Sludge, treated biowaste and soil - Determination of dioxins and furans and dioxin-like polychlorinated biphenyls by gas chromatography with high resolution mass selective detection (HR GC-MS)

This Technical Specification specifies a method for quantitative determination of 17 2,3,7,8-chlorine substituted dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls in sludge, treated biowaste and soil using liquid column chromatographic clean-up methods and GC/HRMS.
The analytes to be determined with this Technical Specification are listed in Table 2.
(...)
The limit of detection depends on the kind of sample, the congener, the equipment used and the quality of chemicals used for extraction and clean-up. Under the conditions specified in this Technical Specification, limits of detection better than 1 ng/kg (expressed as dry matter) can be achieved.
This method is "performance based". It is permitted to modify the method if all performance criteria given in this method are met.
NOTE   In principle this method can also be applied for sediments, mineral wastes and for vegetation. It is the responsibility of the user of this Technical Specification to validate the application for these matrices.

Schlamm, behandelter Bioabfall und Boden - Bestimmung von Dioxinen und Furanen sowie Dioxin vergleichbaren polychlorierten Biphenylen mittels Gaschromatographie und hochauflösender massenspektrometrischer Detektion (HR GC-MS)

Diese Technische Spezifikation legt ein Verfahren fest zur quantitativen Bestimmung von
17 2,3,7,8-chlorsubstituierten Dibenzo-p-dioxinen und Dibenzofuranen sowie dioxinähnlichen polychlorierten
Biphenylen in Schlamm, Bioabfall und Boden mittels flüssigchromatographischer Reinigungsverfahren und
GC/HRMS.
Die nach dieser Technischen Spezifikation bestimmbaren Analyten enthält Tabelle 1.
Die Nachweisgrenze hängt von der Art der Probe, vom Kongener, von den verwendeten Geräten und von der
Qualität der zur Extraktion und zur Reinigung verwendeten Chemikalien ab. Nach den in dieser Technischen
Spezifikation festgelegten Qualitätsanforderungen können Nachweisgrenzen erreicht werden, die besser als
1 ng/kg (Trockenmasse) sind.
Dieses Verfahren ist „leistungsbasiert“. Es ist zulässig, das Verfahren abzuändern, wenn alle für dieses
Verfahren angegebenen Leistungskriterien erfüllt sind.
ANMERKUNG Grundsätzlich kann dieses Verfahren auch auf Sedimente, mineralische Abfälle und Pflanzen
angewendet werden. Der Anwender dieser Technischen Spezifikation ist dafür verantwortlich, die Anwendung für diese
Matrizes zu validieren. Für Messungen komplexer Matrizes, wie z.B. an Pflanzen adsorbierte Flugasche, kann eine
erweiterte Reinigung erforderlich sein. Dies kann auch für Sedimente und mineralische Abfälle zutreffen.

Boues, biodéchets traités et sols - Détermination des dioxines et furanes et polychlorobiphényles de type dioxine par chromatographie en phase gazeuse avec spectrométrie de masse à haute résolution (CG-SMHR)

La présente Spécification technique définit une méthode pour la détermination quantitative de 17 polychlorodibenzo p dioxines et polychlorodibenzofuranes substitués par des atomes de chlore en 2,3,7,8 et de polychlorobiphényles de type dioxine dans les boues, les biodéchets traités et les sols à l’aide de méthodes de purification chromatographique sur colonne et d’analyse par chromatographie en phase gazeuse avec spectrométrie de masse haute résolution (CG/SMHR).
Les analytes devant être déterminés selon la présente Spécification technique sont énumérés au Tableau 1.
La limite de détection dépend du type d’échantillon, du congénère, de l’équipement utilisé et de la qualité des produits chimiques utilisés pour l’extraction et la purification. Dans les conditions spécifiées dans la présente Spécification technique, des limites de détection meilleures que 1 ng/kg (exprimées en matière sèche) peuvent être atteintes.
Cette méthode est « basée sur la performance ». Il est permis de modifier la méthode si tous les critères de performance donnés dans cette méthode sont remplis.
NOTE   En principe, cette méthode peut être également appliquée pour les sédiments, les déchets minéraux et les végétaux. Il appartient à l’utilisateur de la présente Spécification technique de valider l’application pour ces matrices. Pour les mesures dans les matrices complexes telles que les cendres volantes d’incinération adsorbées sur des végétaux, une amélioration de la purification peut s’avérer nécessaire. Ceci peut également s’appliquer aux sédiments et aux déchets minéraux.

