1、October 2007DEUTSCHE 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!$IUy“1385086www
2、.din.deDDIN EN ISO 15181-3Paints 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 inthe extract (ISO 15181-3:2007)English version
3、 of DIN EN ISO 15181-3:2007-10Beschichtungsstoffe Bestimmung der Auswaschrate von Bioziden aus Antifouling-Beschichtungen Teil 3: Berechnung der Auswaschrate von Zink-Ethylenbis(dithiocarbamat) (Zineb) durchBestimmung der Konzentration von Ethylenthioharnstoff im Extrakt (ISO 15181-3:2007)Englische
4、Fassung DIN EN ISO 15181-3:2007-10www.beuth.deDocument comprises 18 pages DIN EN ISO 15181-3:2007-10 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 15181-3 whi
5、ch was prepared by ISO/TC 35/SC 9 “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
6、Committee NA 002-00-07 AA Allgemeine 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 bioc
7、ides 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-trip
8、henylborane (PTPB) concentration in the extract and calculation of the release (at draft stage) Part 5: Calculation of the tolylfluanid and dichlofluanid release rate by determination of the concentration of dimethyltolylsulfamide (DMST) and dimethylphenylsulfamide (DMSA) in the extract (at draft st
9、age) The DIN Standards corresponding to the International Standards referred to in the EN are as follows: ISO 3696 DIN ISO 3696 ISO 15181-1 DIN EN ISO 15181-1 National Annex NA (informative) Bibliography DIN EN ISO 15181-1, Paints and varnishes Determination of release rate of biocides from antifoul
10、ing paints Part 1: General method for extraction of biocides DIN ISO 3696, Water for analytical laboratory use Specification and test methods EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 15181-3 June 2007 ICS 87.040 English Version Paints and varnishes - Determination of release rate of
11、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 - Dtermination du taux de lixiviation des biocides contenus dans les p
12、eintures antisalissures - Partie 3: Calcul du taux de lixiviation de lthylne-bis (dithiocarbamate) de zinc (zinbe) par dtermination de la concentration dthylnethioure dans lextrait (ISO 15181-3:2007) Beschichtungsstoffe - Bestimmung der Auswaschrate von Bioziden aus Antifouling-Beschichtungen - Teil
13、 3: Berechnung der Auswaschrate von Zink-Ethylenbis(dithiocarbamat) (Zineb) durch Bestimmung der Konzentration von Ethylenthioharnstoff im Extrakt (ISO 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 w
14、hich 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
15、 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 nation
16、al 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 Un
17、ited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 1518
18、1-3:2007: EContents Page 2 EN ISO 15181-3:2007 (E) Foreword 3 Introduction 4 1 Scope .5 2 Normative references .5 3 Principle 6 4 Supplementary information required for the zineb extraction procedure .6 5 Apparatus 6 6 Reagents and materials .7 7 Test samples .7 8 Procedure 7 9 Calculation and expre
19、ssion of results .9 10 Validation of the method .12 11 Test report .12 Annex A (normative) Supplementary information required for the zineb extraction procedure 14 Annex B (informative) Additional information on zineb and ETU .15 Bibliography .16 3 EN ISO 15181-3:2007 (E) Foreword This document (EN
20、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 publica
21、tion 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
22、 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
23、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. Introduction By using standard conditions of temperature, salinity and pH at low biocide concentrations in the surrounding artificial seawater, a repeatable valu
24、e 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
25、 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
26、 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 e
27、ither 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-servic
28、e 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 relations
29、hip 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 generati
30、ng 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 relea
31、se rate from antifouling coatings under real-life conditions to be obtained. This can be accomplished through the application of appropriate correction factors2. 4 EN ISO 15181-3:2007 (E) 1 Scope This part of ISO 15181 specifies the apparatus and analytical method for determining the amount of zineb
32、 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
33、 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 1
34、5181 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
35、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 2,9 gcm2d1to 500 gcm2d1. The quantitative measurement of release rates below this range will require the use of an analytical method with a lower limit of
36、 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 editio
37、n 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 AST
38、M D 6442-06, Standard Test Method for Determination of Copper Release Rate from Antifouling Coatings in Substitute Ocean Water 5 EN 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
39、 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 alterna
40、tive analytical method, provided that it demonstrates a limit of quantitation for ETU in artificial seawater of 6 g/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 Supplem
41、entary 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 instru
42、ment, which has a limit of quantitation for ETU in artificial seawater of 6 g/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
43、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 makin
44、g 25 l 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 m) or equivalent. 5.1.5 Column oven, providing a constant colu
45、mn temperature within the range 20 C to 40 C. 5.1.6 Electronic data-processing system, capable of controlling the HPLC system, acquiring data and automatically integrating peak areas. 5.2 Reflux apparatus, consisting of the components specified in 5.2.1 to 5.2.3. 5.2.1 Borosilicate glass flask, volu
46、me 50 ml. 5.2.2 Reflux condenser. 5.2.3 Heating device, for example a heating mantle or hotplate, capable of refluxing seawater. 5.3 Dispensers, automatic or repeating, for reagents. 5.4 Pipettes, with disposable tips. 5.5 Volumetric flasks, volume 100 ml, 200 ml and 500 ml. 5.6 Syringes, glass or d
47、isposable, volume 5 ml. 5.7 Syringe filters, disposable, PVDF membrane, pore size 0,45 m. 6 EN ISO 15181-3:2007 (E) 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 t
48、heir 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
49、aqueous solution, 37 % by mass. 6.1.2 Hydrochloric acid, aqueous solution, 10 % by volume. 6.2 Ethylenethiourea (ETU), with a certified mass fraction of ETU of at least 99,0 %. 6.3 Artificial seawater, as defined in ISO 15181-1. 6.4 Water, conforming to the requirements of grade 2 of ISO 3696. 6.5 Methanol, HPLC grade. 6.6 Sodium dihydrogen phosphate monohydrate. 6.7 Sodium hydroxide, aqueous solution, 0,1 mol/l. 6.8 Orthophosphoric acid, aqueous solution, 85 % by mass. 7 Test samples Use extracts taken from the rele
