1、BSI Standards Publication PD CEN/TS 16692:2015 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 spectrometryPD CEN/TS 16692:2015 PUBLISHED DOCUMENT National foreword Thi
2、s Published Document is the UK implementation of CEN/TS 16692:2015. The UK participation in its preparation was entrusted to Technical Committee EH/3/2, Physical chemical and biochemical methods. A list of organizations represented on this committee can be obtained on request to its secretary. This
3、publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2015. Published by BSI Standards Limited 2015 ISBN 978 0 580 84470 6 ICS 13.060.50 Compliance with a British Standard cannot confer
4、 immunity from legal obligations. This Published Document was published under the authority of the Standards Policy and Strategy Committee on 30 April 2015. Amendments issued since publication Date Text affectedPD CEN/TS 16692:2015TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATI
5、ON CEN/TS 16692 April 2015 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)
6、dans la totalit des chantillons 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
7、 (SPE) mit SPE-Disks und Gaschromatographie 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 w
8、ill be requested to submit 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 appro
9、priate form. It is permissible 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 R
10、epublic, 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 and United Kingdom. EUROP
11、EAN 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. CEN/TS 16692:2015 EP
12、D CEN/TS 16692:2015 CEN/TS 16692:2015 (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 proce
13、dure 10 8.3 Extraction with 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
14、-step . 13 9.3 Calibration of 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
15、chromatographic conditions and 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-u
16、p column . 22 D.3 Eluent for cleaning extract . 22 D.4 Clean-up of extract . 22 Bibliography . 23 PD CEN/TS 16692:2015 CEN/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. Att
17、ention is drawn to the possibility 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 a
18、nd the European Free Trade Association, 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
19、 following countries are bound 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, Net
20、herlands, Norway, Poland, Portugal, 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
21、 problems, if any, associated 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
22、be carried out by suitably trained staff. PD CEN/TS 16692:2015 CEN/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 fo
23、r inland as well as other surface 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
24、certain requirements as regards 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 Commi
25、ssion mandated CEN to develop 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. T
26、he annual average environmental 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 t
27、o particles may be substantial. 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/
28、TS 16692:2015 CEN/TS 16692:2015 (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
29、 water samples), groundwater, drinking 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
30、 water samples were not included 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
31、 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 (including any amendments) applies. EN ISO 3696, Water for analytical laboratory use - Speci
32、fication 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 TBT in the whole water sample is derivatized while stirring thoroughly. The derivatized target analyte is extracted using solid phase extraction
33、with SPE disks and subsequently 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 rea
34、ction mode. Water samples of 1 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 (NaEt 4 B) to the water samples, while rigorously stirring. Solid phase disk extraction is used for extracti
35、ng ethylated TBT with mainly hexane 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 mo
36、de for separation and detection. 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 proce
37、ss and is added to each sample. Tetra-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. Gla
38、ssware can become contaminated. Heat 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 occur
39、s via the injection needle. Verify 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
40、 significant PD CEN/TS 16692:2015 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
41、one batch for both measurement and 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
42、 use. Pre-cleaning can be achieved 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
43、Reagents The reagents shall be free 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
44、 better in order to obtain low blanks. 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.
45、 5.3 Nitrogen of high purity, i.e. minimum 99,996 % by volume, for concentration by evaporation. 5.4 Solvents for extraction, chromatography and preparation of reference solutions. hexane, C 6 H 14 , (boiling point: 69 C); iso-octane, C 8 H 18(boiling point: 99 C); iso-propanol, C 3 H 7 OH (boiling
46、point: 82 C); methanol, CH 3 OH (boiling point: 65 C). 5.5 Acetate buffer solution, solution, c(CH 3 COONa) = 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(HNO 3 ) = 10 % volume fraction. 5.9 Aluminium oxid
47、e, activated at 800 C for 4 h, (10 2) % deactivated. 5.10 Sodiumtetraethylborate, w(NaEt 4 B) = 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 c
48、ommercially available pure substance (Table 1). The stock 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, p
49、rotected from light. Stock solutions with concentrations 1 mg/g are stable for at least 12 months and at least 3 months for concentrations 1 g/g. PD CEN/TS 16692:2015 CEN/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 s
