EN ISO 15181-6:2014

SLOVENSKI STANDARD
01-julij-2014
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Paints and varnishes - Determination of release rate of biocides from antifouling paints -
Part 6: Determination of tralopyril release rate by quantitation of its degradation product
in the extract (ISO 15181-6:2012)
Beschichtungsstoffe - Bestimmung der Auswaschrate von Bioziden aus Antifouling-
Beschichtungen - Teil 6: Bestimmung der Auswaschrate von Tralopyril durch
Quantifizierung seiner Abbauprodukte im Extrakt (ISO 15181-6:2012)
Peintures et vernis - Détermination du taux de lixiviation des biocides contenus dans les
peintures antisalissures - Partie 6: Calcul du taux de lixiviation du tralopyril par
détermination de la concentration de son produit de dégradation dans l'extrait (ISO
15181-6:2012)
Ta slovenski standard je istoveten z: EN ISO 15181-6:2014
ICS:
87.040 Barve in laki Paints and varnishes
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN ISO 15181-6
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2014
ICS 87.040
English Version
Paints and varnishes - Determination of release rate of biocides
from antifouling paints - Part 6: Determination of tralopyril
release rate by quantitation of its degradation product in the
extract (ISO 15181-6:2012)
Peintures et vernis - Détermination du taux de lixiviation des Beschichtungsstoffe - Bestimmung der Auswaschrate von
biocides contenus dans les peintures antisalissures - Partie Bioziden aus Antifouling-Beschichtungen - Teil 6:
6: Calcul du taux de lixiviation du tralopyril par Bestimmung der Auswaschrate von Tralopyril durch
détermination de la concentration de son produit de Quantifizierung seiner Abbauprodukte im Extrakt (ISO
dégradation dans l'extrait (ISO 15181-6:2012) 15181-6:2012)
This European Standard was approved by CEN on 8 May 2014.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same
status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2014 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 15181-6:2014 E
worldwide for CEN national Members.

Contents Page
Foreword .3
Foreword
The text of ISO 15181-6:2012 has been prepared by Technical Committee ISO/TC 35 “Paints and varnishes”
of the International Organization for Standardization (ISO) and has been taken over as EN ISO 15181-6:2014
by Technical Committee CEN/TC 139 “Paints and varnishes” the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by December 2014, and conflicting national standards shall be withdrawn
at the latest by December 2014.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech
Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece,
Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.
Endorsement notice
The text of ISO 15181-6:2012 has been approved by CEN as EN ISO 15181-6:2014 without any modification.

INTERNATIONAL ISO
STANDARD 15181-6
First edition
2012-07-15
Paints and varnishes — Determination
of release rate of biocides from
antifouling paints —
Part 6:
Determination of tralopyril release
rate by quantitation of its degradation
product in the extract
Peintures et vernis — Détermination du taux de lixiviation des
biocides contenus dans les peintures antisalissures —
Partie 6: Calcul du taux de lixiviation du tralopyril par quantitation
de son produit de dégradation dans l’extrait
Reference number
ISO 15181-6:2012(en)
©
ISO 2012
ISO 15181-6:2012(en)
© ISO 2012
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any
means, electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the
address below or ISO’s member body in the country of the requester.
ISO copyright office
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Tel. + 41 22 749 01 11
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E-mail copyright@iso.org
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Published in Switzerland
ii © ISO 2012 – All rights reserved

