CEN/TS 16190:2012

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
• ICS: 13.030.01 - Wastes in general
• Technical Committee: CEN/TC 444 - Environmental characterization
• Drafting Committee: CEN/TC 444/WG 2 - Organic analysis
• Current Stage: 9960 - Withdrawal effective - Withdrawal
• Completion Date: 19-Dec-2018
• Directive: 86/278/EEC - Protection of the environment, and in particular of the soil, when sewage sludge is used in agriculture
• Mandate: M/330 - Mandate given to CEN for the development of horizontal standards in the fields of sludge, biowaste and soil.
• Ref Project: SIST-TS CEN/TS 16190:2012 - 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)

Relations

• Replaced By: EN 16190:2018 - Soil, treated biowaste and sludge - Determination of dioxins and furans and dioxin-like polychlorinated biphenyls by gas chromatography with high resolution mass selective detection (HR GC-MS)
• Effective Date: 22-Mar-2017

Standards Content (Sample)

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

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.

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
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

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, Rom
...