1、BSI Standards PublicationBS EN 16693:2015Water quality Determinationof organochlorine pesticides(OCP) in whole water samples Method using solid phaseextraction (SPE) with SPE-disks combined with gaschromatography massspectrometry (GC-MS)BS EN 16693:2015 BRITISH STANDARDNational forewordThis British
2、Standard is the UK implementation of EN 16693:2015.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 beobtained on request to its secretary.This publication does not
3、purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2015.Published by BSI Standards Limited 2015ISBN 978 0 580 84519 2ICS 13.060.50Compliance with a British Standard cannot confer immunity fromlegal obligat
4、ions.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 30 September 2015.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS EN 16693:2015EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16693 September 2015 ICS 13.0
5、60.50 English Version Water quality - Determination of organochlorine pesticides (OCP) in whole water samples - Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography mass spectrometry (GC-MS) Qualit de leau - Dosage des pesticides organochlors (POC) dans la totali
6、t de lchantillon deau - Mthode par extraction en phase solide (SPE) avec disques SPE, avec couplage chromatographie en phase gazeuse-spectromtrie de masse (CG-SM) Wasserbeschaffenheit - Bestimmung von Organochlorpestiziden (OCP) in Gesamtwasserproben - Verfahren mittels Festphasenextraktion (SPE) mi
7、t SPE-Disks in Verbindung mit Gaschromatographie - Massenspektrometrie (GC-MS) This European Standard was approved by CEN on 27 June 2015. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a nation
8、al 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 exists in three official versions (English, French, German). A versi
9、on 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 standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Cz
10、ech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. E
11、UROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16693:2015 EB
12、S EN 16693:2015EN 16693:2015 (E) 2 Contents Page European foreword . 3 Introduction 4 1 Scope 5 2 Normative references 7 3 Principle . 7 4 Interferences 7 4.1 Interferences with sampling and extraction . 7 4.2 Interferences with GC-MS . 8 5 Reagents . 8 6 Apparatus . 9 7 Sampling 10 8 Procedure 10 8
13、.1 Sample preparation and extraction 10 8.2 Extraction by SPE-disks . 11 8.3 Solvent concentrating . 11 8.4 Gas chromatography . 12 8.5 Identification of individual compounds by means of GC-MS 12 8.6 Blank value measurements 12 9 Calibration 13 9.1 General requirements 13 9.2 Calibration of the GC-s
14、tep . 14 9.3 Calibration of the total procedure using the internal standard 14 9.4 Determination of procedural recovery values 15 10 Calculation of the results . 16 11 Expression of results . 17 12 Test report 17 Annex A (informative) Suitable gas chromatographic conditions and example chromatograms
15、 GC-conditions of example chromatograms in Figure A.1 18 Annex B (informative) Repeatability and reproducibility data . 23 Annex C (informative) Examples of suitable SPE-disks . 27 Annex D (informative) Examples of internal standards . 28 Bibliography . 29 BS EN 16693:2015EN 16693:2015 (E) 3 Europea
16、n foreword This document (EN 16693:2015) has been prepared by Technical Committee CEN/TC 230 “Water analysis”, the secretariat of which 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
17、 by March 2016, and conflicting national standards shall be withdrawn at the latest by March 2016. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. Attention is drawn to the possibility that some of the elements of this
18、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 organisations of the following countries are bound to implement this European Standa
19、rd: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spai
20、n, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16693:2015EN 16693:2015 (E) 4 Introduction WARNING Persons using this European Standard should be familiar with usual laboratory practice. This European Standard does not purport to address all of the safety problems, if any, associated wi
