BS ISO 24293-2009 Water quality - Determination of individual isomers of nonylphenol - Method using solid phase extraction (SPE) and gas chromatography mass spectrometry (GC MS)《水质.pdf

1、BS ISO24293:2009ICS 13.060.50NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDWater quality Determination ofindividual isomers ofnonylphenol Methodusing solid phaseextraction (SPE) andgas chromatography/mass spectrometry(GC/MS)This British Standardwas published u

2、nder theauthority of the StandardsPolicy and StrategyCommittee on 31 August2009 BSI 2009ISBN 978 0 580 55676 0Amendments/corrigenda issued since publicationDate CommentsBS ISO 24293:2009National forewordThis British Standard is the UK implementation of ISO 24293:2009.The UK participation in its prep

3、aration 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 provisionsof a contract. Users are responsible

4、 for its correct application.Compliance with a British Standard cannot confer immunityfrom legal obligations.BS ISO 24293:2009Reference numberISO 24293:2009(E)ISO 2009INTERNATIONAL STANDARD ISO24293First edition2009-07-15Water quality Determination of individual isomers of nonylphenol Method using s

5、olid phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) Qualit de leau Dtermination des isomres individuels de nonylphnol Mthode par extraction en phase solide (SPE) et chromatographie en phase gazeuse/spectromtrie de masse (GC/MS) BS ISO 24293:2009ISO 24293:2009(E) PDF disclaim

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9、D 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 mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISOs membe

10、r 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.org Published in Switzerland ii ISO 2009 All rights reservedBS ISO 24293:2009ISO 24293:2009(E) ISO 2009 All rights reserved

11、iiiContents Page Foreword iv Introduction v 1 Scope . 1 2 Normative references . 1 3 Principle. 2 4 Reagents 2 5 Apparatus 3 6 Sampling and sample pretreatment 4 7 Procedures 4 7.1 Solid phase extraction 4 7.2 Clean up. 5 7.3 GC/MS operating conditions . 5 7.4 Blank determination . 5 7.5 Identificat

12、ion 5 8 Calibration . 7 8.1 General requirements. 7 8.2 Calibration over the total procedure with internal standard 7 9 Calculation. 8 9.1 Calculation of contribution of individual isomers of nonylphenol in technical mixture. 8 9.2 Calculation of relative response factor of individual isomers of non

13、ylphenol 8 9.3 Quantification of individual isomers of nonylphenol using relative response factor . 9 9.4 Calculation of internal standard recovery 9 10 Expression of results . 10 11 Test report . 10 Annex A (informative) Sorbent example 11 Annex B (informative) Suitable capillary column 12 Annex C

14、(informative) Examples of chromatograms 13 Annex D (informative) Example of FID chromatogram and composition ratio (%) of isomers in 4-nonylphenol standard. 16 Annex E (informative) Method performance data . 18 Annex F (informative) Description of the matrices of the samples used for the interlabora

15、tory trial. 21 Bibliography . 24 BS ISO 24293:2009ISO 24293:2009(E) iv ISO 2009 All rights reservedForeword 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 c

16、arried 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 wor

17、k. 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 Inter

18、national 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 th

19、e 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 24293 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods. BS ISO 24293:2009I

20、SO 24293:2009(E) ISO 2009 All rights reserved vIntroduction The user should be aware that particular problems could require the specifications of additional marginal conditions. BS ISO 24293:2009BS ISO 24293:2009INTERNATIONAL STANDARD ISO 24293:2009(E) ISO 2009 All rights reserved 1Water quality Det

21、ermination of individual isomers of nonylphenol Method using solid phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) WARNING Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport to address all of the safety

22、 problems, if any, associated 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 Stan

23、dard be carried out by suitably qualified staff. 1 Scope This International Standard specifies a method for the determination of selected individual isomers of nonylphenol in non-filtered samples of drinking water, waste water, ground water and surface water. The method is applicable in concentratio