Blato, obdelani biološki odpadki in tla - Določevanje dioksinov in furanov in dioksinom podobnih polikloriranih bifenilov s plinsko kromatografijo z masno selektivnim detektorjem visoke ločljivosti (HR GC/MS)

Ta tehnična specifikacija določa metodo za kvantitativno določevanje 17 2,3,7,8-klor substituiranih dibenzo-p-dioksinov in dibenzofuranov ter dioksinom podobnih polikloriranih bifenilov v blatu, obdelanih bioloških odpadkih in tleh z metodami kromatografskega čiščenja v koloni, napolnjeni s tekočino, in plinsko kromatografijo/masno spektrometrijo visoke ločljivosti (GC/HRMS). Meja detekcije je odvisna od vrste vzorca, kongenerja, uporabljene opreme in kakovosti kemikalij, uporabljenih pri ekstrakciji in čiščenju. Pod pogoji, določenimi v tej tehnični specifikaciji, se lahko dosežejo meje detekcije, boljše od 1 ng/kg (izraženo kot suha snov). Ta metoda »temelji na učinkovitosti«. Metodo je mogoče spremeniti, če so izpolnjena vsa merila učinkovitosti, ki so v njej navedena.

General Information

Status
Withdrawn
Publication Date
21-Feb-2012
Withdrawal Date
18-Dec-2018
Current Stage
9960 - Withdrawal effective - Withdrawal
Completion Date
19-Dec-2018

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SLOVENSKI STANDARD
SIST-TS CEN/TS 16190:2012
01-junij-2012
%ODWRREGHODQLELRORãNLRGSDGNLLQWOD'RORþHYDQMHGLRNVLQRYLQIXUDQRYLQ
GLRNVLQRPSRGREQLKSROLNORULUDQLKELIHQLORYVSOLQVNRNURPDWRJUDILMR]PDVQR
VHOHNWLYQLPGHWHNWRUMHPYLVRNHORþOMLYRVWL +5*&06

Sludge, treated biowaste and soil - Determination of dioxins and furans and dioxin-like

polychlorinated biphenyls by gas chromatography with high resolution mass selective

detection (HR GC-MS)
Schlamm, behandelter Bioabfall und Boden - Bestimmung von Dioxinen und Furanen

sowie Dioxin vergleichbaren polychlorierten Biphenylen mittels Gaschromatographie und

hochauflösender massenspektrometrischer Detektion (HR GC-MS)
Boue, biodéchet traité et sol - Détermination des dioxine et furane et biphényls

polychlorés de type dioxine par chromatographie en phase gazeuse-spectrométrie de

masse (HR GC-MS)
Ta slovenski standard je istoveten z: CEN/TS 16190:2012
ICS:
13.030.20 7HNRþLRGSDGNL%ODWR Liquid wastes. Sludge
13.080.10 .HPLMVNH]QDþLOQRVWLWDO Chemical characteristics of
soils
SIST-TS CEN/TS 16190:2012 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST-TS CEN/TS 16190:2012
---------------------- Page: 2 ----------------------
SIST-TS CEN/TS 16190:2012
TECHNICAL SPECIFICATION
CEN/TS 16190
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2012
ICS 13.030.01
English Version
Sludge, treated biowaste and soil - Determination of dioxins and
furans and dioxin-like polychlorinated biphenyls by gas
chromatography with high resolution mass selective detection
(HR GC-MS)

Boues, biodéchets traités et sols - Détermination des Schlamm, behandelter Bioabfall und Boden - Bestimmung

dioxines et furanes et polychlorobiphényles de type dioxine von Dioxinen und Furanen sowie Dioxin vergleichbaren

par chromatographie en phase gazeuse avec spectrométrie polychlorierten Biphenylen mittels Gaschromatographie und

de masse à haute résolution (CG-SMHR) hochauflösender massenspektrometrischer Detektion (HR

GC-MS)

This Technical Specification (CEN/TS) was approved by CEN on 24 April 2011 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, 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
Management Centre: Avenue Marnix 17, B-1000 Brussels

© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 16190:2012: E

worldwide for CEN national Members.
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CEN/TS 16190:2012 (E)
Contents Page

Foreword ..............................................................................................................................................................4

Introduction .........................................................................................................................................................5

1 Scope ......................................................................................................................................................6

2 Normative references ............................................................................................................................7

3 Abbreviations .........................................................................................................................................7

