Sludge, treated biowaste and soil - Determination of selected phthalates using capillary gas chromatography with mass spectrometric detection (GC-MS)

This Technical Specification specifies a method for the determination of selected phthalates in sludge, treated biowaste and soil, after extraction and gas chromatographic analysis with mass spectrometric detection.
The method is applicable for the determination of phthalates (see Table 2) at the lowest mass content of 0,1 mg/kg to 0,5 mg/kg (expressed as dry matter), depending on the individual substance.
The applicability of the method to other phthalates not specified in Table 2 is not excluded except the isomeric mixtures e.g. DiNP (Di-isononylphthalate), but shall be verified in each case.

Schlamm, behandelter Bioabfall und Boden - Bestimmung ausgewählter Phthalate mittels kapillarer Gaschromatographie mit massenspektrometrischer Detektion (GC-MS)

Diese Technische Spezifikation legt ein Verfahren zur Bestimmung ausgewählter Phthalate in Schlamm,
behandeltem Bioabfall und Boden nach Extraktion und gaschromatographischer Analyse mit
massenspektrometrischer Detektion fest.
Das Verfahren ist für die Bestimmung von Phthalaten (siehe Tabelle 2) mit einem Mindestmassengehalt von
0,1 mg/kg bis 0,5 mg/kg (angegeben als Trockenmasse), geeignet, abhängig von der jeweiligen Substanz.
Die Anwendbarkeit des Verfahrens auf weitere, in Tabelle 2 nicht angegebene Phthalate, ist bis auf die
Isomerengemische, wie z. B. DINP (Di-isononylphthalat), nicht ausgeschlossen, muss aber für jeden Fall
nachgewiesen werden.

Boues, biodéchets traités et sols - Détermination de certains phtalates par chromatographie en phase gazeuse capillaire avec détection par spectrométrie de masse (CG-SM)

La présente Spécification technique spécifie une méthode pour la détermination de certains phtalates dans
les boues, les biodéchets traités et les sols, après extraction et analyse par chromatographie en phase
gazeuse/spectrométrie de masse.
La méthode est applicable pour la détermination de phtalates (voir Tableau 2) à la plus faible teneur massique
de 0,1 mg/kg à 0,5 mg/kg (exprimée en teneur en matière sèche), selon la substance individuelle.
L'applicabilité de la méthode à d'autres phtalates non spécifiés dans le Tableau 2 n'est pas exclue, à
l'exception des mélanges isomériques tels que DiNP (Di-isononylphtalate), mais elle doit être vérifiée dans
chaque cas.

Blato, obdelani biološki odpadki in tla - Določevanje izbranih ftalatov s kapilarno plinsko kromatografijo z masno selektivno detekcijo (GC/MS)

Ta tehnična specifikacija opredeljuje metodo za določevanje izbranih ftalatov v blatu, obdelanih bioloških odpadkih in tleh po ekstrakciji in plinski kromatografiji z masno selektivno detekcijo. Ta metoda se uporablja za določevanje ftalatov (glejte preglednico 2) pri najnižji masni vsebnosti od 0,1 mg/kg do 0,5 mg/kg (izraženo kot suha snov), odvisno od posamezne snovi. Uporabnost metode pri drugih ftalatih, ki niso navedeni v preglednici 2, ni izključena, razen pri mešanicah izomerov, npr. DiNP (di-izononilftalat), vendar mora biti preverjena pri vsakem posameznem primeru.