21、th 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 according to this European Standard be carried out by suitably trained sta
22、ff. Organochlorine pesticides (OCP) are priority substances listed in Annex X of the EU Water Framework Directive (WFD, Directive 2000/60/EC) for which environmental quality standards (EQS) have been set at EU level for inland waters as well as other surface waters to protect the aquatic environment
23、 against chemical pollution (Directive 2008/105/EC). With the exception of metals, the EQSs are expressed as total concentrations in the whole water sample. Furthermore, analytical methods used in WFD monitoring need to meet certain requirements as regards the minimum limit of quantification and the
24、 maximum tolerable measurement uncertainty (Directive 2009/90/EC). So far, there is no European-wide standardized method available for the determination of OCP in whole water samples fulfilling those requirements. Hence, the European Commission mandated CEN to develop or improve standards in support
25、 of the implementation of the monitoring requirements of WFD. Directive 2008/105/EC has been amended by Directive 2013/39/EU, however this standard has been developed for the analysis of OCP as listed in Annex A of Directive 2008/105/EC. The priority substances list in Annex X of the WFD includes va
26、rious OCPs such as alachlor, endosulfan, hexachlorobenzene, hexachlorocyclohexane isomers, pentachlorobenzene, aldrin, dieldrin, endrin, isodrin, DDT and its metabolites. Annual average environmental quality standards (AA-EQS) values for individual OCP range from 0,000 5 g/l to 0,3 g/l and are defin
27、ed for the concentration in the whole water sample, including suspended particulate matter (SPM) present in the sample. As long as compounds such as OCP, in particular the larger molecular weight ones, sorb strongly to environmental solids, the fraction bound to particles may be substantial. Therefo
28、re it is important to be able to handle whole water samples within the analytical process. Identification and quantification of OCP at trace level concentrations often require both high sensitive chromatographic equipment and effective enrichment steps. BS EN 16693:2015EN 16693:2015 (E) 5 1 Scope Th
29、is European Standard specifies a method for the determination of selected organochlorine pesticides (OCP) (see Table 1), in water samples. The method uses solid-phase extraction with SPE-disks followed by gas chromatography-mass spectrometry (GC-MS). It is applicable to the analysis of OCPs in surfa
30、ce water containing suspended particulate matter (SPM) up to 500 mg/l (whole water samples), drinking water and groundwater. The lower limit of the working range depends on the matrix, on the specific compound to be analyzed and on the sensitivity of the mass spectrometric detection unit. For compou
31、nds listed in Table 1 the limit of determination (LOQ) is at least 30 % of the corresponding AA-EQS value (0,000 15 g/l to 0,1 g/l) according to the requirements of the European Quality Standards Directive (Directive 2008/105/EC) for both inland surface waters and other surface waters. This method m
32、ay be used for the analysis of other OCPs not listed in Table 1 or other types of water. However, it is important to verify its applicability before use. BS EN 16693:2015EN 16693:2015 (E) 6 Table 1 Organochlorine pesticides (OCP) determined by this method Substance Molecular formula Molar mass EC Nu
33、mber aCAS RN bg/mol Alachlor C14H20ClNO2269,77 2401108 15972608 Cyclodiene pesticides: Aldrin Dieldrin Endrin Isodrin C12H8Cl6C12H8Cl6O C12H8Cl6O C12H8Cl6364,91 380,91 380,91 364,91 2062158 2004845 2007757 2073662 309002 60571 72208 465736 DDT-total: op-DDT pp-DDT pp-DDD pp-DDE C14H9Cl5C14H9Cl5C14H9
34、Cl4C14H9Cl4354,49 354,49 320,04 318,03 2123325 2000243 2007830 2007846 789026 50293 72548 72559 Hexachlorobenzene (HCB) C6Cl6284,80 2042739 118741 Hexachlorobutadiene (HCBD) C4Cl6260,76 2017655 87683 Hexachlorocyclohexane c: alpha-HCH beta-HCH delta-HCH gamma-HCH C6H6Cl6C6H6Cl6C6H6Cl6C6H6Cl6290,83 2
35、90,83 290,83 290,83 2062708 2062713 2062729 2004012 319846 319857 319868 58899 Pentachlorobenzene C6HCl5250,34 2101720 608935 Trichlorobenzene c: 1,2,3-TCB 1,2,4-TCB 1,3,5-TCB C6H3Cl3C6H3Cl3C6H3Cl3181,45 181,45 181,45 2017571 2044280 2036086 87616 120821 108703 Endosulfan c: Endosulfan-I (alpha) End
