sure that not more than 25 g
anionic surfactants and 35 g soap are contained in the sample. Evaporate this weighed sample
to dryness. Dissolve the residue in 500 ml ethanol and proceed as described above.

In the case of powders of low apparent density (< 300 g/l) it is recommended to increase the
ethanol ratio in the relation 20:1.

Evaporate the ethanolic filtrate to complete dryness, preferably by means of rotary evaporator.
Repeat the operation if a greater quantity of extract is required. Dissolve the residue in
5 000 ml isopropanol/water mixture.

5.4.3

Preparation of ion-exchange columns

C AT I O N - E X C H AN G E

C O L U M N

Place 600 ml cation-exchange resin (5.3.5) in a 3 000 ml beaker and cover by adding 2 000 ml
hydrochloric acid (5.3.7). Allow to stand for at least two hours, with occasional stirring.
Decant the acid and transfer the resin into the column (5.3.11) by means of deionised water.
The column should contain a glass-wool plug. Wash the column with deionised water at a rate
of 10-30 ml/min until the eluate is free of chloride. Displace the water with 2 000 ml
isopropanol/water mixture (5.3.3) at a rate of 10-30 ml/min. The exchange column is now
ready for operation.

A N I O N - E XC H AN G E

C O L U M N

Place 600 ml anion-exchange resin (5.3.6) in a beaker and cover by adding 2 000 ml
deionised water. Allow the resin to swell for at least two hours. Transfer the resin into the
column by means of deionised water. The column should contain a glass-wool plug.

Wash the column with 0,3 M ammonium bicarbonate solution (5.3.4) until free of chloride.
This requires about 5 000 ml solution. Wash again with 2 000 ml deionised water. Displace
the water with 2 000 ml isopropanol/water mixture (5.3.3) at a rate of 10-30 ml/min. The
exchange column is now in the OH form and ready for operation.

5.4.4.

Ion-exchange procedure

Connect the exchange columns so that the cation-exchange column is placed on top of the
anion-exchange column. Heat the exchange columns to 50 °C using thermostatic control. Heat
5 000 ml of the solution obtained in item 5.4.2 to 60 °C and pass the solution through the
exchanger combination at a rate of 20 ml/min. Wash the columns with 1 000 ml hot
isopropanol/water mixture (5.3.3).

To obtain the non-ionic surfactants collect the filtrate and filter washings and evaporate to
dryness, preferably by means of a rotary evaporator. The residue contains the BiAS. Add
deionised water until a defined volume is obtained and determine the BiAS content in an

49

aliquot. The solution is used as a standard solution of non-ionic surfactants for the
degradation test. The solution should be kept at a temperature below 5 °C.

5.4.5.

Regeneration of ion exchange resins

The cation exchanger is rejected after use.

Passing about 5 000-6 000 ml of ammonium bicarbonate solution (5.3.4) down the column at
a flow rate of approximately 10 ml/min until the eluate is free from anionic surfactants
(methylene blue
resin. Then pass 2 000 ml
isopropanol/water mixture (5.3.3) down the anion exchanger to wash. The anion exchanger is
again ready for operation.

anion-exchange

regenerates

test)

the

50

Figure 1
Activated sludge plant: overviews

I

I

A.
B.
C.
D.
E.
F.
G.
H.
I.

Storage vessel
Dosing device
Aeration chamber (three litres capacity)
Settling vessel
Air-lift pump
Collector
Sintered aerator
Air-flow meter
Air

51

Figure 2
Activated sludge plant: detail
(dimensions in millimetres)

B

A

C

B

A.
B.
C.

Liquid level
Hard PVC
Glass or waterproof plastic (hard PVC)

52

Figure 3
Calculation of biodegradability – Confirmatory test

E

A

B

C

D

F

A.
B.
C.
D.
E.
F.

Running-in period
Period used for calculation (twenty-one days)
Readily biodegradable surfactant
Surfactant not readily biodegradable
Biodegradation (%)
Time (days)

53

Figure 4
Heated exchange column
(dimensions in millimetres)

54