General Information

Status
Published
Publication Date
21-Feb-2012
Current Stage
9060 - Closure of 2 Year Review Enquiry - Review Enquiry
Due Date
02-Dec-2020
Completion Date
02-Dec-2020

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SLOVENSKI STANDARD
SIST-TS CEN/TS 16183:2012
01-junij-2012

%ODWRREGHODQLELRORãNLRGSDGNLLQWOD'RORþHYDQMHL]EUDQLKIWDODWRYVNDSLODUQR

SOLQVNRNURPDWRJUDILMR]PDVQRVHOHNWLYQRGHWHNFLMR *&06

Sludge, treated biowaste and soil - Determination of selected phthalates using capillary

gas chromatography with mass spectrometric detection (GC-MS)
Schlamm, behandelter Bioabfall und Boden - Bestimmung ausgewählter Phthalate

mittels kapillarer Gaschromatographie mit massenspektrometrischer Detektion (GC-MS)

Boues, bio-déchets traités et sols - Détermination de certains phtalates par
chromatographie en phase gazeuse capillaire avec détection par spectrométrie de
masse (CG-SM)
Ta slovenski standard je istoveten z: CEN/TS 16183:2012
ICS:
13.030.20 7HNRþLRGSDGNL%ODWR Liquid wastes. Sludge
13.080.10 .HPLMVNH]QDþLOQRVWLWDO Chemical characteristics of
soils
SIST-TS CEN/TS 16183:2012 en,fr,de

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

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SIST-TS CEN/TS 16183:2012
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SIST-TS CEN/TS 16183:2012
TECHNICAL SPECIFICATION
CEN/TS 16183
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2012
ICS 13.030.01
English Version
Sludge, treated biowaste and soil - Determination of selected
phthalates using capillary gas chromatography with mass
spectrometric detection (GC-MS)

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

certains phtalates par chromatographie en phase gazeuse ausgewählter Phthalate mittels kapillarer

capillaire avec détection par spectrométrie de masse (CG- Gaschromatographie mit massenspektrometrischer

SM) Detektion (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 16183:2012: E

worldwide for CEN national Members.
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Contents Page

Foreword ..............................................................................................................................................................3

Introduction .........................................................................................................................................................4

1 Scope ......................................................................................................................................................5

2 Normative references ............................................................................................................................5

3 Principle ..................................................................................................................................................6

4 Interferences ..........................................................................................................................................6

4.1 General ....................................................................................................................................................6

4.2 Interferences during sampling .............................................................................................................6

4.3 Cross contamination .............................................................................................................................6

4.4 Interferences in gas chromatography .................................................................................................6

5 Reagents .................................................................................................................................................6

6 Apparatus ...............................................................................................................................................8

7 Sampling and sample storage ........................................................................................................... 10

8 Procedure ............................................................................................................................................ 10

8.1 Preparation of glass apparatus ......................................................................................................... 10

8.2 Drying of the sample .......................................................................................................................... 10

8.2.1 General ................................................................................................................................................. 10

8.2.2 Freeze drying ....................................................................................................................................... 10

8.2.3 Drying with sodium sulfate (Na SO ) .............................................................................................. 11

2 4

8.3 Extraction ............................................................................................................................................ 11

8.4 Clean-up ............................................................................................................................................... 11

8.5 Gas chromatography .......................................................................................................................... 12

8.6 Blank monitoring ................................................................................................................................ 12

8.7 Identification of individual compounds ............................................................................................ 12

9 Calibration ........................................................................................................................................... 13

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

9.2 Calibration with internal standard..................................................................................................... 14

9.3 Verification of calibration ................................................................................................................... 14

10 Calculation ........................................................................................................................................... 14

11 Expression of results ......................................................................................................................... 16

12 Precision .............................................................................................................................................. 16

13 Test report ........................................................................................................................................... 16

Annex A (informative) Repeatability and reproducibility data ..................................................................... 17

A.1 Materials used in the interlaboratory comparison study ............................................................... 17

A.2 Interlaboratory comparison results .................................................................................................. 18

Annex B (informative) Example of a reference solution for multipoint calibration ................................... 20

Annex C (informative) Examples for gas chromatographic conditions ..................................................... 22

C.1 Examples for capillary columns ........................................................................................................ 22

C.2 Example of gas chromatographic conditions .................................................................................. 22

Annex D (informative) Flow scheme of the determination of phthalates ................................................... 24

Bibliography ..................................................................................................................................................... 25

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Foreword

This document (CEN/TS 16183:2012) 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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Introduction

This Technical Specification is applicable and validated for several types of matrices as indicated in Table 1

(see also Annex A for the results of the validation).