4 Principle ..................................................................................................................................................7

5 Reagents .................................................................................................................................................8

5.1 Chemicals ...............................................................................................................................................8

5.2 Standards ...............................................................................................................................................8

6 Apparatus and materials .......................................................................................................................8

6.1 General ....................................................................................................................................................8

6.2 Equipment for sample preparation ......................................................................................................8

6.3 Soxhlet extractor....................................................................................................................................8

6.4 Clean-up apparatus ...............................................................................................................................8

6.5 Concentration apparatus ......................................................................................................................9

6.6 Other equipment ....................................................................................................................................9

7 Sample storage and sample pretreatment ....................................................................................... 10

7.1 Sample storage ................................................................................................................................... 10

7.2 Sample pretreatment .......................................................................................................................... 10

8 Extraction and clean-up ..................................................................................................................... 10

8.1 General ................................................................................................................................................. 10

8.2 Extraction ............................................................................................................................................ 10

8.3 Clean-up ............................................................................................................................................... 11

8.3.1 General ................................................................................................................................................. 11

8.3.2 Gel permeation chromatography ...................................................................................................... 12

8.3.3 Multilayer column ............................................................................................................................... 12

8.3.4 Sulfuric acid treatment ....................................................................................................................... 12

8.3.5 Activated carbon column ................................................................................................................... 12

8.3.6 Aluminium oxide column ................................................................................................................... 12

8.3.7 Removal of sulfur................................................................................................................................ 12

8.4 Final concentration of cleaned sample extract ............................................................................... 12

8.5 Addition of recovery standard ........................................................................................................... 13

9 HRGC/HRMS analysis ........................................................................................................................ 13

9.1 General ................................................................................................................................................. 13

9.2 Gas chromatographic analysis ......................................................................................................... 13

9.3 Mass spectrometric detection ........................................................................................................... 13

9.4 Minimum requirements for identification of PCDF/PCDD and PCB .............................................. 15

9.5 Minimum requirements for quantification of PCDF/PCDD and PCB ............................................. 16

9.6 Calibration of the HRGC/HRMS system ........................................................................................... 17

9.6.1 General ................................................................................................................................................. 17

9.6.2 Calibration for 2,3,7,8-congeners ...................................................................................................... 17

9.6.3 Calibration for sum of homologue groups ....................................................................................... 17

9.7 Quantification of HRGC/HRMS results ............................................................................................. 18

9.7.1 Quantification of concentrations of 2,3,7,8-congeners .................................................................. 18

9.7.2 Quantification of recovery rates of C-labelled standards ............................................................ 19

9.7.3 Quantification of sum of homologue groups ................................................................................... 19

9.7.4 Calculation of the toxic equivalent ................................................................................................... 19

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CEN/TS 16190:2012 (E)

9.7.5 Calculation of the limit of detection and the limit of quantification ............................................... 20

10 Precision............................................................................................................................................... 20

11 Test report ............................................................................................................................................ 20

Annex A (informative) Toxic equivalent factors............................................................................................. 21

Annex B (informative) Repeatability and reproducibility data ..................................................................... 23

B.1 Materials used in the interlaboratory comparison study ................................................................ 23

B.2 Interlaboratory comparison results ................................................................................................... 24

Annex C (informative) Examples of extraction and clean-up methods ....................................................... 27

C.1 Example A ............................................................................................................................................ 27

C.1.1 General ................................................................................................................................................. 27

C.1.2 Chemicals ............................................................................................................................................. 27

C.1.3 Procedure ............................................................................................................................................. 28

C.2 Example B: Approved clean-up methods ......................................................................................... 33

Annex D (informative) Examples of operation of GC/HRMS determination ................................................ 35

D.1 Example ................................................................................................................................................ 35

D.1.1 General ................................................................................................................................................. 35

D.1.2 Gas chromatographic analysis .......................................................................................................... 35

D.1.3 Mass spectrometric detection ............................................................................................................ 36

Bibliography ...................................................................................................................................................... 39

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CEN/TS 16190:2012 (E)
Foreword

This document (CEN/TS 16190:2012) has been prepared by Technical Committee CEN/TC 400 “Project

Committee - Horizontal standards in the fields of sludge, biowaste and soil”, 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.

The preparation of this document by CEN is based on a mandate by the European Commission

(Mandate M/330), which assigned the development of standards on sampling and analytical methods for

hygienic and biological parameters as well as inorganic and organic determinants, aiming to make these

standards applicable to sludge, treated biowaste and soil as far as this is technically feasible.

