CEN/TS 16692:2015

SLOVENSKI STANDARD
01-junij-2015
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Water quality - Determination of tributyl tin (TBT) in whole water samples using solid
phase extraction (SPE) and gas chromatography with triple quadrupole mass
spectrometry
Wasserbeschaffenheit - Bestimmung von Tributylzinn (TBT) in Gesamtwasserproben
mittels Festphasenextraktion (SPE) und Gaschromatographie mit Triple-Quadrupol-
Massenspektrometrie
Qualité de l'eau - Dosage du tributylétain (TBT) dans des échantillons d'eau totale par
extraction sur phase solide (SPE) et chromatographie en phase gazeuse avec
spectrométrie de masse triple quadrupôle
Ta slovenski standard je istoveten z: CEN/TS 16692:2015
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL SPECIFICATION
CEN/TS 16692
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
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
Qualité de l'eau - Dosage du tributylétain (TBT) dans la Wasserbeschaffenheit - Bestimmung von Tributylzinn (TBT)
totalité des échantillons d'eau - Méthode par extraction sur in Gesamtwasserproben - Verfahren mittels
phase solide (SPE) avec disques SPE et chromatographie Festphasenextraktion (SPE) mit SPE-Disks und
en phase gazeuse avec spectrométrie de masse triple Gaschromatographie mit Triple-Quadrupole
quadrupôle 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 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 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 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 and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR 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 Ref. No. CEN/TS 16692:2015 E
worldwide for CEN national Members.

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 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 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 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-up column . 22
D.3 Eluent for cleaning extract . 22
D.4 Clean-up of extract . 22
Bibliography . 23

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 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 and 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 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, Netherlands, 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 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 be carried out by suitably trained staff.
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 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 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 Commission 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.
The annual average environmental quality standard (AA-EQS) value for TBT is 0,0002 μg/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. 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.
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, 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 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 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 - 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
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 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.
Wa
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