1、BSI Standards PublicationPD CEN/TS 15968:2010Determination of extractableperfluorooctanesulphonate(PFOS) in coated andimpregnated solid articles,liquids and fire fighting foams Method for sampling,extraction and analysis by LC-qMS or LC-tandem/MSPD CEN/TS 15968:2010 PUBLISHED DOCUMENTNational forewo
2、rdThis Published Document is the UK implementation of CEN/TS15968:2010.The UK participation in its preparation was entrusted to TechnicalCommittee TCI/80, Chemical testing of textiles.A list of organizations represented on this committee can beobtained on request to its secretary.This publication do
3、es not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 85786 7ICS 71.040.50; 71.080.20Compliance with a British Standard cannot confer immunity
4、 fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 31 January 2014.Amendments issued since publicationDate Text affectedPD CEN/TS 15968:2010TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 15
5、968 August 2010 ICS 71.040.50; 71.080.20 English Version Determination of extractable perfluorooctanesulphonate (PFOS) in coated and impregnated solid articles, liquids and fire fighting foams - Method for sampling, extraction and analysis by LC-qMS or LC-tandem/MS Dtermination du sulfonate de perfl
6、uorooctane (SPFO) extractible dans des articles solides couchs et imprgns, des liquides et des mousses anti-incendie - Mthode dchantillonnage, dextraction et danalyse par LC-MS ou LC-MS/MS Bestimmung von extrahierbarem Perfluoroctansulfonat (PFOS) in beschichteten und imprgnierten Feststoffartikeln,
7、 Flssigkeiten und Feuerlschschumen -Verfahren zur Probenahme, Extraktion und Analyse mittels LC-MS oder LC-MS This Technical Specification (CEN/TS) was approved by CEN on 25 October 2009 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two
8、 years the members of CEN will be requested to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at
9、 national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgari
10、a, Croatia, 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 ST
11、ANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2010 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TS 15968:2010: EPD CEN/TS 15968:2010CEN/TS 15968
12、:2010 (E) 2 Contents Page Foreword 4Introduction .51 Scope 62 Normative references 63 Terms and definitions .64 Symbols and abbreviations 75 Principle 76 Apparatus and Reagents 86.1 General 86.2 Equipment 96.3 Reagents for extraction .96.4 Reagents for LC and MS .97 Sampling 107.1 General . 107.2 Co
13、nditioning samples 107.3 Sampling solids 107.4 Sampling products that have separate distinct parts . 107.5 Sampling liquids . 108 Sample pre-treatment . 119 Extraction 119.1 Extraction method for textile, fabrics, leather and paper . 119.2 Clean-up method for textile, fabrics, leather and paper . 11
14、9.3 Dilution method for aqueous fire extinguishing foams 119.4 Extraction method for other liquids 1210 Interference with LC-tandemMS 1211 Analysis . 1211.1 LC-tandemMS operating conditions . 1211.2 Blank determination . 1211.3 Quality Control samples 1211.4 Identification 1212 System suitability te
15、st 1412.1 Calibration . 1412.2 Recovery 1512.3 Blank measurement 1513 Calculation . 1513.1 Calibration curve for quantification 1513.2 Calculation of results after calibration with reference compounds 1613.3 Calculation of results to PFOS equivalents . 1714 Expression of results . 1715 Test report .