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, 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.
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SIST-TS CEN/TS 16190:2012
CEN/TS 16190:2012 (E)
Introduction

Two groups of related chlorinated aromatic ethers are known as polychlorinated dibenzo-p-dioxins (PCDDs)

and polychlorinated dibenzofurans (PCDFs); they consist of a total of 210 individual substances (congeners):

75 PCDDs and 135 PCDFs.

A group of chlorinated aromatic compounds similar to polychlorinated dibenzo-p-dioxins (PCDDs) and

polychlorinated dibenzofurans (PCDFs) is known as polychlorinated biphenyls (PCBs) which consist of

209 individual substances.

PCDDs and PCDFs can form in the combustion of organic materials; they also occur as undesirable by-

products in the manufacture or further processing of chlorinated organic chemicals. PCDDs/PCDFs enter the

environment via these emission paths and through the use of contaminated materials. In fact, they are

universally present at very small concentrations. The 2,3,7,8-substituted congeners are toxicologically

significant. Toxicologically much less significant than the tetrachlorinated to octachlorinated dibenzo-p-

dioxins/dibenzofurans are the 74 monochlorinated to trichlorinated dibenzo-p-dioxins/dibenzofurans.

PCBs have been produced over a period of approximately 50 years until the end of the 1990s for the purpose

of different use in open and closed systems, e. g. as electrical insulators or dielectric fluids in capacitors and

transformers, as specialised hydraulic fluids, as a plasticizer in sealing material. Worldwide more than one

million tons of PCBs were produced.

PCDD/F as well as PCBs are emitted during thermal processes as e. g. waste incineration. In 1997 a group of

experts of the World Health Organisation (WHO) fixed toxicity equivalent factors (TEF) for PCDD and twelve

PCBs, known as dioxin-like PCBs (see Annex A). These twelve dioxin-like PCBs consist of four non-ortho

PCBs and eight mono-ortho PCBs (no or only one chlorine atoms in 2-, 2’-, 6- and 6’-position), having a planar

or mostly planar structure. Dioxin-like PCB can contribute considerably to the total WHO-TEQ.

Only skilled operators who are trained in handling highly toxic compounds should apply the method described

in this Technical Specification.

This Technical Specification is applicable for several types of matrices and validated for municipal sludge (see

also Annex B for the results of the validation).

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.
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CEN/TS 16190:2012 (E)
1 Scope

This Technical Specification specifies a method for quantitative determination of 17 2,3,7,8-chlorine

substituted dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls in sludge, treated

biowaste and soil using liquid column chromatographic clean-up methods and GC/HRMS.

The analytes to be determined with this Technical Specification are listed in Table 1.

Table 1 — Analytes and their abbreviations
Substance Abbreviation
Tetrachlorodibenzo-p-dioxin TCDD
Pentachlorodibenzo-p-dioxin PeCDD
Hexachlorodibenzo-p-dioxin HxCDD
Heptachlorodibenzo-p-dioxin HpCDD
Octachlorodibenzo-p-dioxin OCDD
Tetrachlorodibenzofuran TCDF
Pentachlorodibenzofuran PeCDF
Hexachlorodibenzofuran HxCDF
Heptachlorodibenzofuran HpCDF
Octachlorodibenzofuran OCDF
Polychlorinated biphenyl PCB
Trichlorobiphenyl TCB
Tetrachlorobiphenyl TeCB
Pentachlorobiphenyl PeCB
Hexachlorobiphenyl HxCB
Heptachlorobiphenyl HpCB
Decachlorobiphenyl DecaCB

The limit of detection depends on the kind of sample, the congener, the equipment used and the quality of

chemicals used for extraction and clean-up. Under the conditions specified in this Technical Specification,

limits of detection better than 1 ng/kg (expressed as dry matter) can be achieved.

This method is "performance based". It is permitted to modify the method if all performance criteria given in

this method are met.

