1、BS EN ISO18857-2:2011ICS 13.060.50NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISHSTANDARDWaterqualityDeterminationofselectedalkylphenolsPart2:Gaschromatographic-massspectrometricdeterminationofalkylphenols,theirethoxylatesandbisphenolAinnon-filteredsamplesfollowingsolid
2、-phaseextractionandderivatisationNational forewordThis British Standard is the UK implementation of EN ISO 18857-2:2011. It is identical to ISO 18857-2:2009. It supersedes BS ISO 18857-2:2009, which is withdrawn.The UK participation in its preparation was entrusted by Technical Committee EH/3, Water
3、 quality to EH/3/2, Physical chemical and biochemical methods.A list of organizations represented on this subcommittee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct applicatio
4、n.Compliance with a British Standard cannot confer immunity from legal obligations.BS EN ISO 18857-2:2011This British Standardwas published underthe authority of theStandards Policy andStrategy Committee on 30September 2009 BSI 2011Amendments/corrigenda issued since publicationDate Comments 31 Decem
5、ber 2011 This corrigendum renumbers BS ISO 18857-2:2009 as BS EN ISO 18857-2:2011ISBN 978 0 580 74618 5EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 18857-2 November 2011 ICS 13.060.50 English Version Water quality - Determination of selected alkylphenols - Part 2: Gas chromatographic-mas
6、s spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in non-filtered samples following solid-phase extraction and derivatisation (ISO 18857-2:2009) Qualit de leau - Dosage dalkylphnols slectionns - Partie 2: Dosage par chromatographie en phase gazeuse-spectromtrie de mass
7、e dalkylphnols, de leurs thoxylates et du bisphnol A dans des chantillons non filtrs aprs extraction en phase solide et drivation (ISO 18857-2:2009) Wasserbeschaffenheit - Bestimmung von ausgewhlten Alkylphenolen - Teil 2: Gaschromatographische-massenspektrometrische Bestimmung von Alkylphenolen, de
8、ren Ethoxylaten und Bisphenol A fr nichtfiltrierte Proben unter Verwendung der Festphasenextraktion und Derivatisierung (ISO 18857-2:2009) This European Standard was approved by CEN on 15 October 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the cond
9、itions 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-CENELEC Management Centre or to any CEN member. This European Standard exist
10、s 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-CENELEC Management Centre has the same status as the official versions. CEN members are the national stan
11、dards bodies of Austria, Belgium, Bulgaria, 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
12、United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 1885
13、7-2:2011: EForeword The text of ISO 18857-2:2009 has been prepared by Technical Committee ISO/TC 147 “Water quality” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 18857-2:2011 by Technical Committee CEN/TC 230 “Water analysis” the secretariat of which
14、is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2012, and conflicting national standards shall be withdrawn at the latest by May 2012. Attention is drawn to the possibility tha
15、t 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 or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to
16、 implement this European Standard: Austria, Belgium, Bulgaria, 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, Swede
17、n, Switzerland and the United Kingdom. Endorsement notice The text of ISO 18857-2:2009 has been approved by CEN as a EN ISO 18857-2:2011 without any modification. BS EN ISO 18857-2:2011 EN ISO 18857-2:2011 (E)iiiContents PageForeword ivIntroduction.v1Scope12Normative references13Principle24Interfere
18、nces25Reagents.36Apparatus.47Sampling and sample pretreatment 58Procedure.59Calibration and analysis of samples.810 Expression of results911 Test report10Annex A (informative) Example of a sorbent .11Annex B (informative) Suitable capillary columns12Annex C (informative) Examples of chromatograms13A
19、nnex D (informative) Performance data.17Bibliography18BS EN ISO 18857-2:2011 EN ISO 18857-2:2011 (E)iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normal
20、ly carried out through ISO technical committees. Each member body interested in a subject for which a tec hnical committee has beenestablished has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the
