SIST EN ISO 15181-5:2008

SLOVENSKI STANDARD
01-september-2008
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Paints and varnishes - Determination of release rate of biocides from antifouling paints -
Part 5: Calculation of the tolylfluanid and dichlofluanid release rate by determination of
the concentration of dimethyltolylsulfamide (DMST) and dimethylphenylsulfamide
(DMSA) in the extract (ISO 15181-5:2008)
Beschichtungsstoffe - Bestimmung der Auswaschrate von Bioziden aus Antifouling-
Beschichtungen - Teil 5: Berechung der Auswaschrate von Tolylfluanid und Dichlofluanid
durch Bestimmung der Konzentration von Dimethyltolylsulfamid (DMST) und
Dimethylphenylsulfamid (DMSA) im Extrakt (ISO 15181-5:2008)
Peintures et vernis - Détermination du taux de lixiviation des biocides contenus dans les
peintures antisalissures - Partie 5: Calcul du taux de lixiviation du tolylfluanide et du
dichlofluanide par détermination de la concentration du diméthyl-tolylsulfamide (DMST)
et du diméthyl-phénylsulfamide (DMSA) dans l'extrait (ISO 15181-5:2008)
Ta slovenski standard je istoveten z: EN ISO 15181-5:2008
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 15181-5
NORME EUROPÉENNE
EUROPÄISCHE NORM
May 2008
ICS 87.040
English Version
Paints and varnishes - Determination of release rate of biocides
from antifouling paints - Part 5: Calculation of the tolylfluanid and
dichlofluanid release rate by determination of the concentration
of dimethyltolylsulfamide (DMST) and dimethylphenylsulfamide
(DMSA) in the extract (ISO 15181-5:2008)
Peintures et vernis - Détermination du taux de lixiviation Beschichtungsstoffe - Bestimmung der Auswaschrate von
des biocides contenus dans les peintures antisalissures - Bioziden aus Antifouling-Beschichtungen - Teil 5:
Partie 5: Calcul du taux de lixiviation du tolylfluanide et du Berechung der Auswaschrate von Tolylfluanid und
dichlofluanide par détermination de la concentration du Dichlofluanid durch Bestimmung der Konzentration von
diméthyl-tolylsulfamide (DMST) et du diméthyl- Dimethyltolylsulfamid (DMST) und Dimethylphenylsulfamid
phénylsulfamide (DMSA) dans l'extrait (ISO 15181-5:2008) (DMSA) im Extract (ISO 15181-5:2008)
This European Standard was approved by CEN on 8 May 2008.
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 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 Management Centre has the same status as the
official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 15181-5:2008: E
worldwide for CEN national Members.

Contents Page
Foreword.3

Foreword
This document (EN ISO 15181-5:2008) has been prepared by Technical Committee ISO/TC 35 "Paints and
varnishes" in collaboration with 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 November 2008, and conflicting national standards shall be withdrawn
at the latest by November 2008.
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, Cyprus, Czech
Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and the United Kingdom.
Endorsement notice
The text of ISO 15181-5:2008 has been approved by CEN as a EN ISO 15181-5:2008 without any
modification.
INTERNATIONAL ISO
STANDARD 15181-5
First edition
2008-05-15
Paints and varnishes — Determination of
release rate of biocides from antifouling
paints —
Part 5:
Calculation of the tolylfluanid and
dichlofluanid release rate by
determination of the concentration of
dimethyltolylsulfamide (DMST) and
dimethylphenylsulfamide (DMSA) in the
extract
Peintures et vernis — Détermination du taux de lixiviation des biocides
contenus dans les peintures antisalissures —
Partie 5: Calcul du taux de lixiviation du tolylfluanide et du dichlofluanide
par détermination de la concentration du diméthyl-tolylsulfamide
(DMST) et du diméthyl-phénylsulfamide (DMSA) dans l'extrait

Reference number
ISO 15181-5:2008(E)
©
ISO 2008
ISO 15181-5:2008(E)
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Published in Switzerland
ii © ISO 2008 – All rights reserved

ISO 15181-5:2008(E)
Contents Page
Foreword. iv
Introduction . v
1 Scope . 1
2 Normative references . 1
3 Principle. 2
4 Supplementary information . 2
5 Apparatus . 2
6 Reagents and materials . 3
7 Test samples . 3
8 Preparation of calibration standards. 4
9 Recovery and conversion check standards . 5
10 Procedure . 6
11 Calculation and expression of results. 7
12 Validation of the method. 11
13 Test report . 11
Annex A (normative) Supplementary information . 13
Annex B (informative) Additional information on tolylfluanid, DMST, dichlofluanid and DMSA. 14
Bibliography . 17