NOTE In principle this method can also be applied for sediments, mineral wastes and for vegetation. It is the

responsibility of the user of this Technical Specification to validate the application for these matrices. For measurement in

complex matrices like fly ashes adsorbed on vegetation it can be necessary to further improve the clean up. This can also

apply to sediments and mineral wastes.
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CEN/TS 16190:2012 (E)
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 16179, Sludge, treated biowaste and soil — Guidance for sample pretreatment
3 Abbreviations
PCB Polychlorinated biphenyls
PCDD/PCDF or PCDD/F Polychlorinated dibenzo-p-dioxins/dibenzofurans

I-TEF NATO/CCMS International toxic equivalent factor proposed by NATO-CCMS in 1988 (for

detailed description, see Annex A)

I-TEQ International toxic equivalent obtained by multiplying the mass determined with

the corresponding I-TEF including PCDDs and PCDFs (for detailed description,
see Annex A). Should only be used for comparison with older data

WHO-TEF Toxic equivalent factor proposed by WHO in 2005 (for detailed description, see

Annex A)
WHO-TEQ Toxic equivalent obtained by multiplying the mass determined with the
corresponding WHO-TEF including PCDD, PCDF and PCB (for detailed
description, see Annex A). WHO-TEQ , WHO-TEQ should be used to
PCB PCDD/F
distinguish different compound classes
4 Principle

This Technical Specification is based on the use of gas chromatography/mass spectrometry combined with

the isotope dilution technique to enable the separation, detection and quantification of PCDD/PCDF and

dioxin-like PCB in sludge, biowaste and soil. For the isotope dilution method 17 labelled PCDD/F and

12 labelled PCB internal standards are used. The extracts for the GC-MS measurements contain one or two

recovery standards. The gas chromatographic parameters offer information which enables the identification of

congeners (position of chlorine substitutes) whereas the mass spectrometric parameters enable the

differentiation between isomers with different numbers of chlorine substitutes and between dibenzo-p-dioxins,

furans and PCB.

C -labelled PCDD/F and PCB congeners are added to the sample prior to extraction and HRGC/HRMS

measurement. Losses during extraction and clean-up are detected and compensated by using these added

congeners as internal standards for quantification together with recovery standards which are added just

before the HRGC/HRMS analysis. For the determination of these substances it is necessary to separate

PCBs from PCDDs/PCDFs and vice versa.

The main purpose of the clean-up procedure of the raw sample extract is the removal of sample matrix

components, which may overload the separation method, disturb the quantification or otherwise severely

impact the performance of the identification and quantification method and the separation of PCDD/F from

dioxin-like PCB. Furthermore, the enrichment of the analytes in the final sample extract is achieved. Extraction

procedures are usually based on Soxhlet or equivalent extraction methods of dried, preferably freeze dried,

samples. Sample clean-up is usually carried out by multi-column liquid chromatographic techniques using

different adsorbents. The determination of PCDD/F and PCBs is based on quantification by the isotope-

dilution technique using HRGC/HRMS.
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SIST-TS CEN/TS 16190:2012
CEN/TS 16190:2012 (E)
5 Reagents
5.1 Chemicals

Solvents used for extraction and clean-up shall be of pesticide grade or equivalent quality and checked for

blanks. Adsorbents like aluminium oxide, silica gel, diatomaceous earth and others used for clean-up shall be

of analytical grade quality or better and pre-cleaned and activated if necessary.

NOTE See Annex C for a specific list of solvents and chemicals.
5.2 Standards
 C-spiking solution for PCDD/F (internal Standard);
 C-spiking solution for PCB (internal Standard);
 Calibration solutions PCDD/F;
 Calibration solutions PCB;
 Recovery standard PCDD/F;
 Recovery standard PCB.
NOTE See Annex C for examples of concentration of the standard solutions.
6 Apparatus and materials
6.1 General

The apparatus and materials listed below are meant as minimum requirements for "conventional" sample

treatment with Soxhlet extraction and column chromatographic clean-up. Additional apparatus and materials

may be necessary due to different methods of sample extraction and clean-up methods.

6.2 Equipment for sample preparation

6.2.1 Laboratory fume hood, of sufficient size to contain the sample preparation equipment listed below.

6.2.2 Desiccator.

6.2.3 Balances, consisting of an analytical type capable of weighing 0,1 mg and a top-loading type capable

of weighing 10 mg.
6.3 Soxhlet extractor

6.3.1 Soxhlet, 50 mm internal diameter, 150 ml or 250 ml capacity with 500 ml round bottom flask.

6.3.2 Thimble, 43 mm × 123 mm, to fit Soxhlet.
6.3.3 Hemispherical heating mantle, to fit 500 ml round-bottom flask.
6.4 Clean-up apparatus

6.4.1 Disposable pipettes, either disposable Pasteur pipettes, or disposable serological pipettes.

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SIST-TS CEN/TS 16190:2012
CEN/TS 16190:2012 (E)
6.4.2 Glass chromatographic columns, of the following sizes:

 150 mm length × 8 mm internal diameter, with coarse-glass frit or glass-wool plug, 250 ml reservoir and

glass or polytetrafluoroethylene (PTFE) stopcock;

 200 mm length × 15 mm internal diameter, with coarse-glass frit or glass-wool plug, 250 ml reservoir and

glass or PTFE stopcock;

 300 mm length × 25 mm internal diameter, with coarse-glass frit or glass-wool plug, 300 ml reservoir and

glass or PTFE stopcock.

