1、BSI Standards PublicationPD CEN/TS 16692:2015Water quality Determinationof tributyltin (TBT) in wholewater samples Methodusing solid phase extraction(SPE) with SPE disks and gaschromatography with triplequadrupole mass spectrometryPD CEN/TS 16692:2015 PUBLISHED DOCUMENTNational forewordThis Publishe
2、d Document is the UK implementation of CEN/TS16692:2015.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
3、 not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2015. Published by BSI StandardsLimited 2015ISBN 978 0 580 84470 6ICS 13.060.50Compliance with a British Standard cannot confer immunity fromlegal ob
4、ligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 30 April 2015.Amendments issued since publicationDate Text affectedPD CEN/TS 16692:2015TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 16692 April 2015
5、ICS 13.060.50 English Version Water quality - Determination of tributyltin (TBT) in whole water samples - Method using solid phase extraction (SPE) with SPE disks and gas chromatography with triple quadrupole mass spectrometry Qualit de leau - Dosage du tributyltain (TBT) dans la totalit des chantil
6、lons deau - Mthode par extraction sur phase solide (SPE) avec disques SPE et chromatographie en phase gazeuse avec spectromtrie de masse triple quadruple Wasserbeschaffenheit - Bestimmung von Tributylzinn (TBT) in Gesamtwasserproben - Verfahren mittels Festphasenextraktion (SPE) mit SPE-Disks und Ga
7、schromatographie mit Triple-Quadrupole Massenspektrometrie This Technical Specification (CEN/TS) was approved by CEN on 1 April 2014 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit
8、their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It is permissi
9、ble to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
10、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 and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDI
11、ZATION 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. CEN/TS 16692:2015 EPD CEN/TS 16692:2015CEN/TS 1
12、6692:2015 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Normative references 5 3 Principle 5 4 Interferences 5 5 Reagents .6 6 Apparatus .8 7 Sampling .9 8 Procedure .9 8.1 Sample preparation .9 8.2 Derivatization .9 8.2.1 General 9 8.2.2 Derivatization procedure 10 8.3 Extraction with
13、SPE-disks . 10 8.4 Clean-up of the extract . 11 8.5 Solvent concentration step 11 8.6 Gas chromatograph 11 8.7 Identification of individual compounds by GC-MS . 11 8.8 Blank value measurements . 12 9 Calibration . 12 9.1 General requirements . 12 9.2 Calibration of the GC-step . 13 9.3 Calibration o
14、f the total procedure using the internal standard . 14 9.4 Determination of procedural recovery values . 15 9.5 Determination of derivatization standard recovery . 15 10 Calculation . 16 11 Expression of results . 17 12 Test report . 17 Annex A (informative) Suitable gas chromatographic conditions a
15、nd example chromatograms . 18 Annex B (informative) Repeatability and reproducibility data . 20 Annex C (informative) Example of conditions for automated solid-phase extraction 21 Annex D (informative) Silica clean-up 22 D.1 Silica for the clean-up column . 22 D.2 Clean-up column . 22 D.3 Eluent for
16、 cleaning extract . 22 D.4 Clean-up of extract . 22 Bibliography . 23 PD CEN/TS 16692:2015CEN/TS 16692:2015 (E) 3 Foreword This document (CEN/TS 16692:2015) has been prepared by Technical Committee CEN/TC 230 “Water analysis”, the secretariat of which is held by DIN. Attention is drawn to the possib
17、ility that 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. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade As
18、sociation, and supports essential requirements of the Water Framework Directive (WFD, 2000/60/EC), and the Directive on Environmental Quality Standards (Directive 2008/105/EC). According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are boun
19、d to announce this Technical Specification: 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, Por
20、tugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. WARNING Persons using this Technical Specification should be familiar with usual laboratory practice. This Technical Specification does not purport to address all of the safety problems, if any, associated
21、 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 according to this Technical Specification be carried out by suitably tr
22、ained staff. PD CEN/TS 16692:2015CEN/TS 16692:2015 (E) 4 Introduction Tributyltin (TBT) is a priority substance 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 as well as other surf
23、ace waters to protect the aquatic environment 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 regard
24、s the minimum limit of quantification and the maximum tolerable measurement uncertainty (Directive 2009/90/EC). So far, there is no standardized method available for the determination of TBT in whole water samples fulfilling those requirements. Hence, the European Commission mandated CEN to develop
25、or improve standards in support 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 TBT as listed in Annex A of Directive 2008/105/EC. The annual average environmenta
26、l quality standard (AA-EQS) value for TBT is 0,0002 g/l and is defined for the concentration in the whole water sample, including suspended particulate matter (SPM) present in the sample. As compounds like TBT, sorb strongly to environmental solids, the fraction bound to particles may be substantial
27、. Therefore it is important to be able to handle whole water samples within the analytical process. Identification and quantification of TBT at trace level concentrations often require both high sensitive chromatographic equipment and effective enrichment steps. PD CEN/TS 16692:2015CEN/TS 16692:2015
28、 (E) 5 1 Scope This Technical Specification specifies a method for the determination of tributyltin cation (TBT) in whole water samples. It is applicable to the analysis of TBT in surface water, which may contain suspended particulate matter (SPM) up to 500 mg/l (whole water samples), groundwater, d
29、rinking water and seawater. The working range is 0,04 ng/l to 20 ng/l. The LOQ will be mainly determined by the blank value obtained during validation of this method. NOTE 1 The method has been successfully applied to seawater samples during method development, but sea water samples were not include
30、d in the interlaboratory comparison. NOTE 2 In this document TBT is synonymous for tributyltin cation. NOTE 3 Near the lower limit of the working range the measurement uncertainties may be higher. 2 Normative references The following documents, in whole or in part, are normatively referenced in this
31、 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 (including any amendments) applies. EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO
32、3696) EN ISO 5667-3, Water quality - Sampling - Part 3: Preservation and handling of water samples (ISO 5667-3) 3 Principle TBT in the whole water sample is derivatized while stirring thoroughly. The derivatized target analyte is extracted using solid phase extraction with SPE disks and subsequently
33、 concentrated by evaporation. An aliquot of the extract is brought on the gas chromatograph with programmed temperature vaporizing - large volume injection (PTV-LVI) and identified and quantified with a triple quadrupole mass spectrometric detection in single GC-MS reaction mode. Water samples of 1
34、l are spiked with internal standards and brought to pH 4 to pH 5 with a sodium acetate buffer. Subsequently, TBT is ethylated by adding sodium tetra ethylborate (NaEt4B) to the water samples, while rigorously stirring. Solid phase disk extraction is used for extracting ethylated TBT with mainly hexa
35、ne as a solvent. The extract is then brought to pH 12 with sodium hydroxide 1. The final extract is then concentrated to 300 l. A volume of 20 l is injected into the gas chromatograph using a PTV-LV injection technique followed by GC-MS/MS in single GC-MS reaction mode for separation and detection.