ISO 15181-5:2008(E)
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 15181-5 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
The following part is under preparation:
⎯ Part 6: Determination of tralopyril release rate by quantification of its degradation product 3-bromo-5-
(4-chlorophenyl)-4-cyano-1H-pyrrole-2-carboxylic acid (BCCPCA) in the extract

iv © ISO 2008 – All rights reserved

ISO 15181-5:2008(E)
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 will, however, depend 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
in a particular area.
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 rates 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 obtained using this generic test method significantly overestimate the release rates of biocides under
in-service conditions. Published results demonstrate that the results of this test method are generally higher
by a factor of about 10 or more for several commercial antifouling coatings than direct in situ measurements of
[1, 2]
copper and organotin release rates from in-service ship hulls . A similar relationship is expected to be
found for other biocides. Realistic estimates of the biocide release rate 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 environmental inputs be taken into account to
allow a more accurate estimate of the biocide release rate from antifouling coatings under real-life conditions
[2]
to be obtained. This can be accomplished through the application of appropriate correction factors .

INTERNATIONAL STANDARD ISO 15181-5:2008(E)

Paints and varnishes — Determination of release rate of
biocides from antifouling paints —
Part 5:
Calculation of the tolylfluanid and dichlofluanid release rate by
determination of the concentration of dimethyltolylsulfamide
(DMST) and dimethylphenylsulfamide (DMSA) in the extract
1 Scope
This part of ISO 15181 specifies the apparatus and analytical method for determining the amount of
tolylfluanid and dichlofluanid that has been released from an antifouling paint into artificial seawater in
accordance with the procedure given in ISO 15181-1.
Tolylfluanid and dichlofluanid are unstable in the marine environment and degrade to form
dimethyltolylsulfamide (DMST) and dimethylphenylsulfamide (DMSA), respectively. This part of ISO 15181
specifies a method for converting the released species into these degradation products, quantifying their
concentration in the treated artificial seawater samples, and gives the final calculation for the release rate of
tolylfluanid and dichlofluanid under the specified laboratory conditions.
This part of ISO 15181 is designed to allow the concurrent determination of tolylfluanid, dichlofluanid and
other biocides that can be released by a given antifouling paint (for example, copper) 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 method
−2 −1 −2 −1
are from 1,3 µg⋅cm ⋅d to 500 µg⋅cm ⋅d . The quantitation of release rates lower than this range will
require the use of an analytical method with a lower limit of quantitation for tolylfluanid, dichlofluanid, or both
(as appropriate) in artificial seawater than that specified in Clause 3 and in 5.1.
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 D 6442-06, Standard Test Method for Determination of Copper Release Rate from Antifouling Coatings
in Substitute Ocean Water
ISO 15181-5:2008(E)
3 Principle
The amount of tolylfluanid released from a test cylinder into artificial seawater by the method given in
ISO 15181-1 is determined by promoting the degradation of the tolylfluanid in the leachate under controlled
conditions and subsequently quantifying the concentration of the degradation product, dimethyltolylsulfamide
(DMST), by a high-performance liquid chromatography (HPLC) method or by an alternative analytical method,
provided that it has a limit of quantitation for tolylfluanid in artificial seawater of 7 µg/l or less. The release rate
of the biocide under the specified laboratory conditions is then calculated as tolylfluanid.
The amount of dichlofluanid released from a test cylinder into artificial seawater by the method given in
ISO 15181-1 is determined by promoting the controlled degradation of the dichlofluanid in the leachate, and
quantifying the concentration of the degradation product, dimethylphenylsulfamide (DMSA), by a similar HPLC
method or by an alternative analytical method, provided that it demonstrates a limit of quantitation for
dichlofluanid in artificial seawater of 7 µg/l or less. The release rate of the biocide under the specified
laboratory conditions is then calculated as dichlofluanid.
Additional information on tolylfluanid, dichlofluanid, DMST and DMSA is given in Annex B.
4 Supplementary information
The items of supplementary information required to be able to use the general extraction procedure, described
in ISO 15181-1, for dichlofluanid and tolylfluanid are given in Annex A.
5 Apparatus
5.1 High-performance liquid chromatograph (HPLC), or other suitable instrument, which has a limit of
quantitation for tolylfluanid, dichlofluanid, or both (as appropriate) in artificial seawater of 7 µg/l or less. The
limit of quantitation shall be determined by the general procedure given in Annex 2 of ASTM D 6442-06
(Determination of the LOQ for Copper in Substitute Ocean Water for the Analytical Method), suitably modified
for tolylfluanid, dichlofluanid, or both (as appropriate). If HPLC is used, the system shall, where possible,
include the components specified in 5.1.1 to 5.1.6.
5.1.1 Gradient-programmed pump, capable of achieving a pressure of 150 bar and a flow-rate of
0,5 ml/min.
5.1.2 Ultraviolet detector, capable of monitoring at 195 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 2,0 mm and a length
of 150 mm, packed with a microparticulate octadecylsilane (C-18, end-capped) stationary phase (mean
particle size 5,0 µm) or equivalent, and equipped with a reverse-phase pre-column with an internal diameter of
4,6 mm and a length of 30 mm, packed with a microparticulate octadecylsilane (C-18, end-capped) stationary
phase (mean particle size 5,0 µm) or equivalent.
5.1.5 Column oven, providing a constant column temperature of 40 °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 Glass vials, volume 30 ml, screw-topped.
5.3 Dispensers, automatic or repeating, for reagents.
5.4 Pipettes, with disposable tips.
2 © ISO 2008 – All rights reserved

