1、BS ISO25101:2009ICS 13.060.50NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDWater quality Determination ofperfluorooctanesulfonate (PFOS) andperfluorooctanoate(PFOA) Method forunfiltered samplesusing solid phaseextraction and liquidchromatography/massspectromet
2、ry-This British Standardwas published under theauthority of the StandardsPolicy and StrategyCommittee on 30 April2009. BSI 2009ISBN 978 0 580 55434 6Amendments/corrigenda issued since publicationDate CommentsBS ISO 25101:2009National forewordThis British Standard is the UK implementation of ISO 2510
3、1:2009.The UK participation in its preparation was entrusted to TechnicalCommittee EH/3/2, Physical chemical and biochemical methods.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisi
4、onsof a contract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunityfrom legal obligations.BS ISO 25101:2009Reference numberISO 25101:2009(E)ISO 2009INTERNATIONAL STANDARD ISO25101First edition2009-03-01Water quality Determination of perfluoro
5、octanesulfonate (PFOS) and perfluorooctanoate (PFOA) Method for unfiltered samples using solid phase extraction and liquid chromatography/mass spectrometry Qualit de leau Dtermination du sulfonate de perfluorooctane (PFOS) et de loctanoate perfluor (PFOA) Mthode par extraction en phase solide et chr
6、omatographie liquide/spectromtrie de masse pour des chantillons non filtrs BS ISO 25101:2009ISO 25101:2009(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which
7、 are embedded are licensed to and installed on the computer performing the editing. In downloading this file, parties accept therein the responsibility of not infringing Adobes licensing policy. The ISO Central Secretariat accepts no liability in this area. Adobe is a trademark of Adobe Systems Inco
8、rporated. Details of the software products used to create this PDF file can be found in the General Info relative to the file; the PDF-creation parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In the unlikely event th
9、at a problem relating to it is found, please inform the Central Secretariat at the address given below. COPYRIGHT PROTECTED DOCUMENT ISO 2009 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanic
10、al, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.or
11、g Published in Switzerland ii ISO 2009 All rights reservedBS ISO 25101:2009ISO 25101:2009(E) ISO 2009 All rights reserved iiiContents Page Foreword iv 1 Scope . 1 2 Normative references . 1 3 Principle. 1 4 Interferences . 2 5 Reagents 3 6 Apparatus 4 7 Sampling and sample pretreatment 4 8 Procedure
12、 4 9 Calibration . 6 10 Calculation. 8 11 Expression of results . 9 12 Test report . 9 Annex A (informative) Examples of suitable sorbents. 10 Annex B (informative) Suitable HPLC columns. 11 Annex C (informative) Examples of HPLC MS/MS chromatograms 12 Annex D (informative) Conditions for analysis o
13、f PFOS and PFOA using a single MS 15 Annex E (informative) Precision data. 16 Annex F (informative) Details of the samples used for the interlaboratory trial 17 Bibliography . 19 BS ISO 25101:2009ISO 25101:2009(E) iv ISO 2009 All rights reservedForeword ISO (the International Organization for Standa
14、rdization) 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 t
15、o 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 Sta
16、ndards 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 In
17、ternational 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 2510
18、1 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods. BS ISO 25101:2009INTERNATIONAL STANDARD ISO 25101:2009(E) ISO 2009 All rights reserved 1Water quality Determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoat
19、e (PFOA) Method for unfiltered samples using solid phase extraction and liquid chromatography/mass spectrometry WARNING Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport to address all of the safety problems, if any, associat
20、ed with its use. It is the responsibility of the user 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 International Standard be carried out by suit
21、ably qualified staff. 1 Scope This International Standard specifies a method for the determination of the linear isomers of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) in unfiltered samples of drinking water, ground water and surface water (fresh water and sea water) using high-per
