1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58trichloroacetic acid and selected haloacetic acids Method using gas chromatography (GC-ECD and/or G
2、C-MS detection) after liquid-liquid extraction and derivatizationThe European Standard EN ISO 23631:2006 has the status of a British StandardICS 13.060.50Water quality Determination of dalapon, BRITISH STANDARDBS EN ISO 23631:2006Incorporating corrigendum no. 1BS EN ISO 23631:2006This British Standa
3、rd was published under the authority of the Standards Policy and Strategy Committee on 31 March 2006 BSI 2007ISBN 0 580 47994 3Compliance with a British Standard cannot confer immunity from legal obligations.Amendments issued since publicationAmd. No. Date Comments17048 Corrigendum No. 130 March 200
4、7 Addition of Annex ZANational forewordThis British Standard was published by BSI. It is the UK implementation of EN ISO 23631:2006, incorporating corrigendum February 2007. It is identical with ISO 23631:2006.The UK participation in its preparation was entrusted by Technical Committee EH/3, Water q
5、uality, to Subcommittee 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 corre
6、ct application. EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 23631February 2006ICS 13.060.50 Incorporating corrigendum February 2007English VersionWater quality - Determination of dalapon, trichloroacetic acidand selected haloacetic acids - Method using gaschromatography (GC-ECD and/or GC-M
7、S detection) after liquid-liquid extraction and derivatization (ISO 23631:2006)Qualit de leau - Dosage du dalapon, de lacidetrichloroactique et dacides haloactiques selectionns -Mthode par chromatographie en phase gazeuse(dtection CG-DCE et/ou CG-SM) aprs extraction liquide-liquide et drivatisation
8、(ISO 23631:2006)Wasserbeschaffenheit - Bestimmung von Dalapon,Trichloressigsure und ausgewhlten Halogenessigsuren- Verfahren mittels Gaschromatographie (GC-ECDund/oder GC-MS-Detektion) nach Flssig-Flssig-Extraktion und Derivatisierung (ISO 23631:2006)This European Standard was approved by CEN on 16
9、January 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be ob
10、tained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secr
11、etariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portu
12、gal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means res
13、ervedworldwide for CEN national Members.Ref. No. EN ISO 23631:2006: EForeword This document (EN ISO 23631:2006) has been prepared by Technical Committee ISO/TC 147 “Water quality“ in collaboration with Technical Committee CEN/TC 230 “Water analysis“, the secretariat of which is held by DIN. This Eur
14、opean Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by August 2006, and conflicting national standards shall be withdrawn at the latest by August 2006. According to the CEN/CENELEC Internal Regulations, the nati
15、onal standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Po
16、rtugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Endorsement notice The text of ISO 23631:2006 has been approved by CEN as EN ISO 23631:2006 without any modifications. EN ISO 23631:2006Reference numberISO 23631:2006(E)INTERNATIONAL STANDARD ISO23631First edition200
17、6-02-01Water quality Determination of dalapon, trichloroacetic acid and selected haloacetic acids Method using gas chromatography (GC-ECD and/or GC-MS detection) after liquid-liquid extraction and derivatization Qualit de leau Dosage du dalapon, de lacide trichloroactique et dacides haloactiques sle
18、ctionns Mthode par chromatographie en phase gazeuse (dtection CG-DCE et/ou CG-SM) aprs extraction liquide-liquide et drivatisation EN ISO 23631:2006ii iiiContents Page Foreword iv Introduction v 1 Scope . 1 2 Normative references . 2 3 Principle. 2 4 Interferences . 2 5 Reagents 2 6 Apparatus 5 7 Sa
19、mpling and sample pre-treatment. 7 8 Procedure 7 9 Calibration . 10 10 Calculation. 13 11 Expression of results . 14 12 Test report . 15 Annex A (informative) Examples of gas chromatograms 16 Annex B (informative) Mass spectra of methylated dalapon and haloacetic acids. 19 Annex C (informative) Prec
20、ision data. 23 Bibliography . 24 EN ISO 23631:2006Annex ZA (informative) A-deviations . 25 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 normally carrie
21、d 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 work. IS
22、O 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 Internatio
23、nal 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 the ele
24、ments 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 23631 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods. EN ISO 23631:2006vIntro
25、duction The user should be aware the particular problems could require the specifications of additional marginal conditions. EN ISO 23631:2006blank1Water quality Determination of dalapon, trichloroacetic acid and selected haloacetic acids Method using gas chromatography (GC-ECD and/or GC-MS detectio
26、n) after liquid-liquid extraction and derivatization WARNING Persons using this International Standard should be familiar with normal laboratory practice. This International Standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of
27、the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. Diazomethane is explosive, extremely toxic and severely irritating, causing pulmonary oedema when inhaled in high concentrations. Long-term, low-level exposure may lead to
28、sensitization, resulting in asthma-like symptoms. Also, diazomethane and several of its chemical precursors have been cited as carcinogens. IMPORTANT It is absolutely essential that tests conducted according to this International Standard be carried out by suitably trained staff. 1 Scope This Intern
29、ational Standard specifies a method for the determination of dalapon, trichloroacetic acid (TCA) and selected haloacetic acids (see Table 1) in ground water and drinking water by gas chromatography (GC-ECD and/or GC-MS detection) after liquid-liquid-extraction and derivatization using diazomethane.
