SIST EN ISO 15181-3:2007

SLOVENSKI STANDARD
SIST EN ISO 15181-3:2007
01-september-2007
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Paints and varnishes - Determination of release rate of biocides from antifouling paints -
Part 3: Calculation of the zinc ethylene-bis(dithiocarbamate) (zineb) release rate by
determination of the concentration of ethylenethiourea in the extract (ISO 15181-3:2007)
Beschichtungsstoffe - Bestimmung der Auswaschrate von Bioziden aus Antifouling-
Beschichtungen - Teil 3: Berechnung der Auswaschrate von Zink-Ethylenbis
(dithiocarbamat) (Zineb) durch Bestimmung der Konzentration von Ethylenethioharnstoff
im Extrakt (ISO 15181-3:2007)
Peintures et vernis - Détermination du taux de lixiviation des biocides contenus dans les
peintures antisalissures - Partie 3: Calcul du taux de lixiviation de l'éthylene-bis
(dithiocarbamate) de zinc (zinebe) par détermination de la concentration
d'éthylenethiourée dans l'extrait (ISO 15181-3:2007)
Ta slovenski standard je istoveten z: EN ISO 15181-3:2007
ICS:
87.040 Barve in laki Paints and varnishes
SIST EN ISO 15181-3:2007 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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EUROPEAN STANDARD
EN ISO 15181-3
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2007
ICS 87.040

English Version
Paints and varnishes - Determination of release rate of biocides
from antifouling paints - Part 3: Calculation of the zinc ethylene-
bis(dithiocarbamate) (zineb) release rate by determination of the
concentration of ethylenethiourea in the extract (ISO 15181-
3:2007)
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 3:
Partie 3: Calcul du taux de lixiviation de l'éthylène-bis Berechnung der Auswaschrate von Zink-
(dithiocarbamate) de zinc (zinèbe) par détermination de la Ethylenbis(dithiocarbamat) (Zineb) durch Bestimmung der
concentration d'éthylènethiourée dans l'extrait (ISO 15181- Konzentration von Ethylenethioharnstoff im Extrakt (ISO
3:2007) 15181-3:2007)
This European Standard was approved by CEN on 16 May 2007.
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
© 2007 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 15181-3:2007: E
worldwide for CEN national Members.

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EN ISO 15181-3:2007 (E)





Foreword


This document (EN ISO 15181-3:2007) 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 December 2007, and conflicting national
standards shall be withdrawn at the latest by December 2007.

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 United
Kingdom.


Endorsement notice

The text of ISO 15181-3:2007 has been approved by CEN as EN ISO 15181-3:2007 without any
modifications.

2

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INTERNATIONAL ISO
STANDARD 15181-3
First edition
2007-06-01

Paints and varnishes — Determination of
release rate of biocides from antifouling
paints —
Part 3:
Calculation of the zinc
ethylene-bis(dithiocarbamate) (zineb)
release rate by determination of the
concentration of ethylenethiourea in the
extract
Peintures et vernis — Détermination du taux de lixiviation des biocides
contenus dans les peintures antisalissures —
Partie 3: Calcul du taux de lixiviation de l'éthylène-bis(dithiocarbamate)
de zinc (zinèbe) par détermination de la concentration
d'éthylènethiourée dans l'extrait



Reference number
ISO 15181-3:2007(E)
©
ISO 2007

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ISO 15181-3:2007(E)
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ii © ISO 2007 – All rights reserved

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ISO 15181-3:2007(E)
Contents Page
Foreword. iv
Introduction . v
1 Scope. 1
2 Normative references. 1
3 Principle. 2
4 Supplementary information required for the zineb extraction procedure. 2
5 Apparatus. 2
6 Reagents and materials . 3
7 Test samples. 3
8 Procedure. 3
9 Calculation and expression of results. 5
10 Validation of the method. 8
11 Test report. 8
Annex A (normative) Supplementary information required for the zineb extraction procedure. 10
Annex B (informative) Additional information on zineb and ETU . 11
Bibliography . 12

© ISO 2007 – All rights reserved iii

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ISO 15181-3:2007(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 15181-3 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
iv © ISO 2007 – All rights reserved

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ISO 15181-3:2007(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 the 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
than direct in situ measurements of copper and organotin release rates from in-service ship hulls by a factor of
[1, 2]
about 10 or more for several commercial antifouling coatings . 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 .

© ISO 2007 – All rights reserved v

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INTERNATIONAL STANDARD ISO 15181-3:2007(E)

Paints and varnishes — Determination of release rate
of biocides from antifouling paints —
Part 3:
Calculation of the zinc ethylene-bis(dithiocarbamate) (zineb)
release rate by determination of the concentration of
ethylenethiourea in the extract
1 Scope
This part of ISO 15181 specifies the apparatus and analytical method for determining the amount of zineb that
has been released from an antifouling paint into artificial seawater in accordance with the procedure given in
ISO 15181-1.
Zineb is released from antifouling paints in the form of ionic ethylene-bis(dithiocarbamate) which is unstable in
the marine environment. This part of ISO 15181 describes a method for converting the released species into a
stable degradation product, ethylenethiourea, and determining its concentration in the treated artificial
seawater samples, and gives the final calculation for the release rate of zineb under the specified laboratory
conditions.
This part of ISO 15181 is designed to generally allow the concurrent determination of zineb 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 the procedure given in
ISO 15181-1.
When used in conjunction with ISO 15181-1, the practical limits on the quantitative measurement of release
–2 –1 –2 –1
rates by this method are from 2,9 µg⋅cm ⋅d to 500 µg⋅cm ⋅d . The quantitative measurement of release
rates below this range will require the use of an analytical method with a lower limit of quantitation for
ethylenethiourea in artificial seawater than the limit specified 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 2007 – All rights reserved 1

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ISO 15181-3:2007(E)
3 Principle
The amount of polymeric ethylene-bis(dithiocarbamate) (zineb) released from a test cylinder into artificial
seawater in accordance with the procedure given in ISO 15181-1 is determined by degrading the ethylene-
bis(dithiocarbamate) species in the leachate under controlled conditions and determining the concentration of
the degradation product, ethylenethiourea (ETU), by high-performance liquid chromatography (HPLC) or by
an alternative analytical method, provided that it demonstrates a limit of quantitation for ETU in artificial
seawater of 6 µg/l or less. The release rate of the biocide under the specified laboratory conditions is then
calculated as zineb.
Additional information on zineb and ETU is given in Annex B.
4 Supplementary information required for the zineb extraction procedure
The items of supplementary information required to be able to use the general extraction procedure, described
in ISO 15181-1, for zineb are given in Annex A.
5 Apparatus
5.1 High-performance liquid chromatograph, or other suitable instrument, which has a limit of
quantitation for ETU in artificial seawater of 6 µg/l or less. The limit of quantitation shall be determined by the
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 ETU. 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 and a flow-rate of 1,0 ml/min.
5.1.2 Ultraviolet detector, capable of monitoring at 233 nm.
5.1.3 Autosampler, capable of making 25 µl injections.
5.1.4 Chromatography column: A reverse-phase column with an internal diameter of 4,6 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.
5.1.5 Column oven, providing a constant column temperature within the range 20 °C to 40 °C.
5.1.6 Ele
...