ISO 15181-5:2008(E)
5.5 Volumetric flasks, volume 25 ml and 100 ml.
5.6 Microlitre syringe, capable of accurately dispensing volumes of between 1 µl and 100 µl.
5.7 Syringe, glass or disposable, capable of dispensing 2 ml.
6 Reagents and materials
Suppliers’ material safety data sheets should be consulted for details of any hazards associated with the
reagents listed below, and the risks associated with their use should be assessed. Appropriate protective
clothing and equipment should be utilized.
Unless otherwise specified, use only reagents of recognized analytical grade.
6.1 Cleaning reagents.
Use one of the following reagents for cleaning all the equipment.
6.1.1 Hydrochloric acid, concentrated aqueous solution, 37 % by mass.
6.1.2 Hydrochloric acid, aqueous solution, 10 % by volume.
6.2 Tolylfluanid, analytical standard with a certified mass fraction of tolylfluanid of at least 99,0 %, for use
in determining the tolylfuanid release rate. See also Clause 9.
6.3 Dichlofluanid, analytical standard with a certified mass fraction of at least 99,0 %, for use in
determining the dichlofluanid release rate. See also Clause 9.
6.4 Dimethyltolylsulfamide (DMST), analytical standard with a certified mass fraction of at least 99,0 %,
for use in preparing the calibration standard for determination of the tolylfluanid release rate. See also
Clause 8.
6.5 Dimethylphenylsulfamide (DMSA), analytical standard with a certified mass fraction of at least 99,0 %
for use in preparing the calibration standard for determination of the dichlofluanid release rate. See also
Clause 8.
6.6 Artificial seawater, as defined in ISO 15181-1.
6.7 Water, conforming to the requirements of grade 2 of ISO 3696.
6.8 Acetonitrile, HPLC grade.
6.9 Formic acid, minimum 98 % by mass.
NOTE Formic acid may be substituted by acetic acid.
6.10 Sodium hydroxide, aqueous solution 0,1 mol/l.
7 Test samples
Use extracts taken from the release rate measuring containers as described in ISO 15181-1.
ISO 15181-5:2008(E)
8 Preparation of calibration standards
8.1 General
Stock solutions of certified reference standards shall be prepared at approximately 1 000 mg/l and 100 mg/l in
acetonitrile, as described in 8.2 and 8.3. These stock solutions shall then be used to prepare calibration
standards by dilution with artificial seawater acidified to pH 2 to 3 with concentrated hydrochloric acid. A
minimum of 5 calibration standards shall be prepared at concentrations appropriate to the samples being
analysed and to define the working range for the determination of DMST and DMSA.
Where tolylfluanid and dichlofluanid release rates are being concurrently determined, both DMST and DMSA
calibration standards shall be prepared.
8.2 Stock solution A
Weigh, to the nearest 0,1 mg, about 100 mg (M) of DMST or DMSA into a 100 ml (V ) volumetric flask, add
50 ml of acetonitrile, and mix to dissolve. Make up to the mark with acetonitrile and mix well to give a
homogenous solution (dilution factor, f = 1).
i
8.3 Stock solution B
Pi
...