1、February 2009DEUTSCHE NORM English price group 11No part of this standard may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 87.040!$V)/“1510612ww
2、w.din.deDDIN EN ISO 15181-4Paints and varnishes Determination of release rate of biocides from antifouling paints Part 4: Determination of pyridine-triphenylborane (PTPB) concentrationin the extract and calculation of the release rate (ISO 15181-4:2008)English version of DIN EN ISO 15181-4:2009-02Be
3、schichtungsstoffe Bestimmung der Auswaschrate von Bioziden aus Antifouling-Beschichtungen Teil 4: Bestimmung der Konzentration von Pyridintriphenylboran (PTPB) im Extrakt undBerechnung der Auswaschrate (ISO 15181-4:2008)Englische Fassung DIN EN ISO 15181-4:2009-02SupersedesDIN EN ISO 15181-4:2008-12
4、www.beuth.deDocument comprises 20 pagesDIN EN ISO 15181-4:2009-02 2 National foreword This standard falls in the domain of Technical Committee CEN/TC 139 “Paints and varnishes” (Secretariat: DIN, Germany). It is identical with International Standard ISO 15181-4 which was prepared by ISO/TC 35/SC 9 “
5、General test methods for paints and varnishes” (Secretariat: BSI, United Kingdom). The responsible German body involved in its preparation was the Normenausschuss Beschichtungsstoffe und Beschichtungen (Coatings and Coating Materials Standards Committee), Technical Committee NA 002-00-07 AA Allgemei
6、ne Prfverfahren fr Beschichtungsstoffe und Beschichtungen. DIN EN 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 copp
7、er-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 i
8、n theextract and calculation of the release Part 5: Calculation of the tolylfluanid and dichlofluanid release rate by determination of the concentration of dimethyltolylsulfamide (DMST) anddimethylphenylsulfamide (DMSA) in the extract The following part is under preparation: Part 6: Determination of
9、 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 The DIN Standards corresponding to the International Standards referred to in the EN are as follows: ISO 3696 DIN ISO 3696 ISO 15181-1:2007 DI
10、N EN ISO 15181-1:2007-10 Amendments Compared with DIN EN ISO 15181-4:2008-12, the following corrections have been made to the German version only and therefore do not affect the English text: a) In subclause 9.4, key to first equation: Riund Rj bei jedem Paar von aufeinander folgenden Tagen der Prfu
11、ng vom Beginn des Versuches bis zu Tag 14 b) In subclause 9.4, key to second equation: Riund Rj mittlere Auswaschraten, in gcm-2d-1, von PTPB fr jeden Satz von drei Prfzylindern (siehe 9.3) bei jedem Paar von aufeinander folgenden Tagen der Prfung von Tag x bis Tag y bis 45 Tagen, z. B. Previous edi
12、tions DIN EN ISO 15181-4: 2008-12 DIN EN ISO 15181-4:2009-02 3 National Annex NA (informative) Bibliography DIN ISO 3696, Water for analytical laboratory use Specification and test methods DIN EN ISO 15181-1:2007-10, Paints and varnishes Determination of release rate of biocides from antifouling pai
13、nts Part 1: General method for extraction of biocides DIN EN ISO 15181-4:2009-02 4 This page is intentionally blank EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 15181-4August 2008ICS 87.040English VersionPaints and varnishes - Determination of release rate of biocidesfrom antifouling paints
14、 - Part 4: Determination of pyridine-triphenylborane (PTPB) concentration in the extract andcalculation of the release rate (ISO 15181-4:2008)Peintures et vernis - Dtermination du taux de lixiviationdes biocides contenus dans les peintures antisalissures -Partie 4: Dtermination de la concentration d
15、e pyridine-triphnylborane (PTPB) dans lextrait et calcul du taux delixiviation (ISO 15181-4:2008)Beschichtungsstoffe - Bestimmung der Auswaschrate vonBioziden aus Antifouling-Beschichtungen - Teil 4:Bestimmung der Konzentration von Pyridintriphenylboran15181-4:2008)This European Standard was approve
16、d by CEN on 26 July 2008.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandar
17、ds 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 translationunder the responsibility of a CEN member into its own language and notified to th
18、e CEN Management Centre has the same status as theofficial 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, Netherla
19、nds, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2008 CEN All rights of exploitation in any
20、 form and by any means reservedworldwide for CEN national Members.Ref. No. EN ISO 15181-4:2008: E(PTPB) im Extrakt und Berechnung der Auswaschrate (ISOContents Page 1 2 3 4 5 6 7 8 9 10 11 EN ISO 15181-4:2008 (E) DIN EN ISO 15181-4:2009-02 2Introduction 4 Scope 5 Normative references 6 Principle6 Su
21、pplementary information6 Apparatus .6 Reagents and materials 7 Test samples 7 Procedure .7 Calculation and expression of results.9 Annex A (normative) Supplementary information .14 Annex B (informative) Additional information on PTPB15 Bibliography 16 Validation of the method.12 Test report 12 Forew
22、ord. 3 Foreword This document (EN ISO 15181-4:2008) 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 nat
23、ional standard, either by publication of an identical text or by endorsement, at the latest by February 2009, and conflicting national standards shall be withdrawn at the latest by February 2009. Attention is drawn to the possibility that some of the elements of this document may be the subject of p