30、Depending on the matrix, the method is applicable to a concentration range from 0,5 g/l to 10 g/l. The validated reporting limit of TCA and dalapon is about 0,05 g/l (see Table C.1). Detection by electron-capture detector (ECD) in general leads to lower detection limits. Detection by mass spectromet
31、ry (MS) allows analyte identification. This method may be applicable as well to compounds not mentioned in Table 1 or to other types of water. However, it is necessary to verify the applicability of this method for these special cases. Table 1 Haloacetic acids determined by this method Name Molecula
32、r formula Relative molecular mass CAS registry No. Bromochloroacetic acid C2H2BrClO2173,4 5589-96-8 Dalapon aC3H4Cl2O2143,0 75-99-0 Dibromoacetic acid C2H2Br2O2217,8 631-64-1 Dichloroacetic acid C2H2Cl2O2128,9 79-43-6 Monobromoacetic acid C2H3BrO2138,9 79-08-3 Monochloroacetic acid C2H3ClO294,5 79-1
33、1-8 Trichloroacetic acid (TCA) C2HCl3O2163,4 76-03-9 a2,2-Dichloropropionic acid. EN ISO 23631:20062 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 lat
34、est edition of the referenced document (including any amendments) 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 ISO 5667-2, Water quality Sampling Part 2: Guidance on
35、 sampling techniques ISO 5667-3, Water quality Sampling Part 3: Guidance on the preservation and handling of water samples 3 Principle Dalapon, trichloroacetic acid (TCA) and selected haloacetic acids are extracted from the acidified water sample with methyl-tert-butyl ether (MTBE). The extract is c
36、oncentrated by evaporation. The analytes are methylated using diazomethane. The methylated analytes are separated, identified and quantified by means of capillary gas chromatography with electron-capture detection (GC-ECD) and/or mass spectrometry (GC-MS). 4 Interferences 4.1 Interferences with the
37、extraction procedure Suspended particles in the water may interfere with the liquid-liquid-extraction procedure causing problems in layer separation. In this case, filter the water sample through a glass fibre filter (6.15) prior to enrichment. 4.2 Interferences with the gas chromatography and mass
38、spectrometry procedure Interferences may be caused e.g. by the injection system used or by inadequate separation of the analytes. Experienced operators, using the information given in the instrument manuals, may be able to minimize this type of interference. Regular checking of the chromatographic a
39、nd spectrometric system is required to maintain adequate performance. Required system stability should be checked regularly by the use of a GC-standard. Insufficiently purified solvents (5.6) as well as insufficiently purified sodium chloride (5.10) may cause severe interferences. Reagents used in t
40、he method to perform derivatization may lead to interferences in the ECD-chromatograms. Therefore, it is highly recommended that temperatures of the diazomethane building process be carefully kept in limits (see 5.19). 5 Reagents Use solvents and reagents of sufficient purity, i.e. with negligibly l
41、ow impurities compared with the concentration of analytes to be determined. As reagents use, as far as available, “residual grade” or better in order to obtain clean blanks. Check blanks regularly and establish proper charge control. 5.1 Water, complying to grade 1 as defined in ISO 3696:1987, or eq
42、uivalent. EN ISO 23631:200635.2 Operating gases for the gas chromatography/mass spectrometry, of high purity and in accordance with manufacturers specifications. 5.3 Nitrogen, of high purity, i.e. minimum 99,996 % by volume, for concentration by evaporation. 5.4 Diethyl ether, C4H10O. NOTE Stabilize
43、rs may cause interferences. 5.5 Ethanol, C2H5OH. 5.6 Solvents, e.g. ethyl acetate, C4H8O2; acetone, C3H6O. 5.7 Methyl-tert-butyl ether (MTBE), C5H12O. 5.8 Benzoic acid, dissolved in ethanol, c(C7H6O2) 0,2 mol/l. 5.9 N-methyl-N-nitroso-4-toluenesulfonamide, C8H10N2O3S. 5.10 Sodium chloride, NaCl (e.g
44、. heated at 550 C for 4 h). 5.11 Potassium hydroxide solution, w(KOH) 60 %. 5.12 Sodium hydroxide solution, c(NaOH) 0,1 mol/l. 5.13 Sodium thiosulfate pentahydrate, Na2S2O35 H2O. 5.14 Phenolphthalein, C20H14O4. 5.15 Acetic acid, w(CH3COOH) 10 %. 5.16 Mineral acid, e.g. hydrochloric acid, w(HCl) 25 %
45、. 5.17 Methylated reference substances. Methylated reference substances (methyl esters of the acids listed in Table 1) of defined concentration suitable for the preparation of reference solutions for gas chromatography (9.2). 5.17.1 Stock solutions of individual methylated reference substances. As a
46、n example, pipette 50 mg of each of the methylated reference substances into 100 ml volumetric flasks, dissolve in MTBE (5.7) and dilute to volume with MTBE. Store stock solutions at about 18 C, protected from light. They are stable for about 1 year. 5.17.2 Multiple-substance stock solutions of meth
47、ylated reference substances. As an example, transfer 2 ml of each of the solution of the individual substance (5.17.1) into a 100 ml volumetric flask and dilute to volume with MTBE (5.7). Store stock solutions at about 18 C, protected from light. They are stable for about 1 year. 5.17.3 Reference so
48、lutions of methylated reference substances. Solutions of defined concentration suitable for multipoint calibration (working solution for gas chromatography). Prepare the reference solutions by an adequate dilution of the stock solution (5.17.2) with MTBE (5.7). Store reference solutions at a maximum
49、 of 10 C or below (e.g. in a refrigerator), protected from light. They are stable for about 6 months. EN ISO 23631:20064 5.18 Non-methylated reference substances. 5.18.1 General requirements. Reference substances (acids, listed in Table 1) of defined concentration, suitable for the preparation of reference solutions used for spiking water samples. Spike samples for calibration of the total procedure (9.3 and 9.4) and calculation of the overall recovery, i.