36、osulfan-II (beta) C9H6Cl6O3S C9H6Cl6O3S 406,93 406,93 959988 33213659 aEC Number: European inventory of existing commercial substances (EINECS) or European list of notified chemical substances (ELINCS). bCAS RN: Chemical Abstracts Service Registry Number. cMixture of isomers. BS EN 16693:2015EN 1669
37、3:2015 (E) 7 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (includ
38、ing any amendments) applies. EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) EN ISO 5667-3, Water quality - Sampling - Part 3: Preservation and handling of water samples (ISO 5667-3) 3 Principle Organochlorine pesticides present in the whole water sample
39、are extracted by means of solid-phase extraction using solid-phase extraction disks (SPE-disks). Samples shall not be filtered. An internal standard mixture is added to the sample prior to extraction. Extraction by SPE-disks is a fully automatable procedure. It includes a combined extraction of both
40、 the analytes dissolved in the liquid phase of the sample and those adsorbed to the suspended particulate matter. The latter is extracted within the elution step of the procedure. The extract is concentrated by evaporation and the analytes are separated, identified and quantified by capillary gas ch
41、romatography with mass spectrometric detection (GC-MS) using electron impact (EI) ionization mode. The compounds endosulfan-I (alpha) and endosulfan-II (beta) may require additional efforts on either enlargement of sample enrichment and/or large volume injection (LVI) of sample extract. Enlargement
42、of sample enrichment can be achieved by using 2 000 ml sample volume and/or an evaporation of solvent extracts down to a final volume of 0,2 ml or 0,1 ml. 4 Interferences 4.1 Interferences with sampling and extraction To avoid interferences, collect samples according to Clause 7. Sample containers s
43、hall consist of materials that do not alter the sample during the contact time. Plastics and other organic materials shall be avoided during sampling or sample storage. Commercially available SPE-disks can differ frequently in quality. Variations in the selectivity of the materials can occur from ba
44、tch to batch, and therefore might cause significant deviations in the extraction yield. This does not basically impair their suitability, apart from a resulting higher detection limit of individual substances. To ensure that the measuring results have a high accuracy and precision, use materials of
45、one batch for both measurement and calibration. Avoid major fluctuations in the extraction times and elution procedures within one sample sequence when analyzing the samples. Make sure that the disk is effectively dried. This can be achieved by using e.g. a vacuum device equipped with a device to dr
46、y a stream of nitrogen or air before it is applied to the disk. If the vacuum based automated or manually driven equipment uses ambient air from the laboratory environment, which often contains a certain degree of humidity, drying of the disk is, depending from the moisture content of the air, not e
47、ffective and often results in a high amount of residual water in the disk (e.g. 200 l). Therefore additional drying of air before it is applied to the disk is required, e.g. by integration of a drying flask containing calcium chloride (5.9) or another drying agent (desiccant). This procedure results
48、 in very effectively dried disks with low remaining water ( 70 % and up to 120 % are usually achieved. Low or unstable recoveries indicate matrix effects or difficulties during extraction. 10 Calculation of the results Calculate the mass concentration igof substance i in the water sample according t
49、o Formula (5), taking into account Formula (2) using the internal standard I. gIgIgg IgIgiiiiybym= (5) where igis the mass concentration of the target substance i in the water sample, in micrograms per litre (g/l); yigis the measured value of the target substance i in the water sample, e.g. in area units; yIgis the measured value of internal standard I in the water sample, the unit depending on the evaluation, e.g. area unit; Igis the mass concentration of inte