16、 18Annex A (informative) LC-QMS and LC-TOFMS 20Annex B (informative) . 25PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 3 Annex C (informative) Confirmation of compound identity by MS methods 26Bibliography 31PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 4 Foreword This document (CEN/TS 15968:2010) has been
17、prepared by Technical Committee CEN/TC 382 “Project Committee - PFOS”, the secretariat of which is held by NEN. 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 o
18、r all such patent rights. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association and supports essential requirements of REACH (1907/2006), annex XVII, designation 53 1. According to the CEN/CENELEC Internal Regulations, the nat
19、ional standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Nether
20、lands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 5 Introduction For implementation of REACH (1907/2006), annex XVII, designation 53 1 the European Commission asked CEN to develop an European Tec
21、hnical Specification with test methods for measuring levels of PFOS containing compounds in preparations, semi-finished products and articles including textile and coated materials. REACH (1907/2006), annex XVII, designation 53 1 states that the substances that are under the Directive are perfluoroo
22、ctanesulfonates (PFOS), that means substances with the formula C8F17SO2X (where X=OH, Metal salt (O-M+), halide, amide and other derivatives including polymers). PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 6 1 Scope This Technical Specification describes the determination of perfluorooctanesulfonate (
23、PFOS) in concentrated extracts from coated and impregnated solid articles, liquids and fire extinguishing foams using high performance liquid chromatography-tandem mass spectrometry (LC-tandemMS) or quadrupole mass spectrometry (LC-qMS). The method is applicable for a concentration range for PFOS in
24、 the extract solution of 0,5 g/l to 50 g/l. WARNING Persons using this Technical Specification should be familiar with normal laboratory practice. This Technical Specification does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the use
25、r to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted in accordance with this Technical Specification be carried out by suitably qualified staff. 2 Normative references The fo
26、llowing 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. EN 20187, Paper, board and pulps Standard atmosphere fo
27、r conditioning and testing and procedure for monitoring the atmosphere and conditioning of samples (ISO 187:1990) EN ISO 2419, Leather Physical and mechanical tests Sample preparation and conditioning (ISO 2419:2006) EN ISO 3696:1995, Water for analytical laboratory use Specification and test method
28、s (ISO 3696:1987) EN ISO 8130-9, Coating powders Part 9: Sampling (ISO 8130-9:1992) EN ISO 15194, In vitro diagnostic medical devices Measurement of quantities in samples of biological origin Requirements for certified reference materials and the content of supporting documentation (ISO 15194:2009)
29、ISO 8466-1, Water quality Calibration and evaluation of analytical methods and estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration function 3 Terms and definitions For the purposes of this document, the following terms and definitions apply 3.1 analyte
30、substance or chemical constituent that is subjected to measurement 3.2 blank matrix matrix which is largely identical with the analytical one, but does not contain the analyte or contains it in low and known content NOTE Blanks are used to check the analytical process. PD CEN/TS 15968:2010CEN/TS 159
31、68:2010 (E) 7 3.3 constituents all pure chemical materials and substances of which a material is composed 3.4 extract concentrated preparation of the analytes isolated from the treated material 3.5 foams fire extinguishing foams 3.6 overall treated materials materials with a seamless finish 3.7 inte
32、rnal standard compound different from the analyte, present in the sample with known content or added to the sample, simultaneously detected with the analyte, with physical and chemical properties as similar as possible to the analyte 3.8 reference material RM material, sufficiently homogeneous and s
33、table regarding one or more properties, used in calibration, assignment of a value to another material, or quality assurance (conform EN ISO 15194) 3.9 coated materials materials that are treated with chemicals to provide them with water and soil repellent properties; or treated for aesthetic or dec
34、orative reasons 4 Symbols and abbreviations LC-qMS liquid chromatography (LC) coupled with quadrupole mass spectrometry (qMS) LC-tandemMS liquid chromatography (LC) coupled with tandem mass spectrometry (tandemMS) LC-TOFMS liquid chromatography (LC) coupled with time of flight mass spectrometer (TOF