21、 work. ISO collaborates closelywith the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordancewith the rules given in the ISO/IEC Directives, Part 2.The main task of technical committees is to prepare Inte
22、rnational Standards. Draft International Standardsadopted by the technical committees are circulated to the member bodies for voting. Public ation as an International Standard requires approval byat least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of th
23、e elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying an y or all such patent rights. ISO18857-2 was prepared by Technical Committee ISO/TC147, Water quality, Subcommittee SC 2, Physical,chemical and biochemical methods. ISO18857 consists
24、of the following parts, under the general title Water quality Determination of selected alkylphenols: Part1:Method for non-filtered samples using liquid-liquid extraction and gas chromatography with massselective detection Part2: Gas chromatographic-mass spectrometric determination of alkylphenols,
25、their ethoxylates and bisphenol A in non-filtered samples following solid-phase extrac tion and derivatisation BS EN ISO 18857-2:2011 EN ISO 18857-2:2011 (E)vIntroduction The user should be aware that particular problems could require the specifications of additional marginal conditions.BS EN ISO 18
26、857-2:2011 EN ISO 18857-2:2011 (E)BS EN ISO 18857-2:2011 EN ISO 18857-2:2011 (E)INTERNATIONAL STANDA RD 1Water quality Determination of selected alky lphenols Part 2: Gas chromatographic-mass spectrometric determination ofalkylphenols, their ethoxylates and bisphenol A in non-filteredsamples followi
27、ng solid-phase extraction and derivatisation WARNING Persons using this part of ISO 18857should be familiar with normal laboratory practice.This part of ISO 18857 does not purport to address all of the safety problems, if any, associated withits use. It is the responsibility of the user to establish
28、 appropriate safetyand health practices and toensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that testsconducted in accordance with this part of ISO 18857be carried out by suitablyqualified staff.1 Scope This part of ISO18857 specifies a gas chromatog
29、raphic-mass s pectrometric (GC-MS) determination of selected alkylphenols, their ethoxylates and bisphenolA in non-filtered samples of drinking, ground, surface, and waste watersfollowing solid-phase extractionand derivatisation. The lower limit of the working range depends on the matrix, on the spe
30、cific compound to be analysed andon the sensitivityof the mass spectrometric detection unit. The method is applicable in a working range from0,005 g/l to 0,2 g/l for 4-(1,1,3,3-tetramethylbutyl)phenol (OP), and its mono- (OP1 EO) and diethoxylate (OP2 EO), from 0,03 g/l to 0,2 g/l for 4-nonylphenol
31、(mixture of isomers)(NP), and its mono- (NP1 EO) anddiethoxylate (NP 2 EO), and from 0,05 g/l to 0,2 g/l for bisphenol A (BPA). Depending on the matrix, the method is also applicable to waste water in a working range from 0,1 g/l to50g/l for OP, OP 1 EO, OP2 EO and BPA, and from 0,5g/l to 50 g/l for
32、 NP, NP 1 EO and NP 2 EO. The working ranges are based on experimental work carried out in ruggedness testing. Water samples containingsuspended matter at concentrations ofmore than 500 mg/l and waste water samples are extracted bypassinga 100 ml sample through the cartridge. 2 NormativereferencesTh
33、e following referenced documents are indispensable for the application of this document. For datedreferences, only the edition cited applies. For undated references, the latest edition of the referenceddocument (including anyamendments) applies.ISO 3696, Water for analytical laboratory use Specifica
34、tion and test methodsISO 5667-1, Water quality Sampling Part1: Guidance on the design of sampling programmes and sampling techniquesISO 5667-3, Water quality Sampling Part3: Guidance on the preservation and handling of watersamples ISO 8466-1, Water quality Calibration and evaluation of analytical m
35、ethods and estimation of performancecharacteristics Part1: Statistical evaluation of the linear calibration functionEN ISO 18857-2:2011 (E)BS EN ISO 18857-2:2011 2 3 Principle Extraction of the analytes listed in Table 1 from an acidified water sample by so lid-phase extraction, solvent elution, der