ISO 15181-6:2012(en)
Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Supplementary information . 2
5 Apparatus . 2
6 Reagents and materials . 2
7 Test samples . 3
8 Preparation of calibration standards . 3
8.1 General . 3
8.2 Stock solution A . 3
8.3 Stock solution B . 3
8.4 Preparation of calibration standards from stock solutions . 3
9 Recovery and conversion check standards . 4
9.1 General . 4
9.2 Stock solution C . 4
9.3 Stock solution D . 4
9.4 Preparation of recovery and conversion check standards . 4
10 Procedure. 5
10.1 General . 5
10.2 Sample treatment . 5
10.3 Preparation of chromatography eluent . 5
10.4 Instrument calibration . 5
10.5 Conversion and recovery determination . 6
10.6 Sample determination . 6
11 Calculation and expression of results . 6
11.1 Calculation of the tralopyril concentration . 6
11.2 Release rate for each test cylinder . 7
11.3 Mean release rate for each set of three cylinders . 8
11.4 Cumulative tralopyril release . 8
11.5 Mean tralopyril release rate . 8
11.6 Pseudo-steady-state mean tralopyril release rate . 9
12 Validation of the method . 9
13 Test report . 9
Annex A (normative) Supplementary information .11
Annex B (informative) Additional information on tralopyril and BCCPCA .12
Bibliography .14
ISO 15181-6:2012(en)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International
Standards adopted by the technical committees are circulated to the member bodies for voting.
Publication as an International Standard requires approval by at least 75 % of the member bodies
casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 15181-6 was prepared by Technical Committee ISO/TC 35, Paints and varnishes, Subcommittee SC 9,
General test methods for paints and varnishes.
ISO 15181 consists of the following parts, under the general title Paints and varnishes — Determination
of release rate of biocides from antifouling paints:
— Part 1: General method for extraction of biocides
— Part 2: Determination of copper-ion concentration in the extract and calculation of the release rate
— Part 3: Calculation of the zinc ethylene-bis(dithiocarbamate) (zineb) release rate by determination of
the concentration of ethylenethiourea in the extract
— Part 4: Determination of pyridine–triphenylborane (PTPB) concentration in the extract and calculation
of the release rate
— Part 5: Calculation of the tolylfluanid and dichlofluanid release rate by determination of the concentration
of dimethyltolylsulfamide (DMST) and dimethylphenylsulfamide (DMSA) in the extract
— Part 6: Determination of tralopyril release rate by quantitation of its degradation product in the extract
iv © ISO 2012 – All rights reserved