36、A deuterium-labelled TBT substance is used as internal standard for quantification of TBT. A TBT-spiking solution is used for the determination of procedural recovery values. A tri-alkylated spiking solution is used for checking the efficiency of the alkylation process and is added to each sample. T
37、etra-alkylated reference solutions are used for the calibration. 4 Interferences The reagents can contain impurities of organotin compounds, including the derivatization reagent. It is absolutely essential to verify contamination before use by analysis of blanks. Glassware can become contaminated. H
38、eat all used glassware to 450 C, or clean the glassware with a 10 % (volume fraction) nitric acid solution before use, by decontamination overnight. Make sure the GC-system is not contaminated. Regularly refresh the wash solvents to ensure that no contamination occurs via the injection needle. Verif
39、y the GC-system before analysis by analysis of blank solvent. Commercially available solid-phase extraction disks (SPE-disks) differ frequently in quality. Variations in the selectivity of the materials also frequently occur from batch to batch, thus possibly causing significant PD CEN/TS 16692:2015
40、CEN/TS 16692:2015 (E) 6 deviations in 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 show high trueness and precision, use materials of one batch for both measurement and
41、 calibration. Avoid major fluctuations in the extraction times and elution procedures within one sample sequence when analysing the samples. SPE - disks may be contaminated with mono-, di- or tributyltin cation compounds. Verify the contamination of the disks before use. Pre-cleaning can be achieved
42、 by pre-extracting the disks with a derivatization agent. To thoroughly clean magnetic stirrers, they can be shaken in a methanol-hexane solution (9:1, v/v) with 1 ml of 2 % derivatization agent. Decontaminate overnight and rinse three times with deionized water. 5 Reagents The reagents shall be fre
43、e from impurities possibly interfering 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 reagents use, as far as available “residual grade” or better in order to obtain low bla
44、nks. Verify by blank determinations and, if necessary, apply additional cleaning steps. 5.1 Water, Grade 1 according to EN ISO 3696. 5.2 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.
45、 minimum 99,996 % by volume, for concentration by evaporation. 5.4 Solvents for extraction, chromatography and preparation of reference solutions. hexane, C6H14, (boiling point: 69 C); iso-octane, C8H18(boiling point: 99 C); iso-propanol, C3H7OH (boiling point: 82 C); methanol, CH3OH (boiling point:
46、 65 C). 5.5 Acetate buffer solution, solution, c(CH3COONa) = 4 mol/l. 5.6 Sodium hydroxide, solution, c(NaOH) = 10 mol/l. 5.7 Hydrochloric acid, w(HCl) = 36 % to 38 % mass fraction. 5.8 Nitric acid, v(HNO3) = 10 % volume fraction. 5.9 Aluminium oxide, activated at 800 C for 4 h, (10 2) % deactivated
47、. 5.10 Sodiumtetraethylborate, w(NaEt4B) = 2 % mass fraction, (CAS Registry Number 15523-24-7). 5.11 Reference ethyl-TBT stock solution This substance is used for the calibration. Use a commercially available solution, e. g. in iso-octane or the commercially available pure substance (Table 1). The s
48、tock solution is prepared by dissolving, e. g. 5 mg of the reference substance (precision of 0,001 mg) in 20 g of an appropriate solvent (precision of 0,01 g) e. g. hexane or iso-octane. Store stock solutions at temperatures between 1 C and 5 C, protected from light. Stock solutions with concentrati
49、ons 1 mg/g are stable for at least 12 months and at least 3 months for concentrations 1 g/g. PD CEN/TS 16692:2015CEN/TS 16692:2015 (E) 7 5.12 Reference TBT stock solution This substance is used for spiking water samples for determination of procedural recovery values. Use a commercially available solution of TBT, e. g. TBT-chloride in iso-octane or the commercially available pure substance (Table 1). Stock solution is prepared as described in 5.11, with e. g. iso-propanol or methanol as solvent. Stock solutions with concentrations 1 mg/g are