24、ns between 0,001 g/l and 0,1 g/l for individual isomers and from 0,01 g/l to 0,2 g/l for the sum of 4-nonylphenol (mixture of isomers). Depending on the matrix, the method is also applicable to waste water in concentrations between 0,1 g/l and 50 g/l. 2 Normative references The following referenced

25、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 metho

26、ds 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 estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration functi

27、on BS ISO 24293:2009ISO 24293:2009(E) 2 ISO 2009 All rights reserved3 Principle Extraction of the analytes listed in Table 1 from the acidified water sample by solid phase extraction, solvent elution and determination by gas chromatography with mass spectrometric detection. The thirteen isomers list

28、ed (eleven identified isomers and two isomers with tentative identification) constitute more than 90 % of the 4-nonylphenol isomers that are detectable in technical products and in environmental samples in general. Water samples containing more than 500 mg/l of suspended matter and waste water sampl

29、es are extracted by passing 100 ml of the sample through the solid phase extraction cartridge (5.2). Table 1 Analytes determinable by this method Analyte Formula Abbreviation 4-(2,4-Dimethylheptan-4-yl)phenol C15H24O NP1 4-(2,4-Dimethylheptan-2-yl)phenol C15H24ONP2 4-(3,6-Dimethylheptan-3-yl)phenol

30、C15H24ONP3 4-(3,5-Dimethylheptan-3-yl)phenol C15H24O NP4a 4-(2,5-Dimethylheptan-2-yl)phenol C15H24ONP5 4-(3,5-Dimethylheptan-3-yl)phenol C15H24O NP6 a4-(3-Ethyl-2-methylhexan-2-yl)phenol C15H24O NP7 4-(3,4-Dimethylheptan-4-yl)phenolbC15H24O NP8c4-(3,4-Dimethylheptan-3-yl)phenol C15H24O NP9e4-(3,4-Di

31、methylheptan-4-yl)phenol C15H24O NP10c4-(2,3-Dimethylheptan-2-yl)phenol C15H24O NP11 4-(3-Methyloctan-3-yl)phenol C15H24O NP12 4-(3,4-Dimethylheptan-3-yl)phenoldC15H24ONP13eaPossible enantiomer. bInformation from MAKINO et al.6cPossible enantiomer. dInformation from KATASE et al.5ePossible enantiome

32、r. 4 Reagents Use reagents with negligible concentrations of the compounds of interest compared with the concentrations to be determined. Verify by blank determinations and, if necessary, apply additional cleaning steps. 4.1 Water, grade 1, as specified in ISO 3696. 4.2 Acid, e.g. hydrochloric acid,

33、 w(HCl) = 37 %, or sulfuric acid, c(H2SO4) = 1 mol/l. 4.3 Acetone, C3H6O. 4.4 Methanol, CH3OH. 4.5 Hexane, C6H14. 4.6 Sodium sulfate, anhydrous, Na2SO4, powdered. BS ISO 24293:2009ISO 24293:2009(E) ISO 2009 All rights reserved 34.7 Internal standard solution, 4-n-Nonylphenol (ring-13C6), C9H19-13C6H

34、4-OH solution, = 1 ng/l. Weigh 10 mg of 4-n-nonylphenol in a 100 ml measuring flask and bring to volume with methanol (4.4). Dilute this solution with methanol in the ratio of 1:100. Acetone is not suitable for preparation of standard solution in this method. Alternative internal standards e.g. 4-n-

35、nonylphenol (deuterium label) may be used if internal standard requirements can be met. 4.8 4-nonylphenol solution, = 1 ng/l (calibration standard). Weigh 10 mg of 4-nonylphenol, C15H24O (technical mixture of isomers), CAS No 25154-52-3, in a 100 ml measuring flask and bring to volume with hexane (4

36、.5). Dilute this solution in the ratio of 1:100 with hexane if a calibration over the total procedure is applied. 4.9 Solid phase material, on styrene-divinylbenzene polymer basis, e.g. commercially available packing material (see Annex A). 4.10 Nitrogen, N2, purity W 99,996 % volume fraction, for d

