1、haust 1997 DEUTSCHE NORM DIN EN IS010301 Determination of highly volatile halogenated hydrocarbons in water Gas-chromatographic methods (IS0 10301 : 1997) English version of DIN EN IS0 10301 ICs 13.060.01 Supersedes DIN 38407-4, Descriptors: Water analysis, halogenated hydrocarbons. Wasserbeschaffen
2、heit - Bestimmung leichtflchtiger halogenierter Kohlenwasser- stoffe - Gaschromatographische Verfahren (IS0 10301 : 1997) May 1988 edition, and DIN 38407-5, November 1991 edition. European Standard EN IS0 10301 : 1997 has the status of a DIN Standard. A comma is used as the decimal marker. This stan
3、dard is part of the series Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung - Gemeinsam erfabare Stoffgruppen (Gruppe f) (German standard methods for the examination of water, waste water and sludge - Substance group analysis (group F). National foreword This standard has be
4、en published in accordance with a decision taken by CEN/TC 147 to adopt, without alteration, International Standard IS0 10301 as a European Standard. The responsible German body involved in its preparation was the Normenausschu Wasseiwesen (Water Practice Standards Committee). Expert assistance and
5、specialized laboratories will be required to perform the analysis described in this standard. Depending on the objective of the analysis, a check shall be made in each individual case on whether and to what extent additional boundary conditions will have to be specified. Standard methods published a
6、s DIN Standards are obtainable from Beuth Verlag GmbH, either individually or grouped in volumes. The standard methods included in the loose-leaf publication entitled Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung will continue to be published by VCH Verlagsgesellschaft. T
7、he standard methods relating to the Wasserhaushaltsgesetz (German Water Management Act), the Wasserabgabengesetz (Law on the charges leviable for the discharge of effluent into water), and all the regulations on waste water that have been issued to date are included in DIN-Taschenbuch (DIN Handbook)
8、 230. Continued overleaf. EN comprises 49 pages. Q No pari of this standard may be reproduced without the prior permission of DIN Deutsches Institut fr Normung e.V., Berlin. Beuth Verlag GmbH, Berlin, has the exclusive right of sale for German Standards (DIN-Normen). Ref. No. DIN EN IS0 1030 1 : 199
9、7-08 English price group 14 Sales No. 11 14 01.98 Page 2 DIN EN IS0 10301 :1997-08 Standard methods or draft standards bearing the group title ?German standard methods for the examination of water, waste water and sludge? are classified under the following categories (main titles): General informati
10、on (group A) Physical and physicochemical parameters (group C) (DIN 38402) (DIN 38404) Anions (group D) Cations (group E) Substance group analysis (group F) Gaseous constituents (group G) Parameters characterizing effects and substances (group H) (DIN 38405) (DIN 38406) (DIN 38407) (DIN 38408) (DIN
11、38409) Biological-ecological methods of analysis (group M) (DIN 38410) Microbiological methods (group K) (DIN 3841 1) Bio-assays (group L) (DIN 38412) Individual constituents (group P) (DIN 38413) Sludge and sediments (group S) (DIN 38414) Bio-assays with microorganisms (group T) (DIN 38415) In addi
12、tion to the methods described in the DIN 38402 to DIN 38415 series of standards, there are a number of European Standards available, which also form part of the collection of German standard methods. Information on Parts of these series of standards that have already been published can be obtained f
13、rom the offices of the Normenausschu Wasserwesen, telephone (030) 26 O1 -24 23, or from Beuth Verlag GmbH, Burggrafenstrae 6, D-10787 Berlin. DIN EN 25667-1 and DIN 25667-2 are the standards corresponding to International Standards IS0 5667-1 and IS0 5667-2, respectively, referred to in subclause 1.