ISO 15181-6:2012(en)
Introduction
By using standard conditions of temperature, salinity and pH at low biocide concentrations in the
surrounding artificial seawater, a repeatable value of the release rate under the specified laboratory
conditions can be determined using the method given in this part of ISO 15181, which can be used for
quality assurance and material selection purposes. The actual release rate of biocides from antifouling
paints on ships’ hulls into the environment depends, however, on many factors, such as ship operating
schedules, length of service, berthing conditions, paint condition, as well as temperature, salinity, pH,
pollutants, and biological community.
The results of this test do not reflect environmental biocide release rates for antifouling products and
are not suitable for direct use in the process of generating environmental risk assessments, producing
environmental loading estimates or for establishing release rate limits for regulatory purposes. In
comparison with copper and organotin release rate measurements obtained either by direct or indirect
measurements of the copper release rate from ships’ hulls and from measurements made on panels
exposed in harbours, all available data indicate that the results of this generic test method significantly
overestimate the release rate of biocide under in-service conditions. Published results demonstrate that
the results of this test method are generally higher than direct in-situ measurements of copper and
organotin release rate from the hulls of harboured ships by a factor of about 10 or more for several
[1][2]
commercial antifouling coatings. A similar relationship is expected to be found for other biocides.
Realistic estimates of the biocide release from a ship’s hull under in-service conditions can only be
obtained from this test method if this difference is taken into account.
Where the results of this test method are used in the process of generating environmental risk
assessments, producing environmental loading estimates or for regulatory purposes, it is most strongly
recommended that the relationship between laboratory release rates and actual environment inputs
be taken into account to allow a more accurate estimate of the biocide release rate from antifouling
coatings under real-life conditions to be obtained. This can be accomplished through the application of
[2]
appropriate correction factors.
INTERNATIONAL STANDARD ISO 15181-6:2012(en)
Paints and varnishes — Determination of release rate of
biocides from antifouling paints —
Part 6:
Determination of tralopyril release rate by quantitation of
its degradation product in the extract
1 Scope
This part of ISO 15181 specifies a method for determining the amount of tralopyril that has been released
from an antifouling paint into artificial seawater in accordance with the procedure given in ISO 15181-1.
Tralopyril is unstable in water and degrades hydrolytically to form 3-bromo-5-(4-chlorophenyl)-4-cyano-
1H-pyrrole-2-carboxylic acid (BCCPCA). This part of ISO 15181 specifies a method for accelerating the
conversion of the released tralopyril into this degradation product by heat treatment and quantifying
the concentration of the BCCPCA degradation product in the artificial seawater extract, and gives the
final calculation for the release rate of tralopyril under the specified laboratory conditions.
This part of ISO 15181 is designed to allow the concurrent determination of tralopyril and other biocides
that can be released by a given antifouling paint (for example, zineb) through the analysis of separate
sub-samples of an artificial seawater extract generated in accordance with ISO 15181-1.
When used in conjunction with ISO 15181-1, the practical limits for quantifying release rates by this
−2 −1 −2 −1
method are from 0,36 µg cm d to 270 µg cm d . The quantitation of release rates lower than this
range requires the use of an analytical method with a limit of quantitation for tralopyril in artificial
seawater of less than 2 μg/l.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 15181-1:2007, Paints and varnishes — Determination of release rate of biocides from antifouling
paints — Part 1: General method for extraction of biocides
ASTM D6442-06, Standard test method for determination of copper release rate from antifouling coatings
in substitute ocean water
3 Principle
The quantity of tralopyril released into artificial seawater by the method given in ISO 15181-1 is
determined by accelerating the hydrolytic degradation of the tralopyril in the leachate by heat treatment
under controlled conditions and subsequently quantifying the concentration of the degradation product,
3-bromo-5-(4-chlorophenyl)-4-cyano-1H-pyrrole-2-carboxylic acid (BCCPCA) by high-performance
liquid chromatography (HPLC) or by an alternative method, provided that it demonstrates a limit of
quantitation for tralopyril in artificial seawater of 2 μg/l or less. The release rate of the biocide under
the specified laboratory conditions is then calculated as tralopyril.
NOTE Additional information on tralopyril and BCCPCA is given in Annex B.
ISO 15181-6:2012(en)
4 Supplementary information
The items of supplementary information required to be able to use the general extraction procedure,
described in ISO 15181-1, for tralopyril are given in Annex A.
5 Apparatus
5.1 High-performance liquid chromatograph (HPLC), or other suitable instrument, which
demonstrates a limit of quantitation for tralopyril in artificial seawater by the analytical method of 2 μg/l
or less. The limit of quantitation shall be determined by the general procedure given in ASTM D6442-
06, Annex 2 (determination of the LOQ for copper in substitute ocean water for the analytical method),
suitably modified for tralopyril. If HPLC is used, the system shall, where possible, include the components
specified in 5.1.1 to 5.1.6.
5.1.1 Isocratic pump, capable of achieving a pressure of 150 bar (15 MPa) and a flow-rate of 1,5 ml/min.
5.1.2 Ultraviolet detector, capable of monitoring at 280 nm.
5.1.3 Autosampler, capable of making 200 μl injections.
5.1.4 Chromatography column: a reverse-phase column with an internal diameter of 4,0 mm and a
length of 100 mm, packed with a microparticulate octadecylsilane (C-18, end-capped) stationary phase
(mean particle size 3,0 μm) or equivalent.
5.1.5 Column oven, facilitating a constant column temperature of 35 °C.
5.1.6 Electronic data-processing system, capable of controlling the HPLC system, acquiring data and
enabling automated integration of peak areas.
5.2 Pipettes, with disposable tips.
5.3 Volumetric flasks, glass.
5.4 Thermostatically controlled cabinet, capable of maintaining a temperature of (50 ± 5) °C.
6 Reagents and materials
Suppliers’ material safety data sheets should be consulted
...