22、formance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Other isomers may be reported separately as non-linear isomers and qualified as such. The analytes specified in Table 1 can be determined by this method. The method is applicable to a concentration range of 2,0 ng/l to 10 000 ng/l
23、 for PFOS and 10 ng/l to 10 000 ng/l for PFOA. Depending on the matrix, the method may also be applicable to higher concentrations ranging from 100 ng/l to 200 000 ng/l after suitable dilution of the sample or reduction in sample size. The user should be aware that particular problems could require
24、the specification of additional conditions. 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 ame
25、ndments) applies. ISO 3696:1987, Water for analytical laboratory use Specification and test methods ISO 5667-1, Water quality Sampling Part 1: Guidance on the design of sampling programmes and sampling techniques ISO 8466-1, Water quality Calibration and evaluation of analytical methods and estimati
26、on of performance characteristics Part 1: Statistical evaluation of the linear calibration function 3 Principle The analytes listed in Table 1 are extracted from the water sample by solid-phase extraction followed by solvent elution and then determined by liquid chromatography with tandem mass-spect
27、rometric detection. NOTE This method is also applicable, with some limitations, to determination using high-performance liquid chromatography with single mass-spectrometric (HPLC-MS) detection (see Annex D). BS ISO 25101:2009ISO 25101:2009(E) 2 ISO 2009 All rights reservedTable 1 Analytes determinab
28、le by this method Analyte FormulaaAbbreviation CASbNo.Perfluoro-n-octanesulfonic acid (1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-n-octanesulfonic acid) CF3(CF2)7SO3H PFOS 1763-23-1Perfluoro-n-octanoic acid (pentadecafluoro-n-octanoic acid) CF3(CF2)6COOH PFOAc335-67-1 aThe anion is the analyt
29、e. bCAS = Chemical Abstract System. cPFOA includes the acid and its salts. 4 Interferences 4.1 Interferences with sampling and extraction Sampling containers shall consist of materials that do not change the composition of the sample during sample storage. All types of fluoropolymer plastics, includ
30、ing polytetrafluoroethene (PTFE) and fluoroelastomer materials, shall be avoided during sampling, sample storage and extraction. Glassware shall be avoided for sampling due to potential analyte loss due to adsorption. Sample containers shall be rinsed thoroughly with water (5.1) and methanol (5.5) p
31、rior to use. Sample containers shall be checked for possible background contamination before use. Commercially available adsorbent materials are often of varying quality. Considerable batch-to-batch differences in quality and selectivity of these materials are possible. The recovery of a single subs
32、tance may vary with the concentration. Therefore, check analyte recovery periodically at different concentrations and whenever new batches/lots of reagents or labware are used. 4.2 Interferences with HPLC-MS/MS Substances with similar retention times and producing ions similar to those produced by t
33、he analytes of interest may interfere with the determination. These interferences may lead to incompletely resolved signals or additional signals in the chromatographic pattern of target analytes, or both. Depending on their levels in the sample, such substances may affect the accuracy and precision
34、 of the results. Matrix interferences may be caused by contaminants that are co-extracted from the samples. The extent of matrix interferences varies considerably, depending on the nature of the samples. In drinking water and ground water, matrix interferences are usually negligible, whereas wastewa
35、ter and sea water matrices can be affected by matrix interferences that lead to ionization suppression or enhancement. Interferences from instruments are significant for normal HPLC systems because many parts are made of PTFE and other fluoropolymers. It is necessary to check for possible blank cont
36、amination from individual parts, such as tubing, solvent inlet filters, valve seals and the degassing equipment, and replace these with materials such as stainless steel and polyetheretherketone (PEEK), where possible. The HPLC-vial caps should preferably be free of fluoropolymer material. The proce