14、2 of the EN. Amendments DIN 38407-4, May 1988 edition, and DIN 38407-5, November 1991 edition, have been superseded by the specifications of EN IS0 10301, which is identical to IS0 10301. Previous editions DIN 38407-4: 1988.05; DIN 38407-5: 1991-11. National Annex NA Standards referred to (and not i
15、ncluded in Normative references) DIN EN 25667-1 DIN EN 25667-2 Water quality - Sampling - Part 1 : Guidance on the design of sampling programmes (IS0 5667-1 : 1980) Water quality - Sampling - Part 2: Guidance on sampling techniques (IS0 5667-2:1991) EU ROPEAN STAN DAR D NORME EUROPENNE EUROPISCHE NO
16、RM EN IS010301 April 1997 ICs 13.060.30 Descriptors: Water analysis, halogenated hydrocarbons. English version Water quality Determination of highly volatile halogenated hydrocarbons Gas-chromatographic methods (IS0 10301 : 1997) Qualit de leau - Dosage des hydrocarbures halogns hautement volatils -
17、 Mthodes par chromatographie en phase gazeuse (IS0 10301 : 1997) Wasserbeschaffenheit - Bestimmung leichtflchtiger halogenierter Kohlen- Wasserstoffe - Gaschromatographische Verfahren (IS0 10301 : 1997) This European Standard was approved by CEN on 1997-03-28. CEN members are bound to comply with th
18、e CENLENELEC Internal Regulations which stipulate the conditions 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 Central Secretariat or
19、 to any CEN member. The European Standards exist 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 Central Secretariat has the same status as the official versio
20、ns. CEN members are the national standards bodies of Austria, Belgium, the Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, the Netherlands, Norway, Portugal, Spain, Sweden, Switzerland, and the United Kingdom. CEN European Committee for Standardization
21、 Comit Europen de Normalisation Europisches Komitee fr Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels O 1997. CEN - All rights of exploitation in any form and by any means reserved worldwide for CEN national members. Ref. No. EN IS0 10301 : 1997 E Page 2 EN IS0 10301 : 1997 Forewor
22、d International Standard IS0 10301 : 1997 which was prepared by ISO/TC 147 Water quality of the International Organization for Standardization, has been adopted by Technical Committee CEN/TC 230 Water analysis, the Secretariat of which is held by DIN, as a European Standard. This European Standard s
23、hall be given the status of a national standard, either by publication of an identical text or by endorsement, and conflicting national standards withdrawn, by October 1997 at the latest. In accordance with the CENLENELEC Internal Regulations, the national standards organizations of the following co
24、untries are bound to implement this European Standard: Austria, Belgium, the Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, the Netherlands, Norway, Portugal, Spain, Sweden, Switzerland, and the United Kingdom. Water quality - Determination of highly
25、volatile halogenated hydrocarbons - Gas-chromatographic methods, Endorsement notice The text of the International Standard IS0 10301 :1997 was approved by CEN as a European Standard without any modification. Contents SECTION 1: General 1.1 Scope 1.2 Normative references 1.3 Definition SECTION 2: Liq
26、uid/liquid extraction and analysis by gas chromatography 2.1 Principle 2.2 Interferences 2.3 Reagents 2.4 Apparatus 2.5 Sampling and sample preparation 2.6 Procedure 2.7 Calibration 2.8 Identification and evaluation 2.9 Expression of results 2.10 Precision data 2.11 Test report 7 7 7 7 9 11 11 14 19
27、 21 22 23 SECTION 3: Static headspace method and analysis by gas chromatography 3.1 Principle 3.2 Interferences 3.3 Reagents 3.4 Apparatus 3.5 Sampling 3.6 Procedure 3.7 Calibration 3.8 Identification and evaluation 3.9 Expression of results 3.10 Precision data 3.11 Test report Annex A (informative)
28、 Characteristics of highly volatile halogenated hydrocarbons Annex B (informative) Examples of gas chromatograms for highly volatile halogenated hydrocarbons Annex C (informative) Example of a microseparator Annex D (informative) Sensitivity of electron-capture detector Annex E (informative) Extract
29、ion recovery with pentane Annex F (informative) Qualitative method for testing the quality of “penicillin type“ stoppers Annex G (informative) Collection of samples Page 3 EN IS0 10301 : 1997 24 24 24 24 24 25 26 28 31 33 33 34 35 41 45 46 47 4% 49 Introduction Highly volatile halogenated hydrocarbo
30、ns are used in industrial, commercial and domestic fields, and can enter a water body via waste water and may consequently contaminate drinking water. Furthermore, they can originate from the use of chlorine as an oxidizing agent in water and waste-water treatment. They also can be introduced by ina
31、ppropriate handling. In addition, they can be formed by decomposition of higher molecular mass organohalogen derivatives. In uncontaminated ground water and rain water, the concentrations of halogenated hydrocarbons are generally below 0,l pg/I. In surface water they may be higher, depending on the
32、origin and quality of the water. In untreated waste water the concentrations may reach saturation of the aqueous phase. In general, the solubility of these compounds in organic solvents and in fatty material exceeds their solubility in water. Page 4 EN IS0 10301 : 1997 Compound Section 1 : General Q