36、ivatisation and determination by GC-MS detection.Table 1 Analytes determinable by GC-MS following solid-phase extraction and derivatisationAnalyte Empirical formula Abbreviation CAS a No. 4-(1,1,3,3-Tetramethylbutyl)phenol C 14H 22O OP 140-66-9 4-(1,1,3,3-Tetramethylbutyl)phenol monoethoxylate C 16H
37、 26O 2 OP1 EO 4-(1,1,3,3-Tetramethylbutyl)phenol diethoxylate C 18H 30O 3 OP2 EO 4-Nonylphenol (mixture of isomers) C 15H 24O NP 84852-15-3b4-Nonylphenol monoethoxylate (mixture of isomers) C 17H 28O 2 NP1 EO 4-Nonylphenol diethoxylate (mixture of isomers) C 19H 32O 3 NP2 EO Bisphenol A C 15H 16O 2
38、BPA 80-05-7 a CAS: Chemical Abstracts Service.b The commercially produced nonylphenols are predominantly 4-nonylphenol with a varied and undefined degree of branching in thealkyl groups. Thismixture of isomers falls under the CAS number 84852-15-3, but CAS numbers 104-40-5 (4-nonylphenol, straightch
39、ain) and 25154-52-3 (nonylphenol,straightchain) have also been incorrectly used to denote this isomermixture.4 Interferences 4.1Sampling and extractionSampling containers shall consist of materials that do not change the sa mple when in contact with it. Avoidcontact with plastics and other organic m
40、aterials during sampling, sample storage or extraction. Commercially available adsorbent materials are often of varying quality. Considerable batch-to-batchdifferences in quality and selectivity of this material are possible. The recovery of single substances can varywith the concentration. Therefor
41、e, check the recoveryregularly at different concentrations and whenever newbatches are used. Perform calibration and analysis with material from the same batch. 4.2Gas chromatography-mass spectrometrySubstances with retention times or which produce masses similar to the analytes to be determined can
42、interfere with the determination. These interferences may lead to incompletely resolved signals and to additional signals in the chromatographic patternof NP, NP1 EO and NP 2 EO. They may,depending on their magnitude, affectaccuracy and precision of the analytical results, since all three analytes a
43、re determined from the sum of a cluster of eight to ten chromatographic peaks (Table 3 and AnnexC). It is important that the interfering peaks are not included in the calculations. The presence of interfering compounds can, if necessary, be detected by recording full mass spectra (range of mass frag
44、mentsto monitor m / z = 50 to m / z = 350). Matrix interferences can be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences variesconsiderably, depending on the nature of the sample. In drinking water and groundwater,matrixinterferences usually do not occ
45、ur.BS EN ISO 18857-2:2011 EN ISO 18857-2:2011 (E)35 ReagentsThe reagents shall not have blank values that would interfere with the GC-MS analysis. Use solvents and reagents of sufficient purity, i.e. with negligibly low impurities compared with the concentration of analytes to be determined. As reag
46、ents, use, as far as available, “residual grade” or better inorder to obtain clean blanks. Check blanks regularly and establish proper chargecontrol. 5.1 Water , as specified in ISO3696, grade 1, or equivalent. 5.2 Acid, e.g. hydrochloric acid, w (HCl) = 37 % mass fraction, or su lfuric acid, c (H2
47、SO4 ) = 1 mol/l. 5.3 Acetone , C3 H 6 O.5.4 Internal standard solutions. Examples of suitable internal standards are given in Table 2. Store solutions 5.4.1 and 5.4.2 in a refrigerator protected from light. Check the solutions weeklyprior to use. Table 2 Internal standards No. Name Abbreviation CAS
48、No. 1 4-(1,1,3,3-Tetramethylbutyl)phenol (ring-13C 6 ) OP-13C 6 2 4-(1,1,3,3-Tetramethylbutyl)phenol monoethoxylate (ring-13C 6 ) OP1 EO-13C 6 3 4-(1,1,3,3-Tetramethylbutyl)phenol diethoxylate (ring-13C 6 ) OP2 EO-13C 6 4 4-(3,6-Dimethyl-3-heptyl)phenol (ring-13C 6 ) 363 NP-13C 6 5 4-(3,6-Dimethyl-3
49、-heptyl)phenol monoethoxylate (ring- 13C 6 ) 363 NP 1 EO-13C 6 6 4-(3,6-Dimethyl-3-heptyl)phenol diethoxylate (ring-13C 6 ) 363 NP 2 EO-13C 6 7 Bisphenol A-d16BPA-d16 96210-87-6 5.4.1 Internal standard stock solution. Use commerciallyavailable internal standard solutions or prepare a solution as follows.Weigh 10 mg of each internal standard (Table 2) separatelyin a 100 ml one-mark volumetric flask and makeup to the mark with acetone (5.3) to give a concentration of each internal standard of 100 ng/l. 5.4.2 Interna