37、dural blank including the instrumental blank should preferably be at least 10-fold less than the expected concentrations in real samples. BS ISO 25101:2009ISO 25101:2009(E) ISO 2009 All rights reserved 35 Reagents Use certified or analytical-grade reagents and check contamination levels of target co
38、mpounds by blank determinations. If necessary, carry out additional cleaning steps to ensure background levels are minimized. 5.1 Water, complying with at least grade 3 as specified in ISO 3696:1987. 5.2 Acetic acid, w(CH3COOH) = 99,9 % mass fraction. 5.3 Ammonia solution, w(NH3) = 25 % mass fractio
39、n. 5.4 Ammonium acetate, w(CH3COONH4) = 97 % mass fraction. 5.5 Methanol (CH3OH), HPLC grade. 5.6 Internal-standard solutions: 1,2,3,4-13C4-PFOA, = 1 ng/l. 1,2,3,4-13C4-PFOS, = 1 ng/l. Solutions of the internal standards are available commercially. They shall be diluted to the required concentration
40、s. If the standards are obtained as pure compounds, weigh 10 mg of each standard into a separate 100 ml volumetric flask and make up to the mark with methanol (5.5). Dilute the solution thus obtained initially by a factor of 100 with methanol (5.5). Other internal standards, e.g. 13C5-PFNA perfluoro
41、-n-nonanoic acid, CF3(CF2)6COOH), that meet the internal-standard requirements are acceptable for use. However, the purity of some of these commercially available standards is not adequate and, if such standards are used, the purity shall be determined in the laboratory. Analysis of impurities in st
42、andards shall be carried out prior to using new batches of standards. 5.7 Solutions of reference compounds of the analytes listed in Table 1, 0,1 ng/l, used as calibration standards. Weigh 10 mg of each reference compound into a separate 100 ml volumetric flask and make up to the mark with methanol
43、(5.5). Dilute this solution serially with methanol (5.5) to give an overall dilution of 1:1 000. Standards may also be obtained as solutions if commercially available and diluted to the required concentration. Store solutions 5.6 and 5.7 at a temperature of (4 2) C and bring them to room temperature
44、 prior to use (i.e. before dilution or spiking or injection). 5.8 Acetate buffer, 0,025 mol/l, pH 4. Mix 0,5 ml of acetic acid (5.2) with 349,5 ml of water (5.1). Dissolve 0,116 g of ammonium acetate (5.4) in 60 ml of water (5.1). Mix 200 ml of the diluted acetic acid with 50 ml of the ammonium acet
45、ate solution. 5.9 Ammonia/methanol solution, w = 0,1 % mass fraction. Mix 0,4 ml of 25 % ammonia solution (5.3), with 99,6 ml of methanol (5.5). 5.10 Solid-phase extraction material, copolymer-based. Suitable materials are available commercially (see Annex A). 5.11 Nitrogen (N2), purity 99,996 %. 5.
46、12 Sodium thiosulfate pentahydrate (Na2S2O3 5H2O). BS ISO 25101:2009ISO 25101:2009(E) 4 ISO 2009 All rights reserved6 Apparatus Equipment of which any part may come into contact with the water sample or the extract shall be free from interfering compounds. Clean all labware and apparatus for solid-p
47、hase extraction by rinsing with water (5.1) and methanol (5.5). 6.1 Narrow-neck flat-bottomed polypropene bottles, capacity 1 000 ml, with conical shoulders and screw caps. The bottles and screw caps shall be washed, rinsed with methanol (5.5) and dried before use in order to minimize contamination.
48、 6.2 Solid-phase extraction cartridges, made of inert non-leaching plastic, e.g. polypropene. The cartridges shall be packed with a minimum of 150 mg of solid-phase extraction material (5.10) as sorbent. In general, 150 mg to 250 mg of sorbent (Annex A) in a single cartridge is sufficient for up to
49、1 000 ml of water. 6.3 Vacuum or pressure assembly, for the extraction step. 6.4 Volumetric flasks, with inert stoppers. 6.5 Graduated cylinder, capacity 500 ml. 6.6 Evaporation assembly, using a nitrogen (5.11) stream passing through a stainless-steel needle. 6.7 Vials, made of polypropene or polyethylene not containing fluoropolymer materials, capacity e.g. 1,5 ml, depending on the auto-sampler. 6.8 High-performance liquid chromatograph, temperature-controlled and with all necessary accessories, inclu