24、atent 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,
25、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 IS
26、O 15181-4:2008 has been approved by CEN as a EN ISO 15181-4:2008 without any modification. EN ISO 15181-4:2008 (E) DIN EN ISO 15181-4:2009-02 3Introduction By using standard conditions of temperature, salinity and pH at low biocide concentrations in the surrounding artificial seawater, a repeatable
27、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 environ
28、ment 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 rel
29、ease 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 obtain
30、ed either by direct or indirect measurements of the copper and organotin 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 biocides under in-s
31、ervice 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 about 10 or more for several commercial antifouling coatings1, 2. A similar rela
32、tionship is expected to be found for other biocides. Realistic estimates of the biocide release rate from a ships 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 gen
33、erating 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
34、release rate from antifouling coatings under real-life conditions to be obtained. This can be accomplished through the application of appropriate correction factors2. EN ISO 15181-4:2008 (E) DIN EN ISO 15181-4:2009-02 41 Scope This part of ISO 15181 specifies the apparatus and analytical method for
35、determining the amount of pyridine-triphenylborane (PTPB) that has been released from an antifouling paint into artificial seawater in accordance with the procedure given in ISO 15181-1. It determines the PTPB concentration in the artificial seawater extract and gives the final calculation for the r
36、elease rate of PTPB under the specified laboratory conditions. This part of ISO 15181 is designed to allow the concurrent determination of PTPB 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 seawa
37、ter 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 rates by this method are from 1,8 gcm2d1to 500 gcm2d1. The quantitative measurement of release rates below this rang
38、e will require the concentration step described in the last paragraph in 8.2 or the use of an analytical method with a limit of quantitation for PTPB in artificial seawater which is lower than the limit specified in Clause 3 and in 5.1. 2 Normative references The following referenced documents are i
39、ndispensable 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:
40、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 EN ISO 15181-4:2008 (E) DIN
41、 EN ISO 15181-4:2009-02 53 Principle The quantity of PTPB biocide released into artificial seawater by the method given in ISO 15181-1 is determined by the use of a high-performance liquid chromatograph (HPLC) with UV detection at 220 nm after pre-concentration by solid-phase extraction (SPE), or by
42、 an alternative analytical method provided that it demonstrates a limit of quantitation for PTPB in artificial seawater of 10 g/l or less. The release rate of the biocide under the specified laboratory conditions is then calculated as PTPB. The use of the HPLC method in conjunction with the addition
43、al sample concentration step described in the last paragraph in 8.2 can allow a limit of quantitation for PTPB in artificial seawater of 0,5 g/l to be achieved. NOTE Additional information on PTPB is given in Annex B. Additional background information on the analytical method has been published by T
44、akahashi, et al.3. 4 Supplementary information The items of supplementary information required to be able to use the general extraction procedure, described in ISO 15181-1, for PTPB are given in Annex A. 5 Apparatus 5.1 High-performance liquid chromatograph (HPLC), or other equivalent instrument, wh
45、ich has a limit of quantitation for PTPB in artificial seawater of 10 g/l or less. The limit of quantitation shall be determined by the procedure given in Annex 2 (Determination of the LOQ for Copper in Substitute Ocean Water for the Analytical Method) of ASTM D 6442-06, suitably modified for PTPB.
46、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 220 nm. 5.1.3 Autosampler, capable of making 10
47、l injections. 5.1.4 Chromatography column: A reverse-phase column with an internal diameter of 4,6 mm and a length of 250 mm, packed with a microparticulate octadecylsilane (C-18, end-capped) stationary phase (mean particle size 5,0 m) or equivalent. 5.1.5 Column oven, capable of maintaining a const
48、ant column temperature of 30 C. 5.1.6 Electronic data-processing system, capable of controlling the HPLC system, acquiring data and automatically integrating peak areas. 5.2 Pipettes, with disposable tips. 5.3 Volumetric flasks, made of glass. 5.4 Solid-phase extraction (SPE) cartridges, packed with
49、 360 mg of C-18 sorbent, and sequentially conditioned prior to use with 10 ml of a solvent blend of acetonitrile and pyridine in a ratio of 99:1 parts by volume, then 10 ml of water, and finally 10 ml of artificial seawater. 5.5 Solid-phase extraction system, or equivalent system suitable for use with the extraction cartridges. 5.6 Rotary vacuum evaporator, with heating bath. EN ISO 15181-4:2008 (E) DIN EN ISO 15181-4:2009-02 66 Reagents and materials Suppliers material safety data sheets should be