6.4.3 Oven, capable of maintaining a constant temperature (± 5 °C) in the range of 105 °C to 450 °C for

baking and storage of adsorbents.
6.5 Concentration apparatus
6.5.1 Rotary evaporator, equipped with a variable temperature water bath and:

 vacuum source for rotary evaporator equipped with shutoff valve at the evaporator and vacuum gauge;

 recirculating water pump and chiller, providing cooling water of (9 ± 4) °C (use of tap water for cooling the

evaporator wastes large volumes of water and can lead to inconsistent performance as water

temperatures and pressures vary);

 round-bottom flask, 100 ml and 500 ml or larger, with ground-glass fitting compatible with the rotary

evaporator.

6.5.2 Nitrogen blowdown apparatus, equipped with either a water bath controlled in the range of 30 °C to

60 °C or a heated stream of nitrogen, installed in a fume hood.
6.5.3 Kuderna-Danish concentrator.
6.5.4 Sample vials, of the following types:
 amber glass, nominated volume 2 ml to 5 ml, with PTFE-lined screw cap;
 glass, 0,3 ml, conical, with PTFE-lined screw or crimp cap.
6.6 Other equipment

6.6.1 Gas chromatograph, equipped with a splitless or on-column or temperature programmed injection

port for the use with capillary columns, and an oven temperature programme which enables isothermal hold.

6.6.2 GC column for PCDDs/PCDFs and for isomer specificity for 2,3,7,8-TCDD (e. g. 60 m length ×

0,32 mm internal diameter; 0,25 µm; 5 % phenyl, 94 % methyl, 1 % vinyl silicone bonded-phase fused-silica

capillary column).

6.6.3 Mass spectrometer, 28 eV to 80 eV electron impact ionization, capable of repetitively selectively

monitoring of twelve exact masses minimum at high resolution (> 10 000) during a period of approximately

1 s.

6.6.4 Data system, capable of collecting, recording, and storing mass spectrometric data.

1) Kuderna Danish is an example of a suitable product available commercially. This information is given for the

convenience of users of this Technical Specification and does not constitute an endorsement by CEN of this product.

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SIST-TS CEN/TS 16190:2012
CEN/TS 16190:2012 (E)
7 Sample storage and sample pretreatment
7.1 Sample storage

Samples should be stored in suitable containers with an appropriate closure material such as

polytetrafluoroethylene (PTFE). Samples to be frozen may be stored in aluminium containers pre-cleaned by

heating to 450 °C for minimum 4 h or by rinsing with a non-chlorinated solvent.

Samples should be kept cold (< 8 °C) and in the dark. The sample pretreatment should take place within

three days of sampling. Alternatively, samples may be frozen (–18 °C) directly after sampling and kept frozen

before sample pretreatment.
7.2 Sample pretreatment

Drying and homogenization should be carried out according to EN 16179, if not otherwise specified. Store the

ground material in a desiccator or a tightly closed glass container.
8 Extraction and clean-up
8.1 General

In this Technical Specification the minimum requirements for extraction and clean-up to be met are described

as well as examples of operation. The analyst may use any of the procedures given below and in Annex C or

any suitable alternative procedures.

The determination of PCDDs/PCDFs is based on quantification by the isotope-dilution technique using

HRGC/HRMS. C -labelled 2,3,7,8-chlorine substituted PCDD/PCDF congeners are added at different

stages of the whole method. Losses during extraction and clean-up can be detected and compensated by

using these added congeners as internal standards for quantification together with recovery standards which

are added just before the HRGC/HRMS analysis. However, due to possible differences in the binding and

adsorption characteristics between the native PCDDs/PCDFs and the C -labelled congeners, which are

added during analysis, complete substantiation of the extraction efficiency and compensation of losses during

clean-up is not ensured. Therefore, in addition the applied methods shall be validated thoroughly. Examples of

well-proven extraction and clean-up methods are given in Annex C.
The main purpose of the clea
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