33、uantification limits ua/l 1.1 Scope I 1,1,2.2-Tetrachloroethane 10.05 - 0.1 I This International Standard specifies two methods for the determination of highly volatile halogenated hydrocarbons using gas chromatography. Dichloromethane C h loroform Carbon tetrachloride Ill-Dichloroethane 1,2-Dichior
34、oethane 1,l ,I -Trichloroethane Section 2 specifies a method for the determination by liquid/liquid extraction of highly volatile halogenated hydrocarbons in drinking water, ground water, swimming pool water, most rivers and lakes and many sewage and industrial effluents. Typical values of “quantifi
35、cation limits are given in table 1. 50 0,05 - 0,3 0,Ol - 0,l 1,o - 5 5- 10 0.02 - 0.1 Hexachloroethane cis- 1 , 2-0 ich I oro et h y I e n e trans- 1 ,2-D i c h I oro et h y I e n e Trichloroethylene Tetrachloroethylene Hexachlorobutadiene 0,Ol - 0,05 5 - 50 1-10 0,05 - 0,l o, 1 0.01 Tribromomethane
36、 I Oll 1 .I .2-Trichlorotrifluoroethane 10.1 Section 3 specifies a method for the determination of highly volatile halogenated hydrocarbons in drinking water, surface waters and ground water by a static head- space method. Typical values of “quantification limits“ are given in table 2. In practise,
37、the head-space method is applicable for industrial effluents as a screening method, but in some cases it is necessary to confirm the result by the liquid-liquid extraction method. NOTE : When applying this International Standard, the guide on analytical quality control for water analysis (see ISO/TR
38、 13530) should be followed, especially for the calibration steps. Page 5 EN IS0 10301 : 1997 Com pound Dichlo romet hane C h I oroform Carbon tetrachloride 1,l -Dich loroethane 1,2-Dichloroethane Quantification limits cidl 50 0,3 o, 1 1 O0 1 O0 I 1.1 ,l-Trichloroethane 10.1 I 1,1,2-Trichloroethane 1
39、,l-Dichloroethylene cis- 1,2- Dich I o roet h y I en e trans- 1,2 - D ich I or o et h y I en e Trichloroethylene Tetrachloroethylene 1,2-Dichloropropane 20 10 50 25 02 o, 2 50 I 1,3-Dichlororoane I200 I Di bromomethane Tri bromomethane (Bromoform) 1,2-Di bromoethane Bromoc h I oromet ha ne Bromodich
40、loromethane I Dibromochloromethane I cis+trans-l.3-Dichlororovlene I 10 I 0,3 5 2 1 02 0.3 I 1,1.3-Trifluoroethane II I 1.2 Normative references The following standards contain provisions which, through reference in this text, constitute provisions of this International Standard. At the time of publ
41、ication, the editions indicated were valid. All standards are subject to revision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most recent editions of the standards indicated below. Members of IEC and IS0 maintain regis
42、ters of currently valid International Standards. IS0 5667-1:1980, Water quality - Sampling - Part 1 : Guidance on the design of Sam pl i ng program mes IS0 5667-2:1991, Water quality - Sampling - Part 2 : Guidance on sampling techniques ISOR 13530:- Water quality - Guide to analytical quality contro
43、l for water a na lysis 1) In preparation. Page 6 EN IS0 10301 : 1997 1.3 Definition For the purposes of this International Standard, the following definition applies 1.3.1 highly volatile halogenated hydrocarbons: Fluorinated, chlorinated, brominated and/or iodinated mainly nonaromatic hydrocarbons
44、composed of one to six atoms of car bon. NOTE Their boiling points generally fall within the range of 20 “C to 220 “C at atmospheric pressure (see annex A). Page 7 EN IS0 10301 : 1997 Section 2 : Liquid/liquid extraction and analysis by gas chromatography 2.1 Principle The highly volatile halogenate
45、d hydrocarbons are extracted into an organic solvent. The solution is then analysed by gas chromatography with an electron-capture detector or any other suitable detector. 2.2 Interferences Interferences can be due to the sampling procedure, vials and stoppers, solvents, gases, organic compounds in
46、the laboratory atmosphere and contamination from the autosampler. Procedures for minimizing contamination are given in 2.5 and 2.6. 2.3 Reagents All reagents shall be of sufficient purity so as to not give rise to significant interfering peaks in the gas chromatogram of the solvent extract. The puri
47、ty of reagents shall be verified by a suitable procedure, for example, by blank determinations (see 2.6.4). Reagents can become contaminated by contact with air and other materials, particularly plastics, or by degradation caused by the action of light. Store all reagents in the dark in tightly seal
48、ed all-glass containers or other suitable vessels. 2.3.1 Water for the preparation of calibration solutions and blank The quality of the water used shall be determined. For example, use the following procedure as a suitable preparation method : Place water in a bottle with a conical shoulder, nomina
49、l capacity 2 litres, fitted with a ground-glass stopper, pretreated according to 2.4.2. Determine the content of the highly volatile halogenated hydrocarbons in this water If the water is contaminated, purify as follows : - position a glass delivery tube with a sintered glass distributor a few millimetres above the bottom of the bottle ; - heat the water to approximately 60 “C ; - pass a stream of clean nitrogen (approximately 150-200 ml/min) through the water for 1 h via the bubbler. Let the water cool to room temperature and stopper the bottle ; - store the wa