37、rying of the sorbent packing after sample extraction and for concentration of extracts by evaporation. 4.11 Sodium thiosulfate pentahydrate, Na2S2O3 5 H2O. 4.12 Ethyl acetate, C4H8O2. 4.13 Diethyl ether, C4H10O. 4.14 Corresponding internal standard solution for syringe spike, phenanthrene (d10), C14

38、D10solution, CAS No 85-01-8, = 0,1 ng/l. Weigh 10 mg of phenanthrene (d10) in a 100 ml measuring flask and bring to volume with hexane (4.5). Dilute this solution with hexane in the ratio of 1:1 000. 5 Apparatus Equipment or parts which may come into contact with the water sample or the extract shou

39、ld be free from interfering compounds. Clean all glasswares by rinsing with acetone (4.3). Avoid detergents when using a labware washing machine. Alternatively, heat all glassware, except volumetric wares, to at least 400 C for at least 2 h prior to use. 5.1 Narrow-neck flat-bottomed glass bottles,

40、conical shoulders, preferably brown glass, of capacity 1 000 ml, with glass stoppers or with PTFE-lined screw caps (PTFE = polytetrafluoroethene). Keep samples away from light if brown glass bottles are not available. The bottle and cap liner or glass stopper should be rinsed with acetone (4.3) and

41、dried before use in order to minimize contamination. 5.2 Solid phase extraction cartridges, inert non-leaching plastic, e.g. polypropene or glass. The cartridges should be packed with a minimum of 200 mg of sorbent (4.9). The commercially available disk type may be used provided there is enough info

42、rmation available concerning the sample volume and the required quantity of elution solvent. These cartridges are used for extraction. 5.3 Vacuum or pressure assembly, for the extraction step. 5.4 Volumetric flasks, with inert stopper. 5.5 Quartz wool, rinsed with acetone (4.3). 5.6 Muffle furnace,

43、capable of being maintained at a temperature of 400 C. 5.7 Evaporation assembly, e.g. rotary evaporator with vacuum stabilizer and water bath. BS ISO 24293:2009ISO 24293:2009(E) 4 ISO 2009 All rights reserved5.8 Vials, brown glass with PTFE-lined septa, capacity e.g. 1,5 ml, according to the autosam

44、pler. 5.9 Gas chromatograph/mass spectrometer. The gas chromatograph shall be temperature-programmable, with all required accessories including gases, capillary columns, capillary injector and mass spectrometric detector. The mass spectrometer should be capable of operating over the mass range of in

45、terest and it should be equipped with a data system capable of quantifying ions using selected m/z values. 5.10 Clean up cartridge column, inert non-leaching plastic, e.g. polypropene or glass. The cartridges should be packed with a minimum of 200 mg of sorbent (reverse phase, silica). These cartrid

46、ges are used for clean up. 5.11 Flame ionization detector. 6 Sampling and sample pretreatment Take samples as specified in ISO 5667-1. Use carefully cleaned bottles for sampling (5.1). Fill each bottle only to its shoulder with water to be sampled (approximately 1 000 ml). In the presence of free ch

47、lorine, immediately add approximately 80 mg of sodium thiosulfate pentahydrate (4.11). Other non-interfering substances may be used for dechlorination as well (e.g. sodium sulfite). Acidify the samples with acid (4.2) to pH 3,5. If necessary, store the samples in a refrigerator (2 C to 5 C) and anal

48、yse them as soon as possible, but not later than 2 weeks after sampling. 7 Procedures 7.1 Solid phase extraction 7.1.1 General In general, samples are examined without pretreatment; in other words, suspended solids are not removed prior to analysis. Before starting the analysis, homogenize the sampl

49、es. If blocking of the cartridge packing is likely to occur, use a filter aid, e.g. quartz wool (5.5). 7.1.2 Conditioning of the solid phase material The following procedures are described for commercially available 6 ml polypropylene cartridges (5.2) packed with 200 mg of sorbent (4.9) sandwiched between two polyethylene frits. The manufacturers guidance for other materials of the SPE cartridge shall be preferred. Rinse the cartridge with two 10 ml aliquots of acetone (4.3) and let the c