35、MS) 5 Principle The analytes listed in Table 1, after extraction with methanol, are determined by liquid chromatography with tandem mass spectrometric detection (LC-tandemMS) or liquid chromatography mass spectrometric detection (LC-qMS). The list of analytes is not comprehensive for all possible PF
36、OS derivates. PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 8 Table 1 Analytes determinable by this method Compound name Chemical formula Acronym CAS No. Perfluorooctane sulphonic acid C8F17SO3H PFOS 1763-23-1Perfluorooctane sulphonamide C8F17SO2NH2 PFOSA 754-91-6 N-Methyl-heptadecafluorooctane sulphona
37、mide C8F17SO2NH(CH3) N-Me-FOSA N.A.a N-Ethyl-heptadecafluorooctane sulphonamide C8F17SO2NH(C2H5) N-Et-FOSA N.A.a N-Methyl-heptadecafluorooctane sulphonamidoethanol C8F17SO2N(CH3)CH2CH2OH N-Me-FOSE alcohol 24448-09-7 N-Ethyl-heptadecafluorooctane sulphonamidoethanol C8F17SO2N(C2H5)CH2CH2OH N-Et-FOSE
38、alcohol 1691-99-2 NOTE PFOS may be present in its salt form e.g. potassium salt (CAS 2795-39-3), lithium salt (CAS 29457-72-5), ammonium salt (CAS 29081-56-9) and diethanolamine salt (CAS 70225-39-5). Others may exist. The method described in this protocol is valid for all these different chemical f
39、orms. aN.A.: Not available. This Technical Specification describes the method for determining the PFOS concentration in the following steps: a) sampling (see Clause 7); b) extraction with methanol (see Clause 9); c) clean up of the methanol solution (see 9.2); d) analysis by LC-qMS or LC-tandemMS (s
40、ee Clause 11); e) calculation of the results (see Clause 13). 6 Apparatus and Reagents 6.1 General Sample containers shall be rinsed thoroughly with water (0) and methanol (0) prior to use. Sample containers shall be checked for possible background contamination before use. Equipment or any accessib
41、le part of which that may come into contact with the sample or the extract should be free from interfering compounds. Clean all lab-ware and accessible parts of apparatus for extraction by rinsing with methanol (0). PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 9 6.2 Equipment Use equipment free from gl
42、ass (e.g. PP, PE): cutting die or template and cutting tool to measure and cut area materials (textiles, leather, paper, etc.). Mill to grind granular bulk solids; 125 m sieve; volumetric flasks, with inert stopper; vials, polypropylene or polyethylene; ultrasonic bath, equipped with adjustable and
43、stable bath temperature (20 C to 70 C); concentration equipment (e.g. hydrophilic lipophilic base, SPE, weak anion exchange resin or rotavapor); high performance liquid chromatograph, temperature-controlled and with all required accessories including gases, LC columns, injector and a mass spectromet
44、ric detector either tandemMS or qMS. Alternative methods e.g. LC-/TOFMS are discussed in Annex A. 6.3 Reagents for extraction 6.3.1 Methanol, CH3OH (ultra pure). 6.4 Reagents for LC and MS 6.4.1 Water, complying with at least grade 3 as specified in EN ISO 3696:1995, also applicable for blank determ
45、inations. 6.4.2 Acetic Acid, w(CH3COOH) 99,9 %. 6.4.3 Ammonium acetate, w(CH3COONH4) 97 %. 6.4.4 Formic Acid, w(HCOOH) 99 %. 6.4.5 Methanol, CH3OH (HPLC grade). 6.4.6 Gases for MS. Nitrogen, GC grade 5.0 or better; Collision gas (e.g. Argon); Helium, GC grade 5.0 or better. 6.4.7 Reference solutions
46、. 13Cx-PFOS (e.g. F(CF2)8SO3- H+-, 1,2,3,4-13C4); or 18Ox-PFOS (e.g. F(CF2)8SO3- H+-, 18O2). In addition, when other types of labelled internal standards become available, they may be used. PD CEN/TS 15968:2010CEN/TS 15968:2010 (E) 10 Solutions of the reference compounds are available commercially.
47、They should be diluted to required concentrations. If reference compounds are obtained as neat, weigh 100 mg of each standard separately into a 100 ml volumetric flask and make up to the mark with methanol. Dilute this solution with methanol at a ratio 1:1 000. The impurity levels of the internal st
48、andards should be determined prior to the use of new of every new lot. 6.4.8 Range of calibration solutions, in concentration range 0,5 g/l to 50 g/l. 7 Sampling 7.1 General The chosen sample should be representative for the lot it is taken from. This document describes two different ways of reporti
49、ng results which require two different ways of sample collection. One way is based on the content per area (mass/area). The other way is based on content per mass (mass/percentage). 7.2 Conditioning samples Materials and samples shall be stored preferably at 4 C and in clean containers, see 6.2, before testing. Conditioning of leather s