Table 1 — Matrices for which this Technical Specification is applicable and validated

Matrix Materials used for validation
Sludge Municipal sludge
Biowaste Fresh compost
Soil Sludge amended soil

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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1 Scope

This Technical Specification specifies a method for the determination of selected phthalates in sludge, treated

biowaste and soil, after extraction and gas chromatographic analysis with mass spectrometric detection.

The method is applicable for the determination of phthalates (see Table 2) at the lowest mass content of

0,1 mg/kg to 0,5 mg/kg (expressed as dry matter), depending on the individual substance.

The applicability of the method to other phthalates not specified in Table 2 is not excluded except the isomeric

mixtures e. g. DiNP (Di-isononylphthalate), but shall be verified in each case.
Table 2 — Phthalates that can be determined according to CEN/TS 16183
No Name Formula Abbreviation Molar mass CAS-RN
g/mol
1 Dimethylphthalate C H O DMP 194,2 00131-11-3
10 10 4
2 Diethylphthalate C H O DEP 222,2 00084-66-2
12 14 4
3 Dipropylphthalate C H O DPP 250,3 00131-16-8
14 18 4
4 Di-(2-methyl- C H O DiBP 278,4 00084-69-5
16 22 4
propyl)phthalate
5 Dibutylphthalate C H O DBP 278,4 00084-74-2
16 22 4
6 Butylbenzylphthalate C H O BBzP 312,4 00085-68-7
19 20 4
C H O
7 Dicyclohexylphthalate DCHP 330,4 00084-61-7
20 26 4
8 Di-(2-ethylhexyl)phthalate C H O DEHP 390,6 00117-81-7
24 38 4
9 Dioctylphthalate C H O DOP 390,6 00117-84-0
24 38 4
10 Didecylphthalate C H O DDcP 446,7 00084-77-5
28 46 4
11 Diundecylphthalate C H O DUP 474,4 03648-20-2
30 50 4
a CAS-RN Chemical Abstracts Service Registry Number.
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 15934, Sludge, treated biowaste, soil and waste — Calculation of dry matter fraction after determination of

dry residue or water content
EN 16179, Sludge, treated biowaste and soil — Guidance for sample pretreatment

EN ISO 5667-13, Water quality — Sampling — Part 13: Guidance on sampling of sludges (ISO 5667-13)

EN ISO 5667-15, Water quality — Sampling — Part 15: Guidance on the preservation and handling of sludge

and sediment samples (ISO 5667-15)

EN ISO 22892, Soil quality — Guidelines for the identification of target compounds by gas chromatography

and mass spectrometry (ISO 22892)
ISO 10381-2, Soil quality — Sampling — Part 2: Guidance on sampling techniques
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CEN/TS 16183:2012 (E)
3 Principle

The dried sample, dried by freeze-drying or with sodium sulfate is extracted with ethyl acetate on the shaking

device. An aliquot of the extract is cleaned with aluminium oxide (if necessary) followed by gas

chromatographic separation using capillary columns and identification and quantification of the phthalates by

mass spectrometry.
4 Interferences
4.1 General

Due to their use as plasticizer agents, phthalates are ubiquitous. The sources of phthalates are multiple and

shall be checked and reduced by every laboratory itself. Therefore, special attention shall be paid to avoid

contaminations.
4.2 Interferences during sampling

In order to avoid interferences and cross contaminations, do not use plastic materials (pipes, etc.).

4.3 Cross contamination

Chemicals and analytical equipment can be of various quality. Cross contamination is likely to occur with

laboratory air. Therefore, remove, as far as possible, plastic materials from the laboratory. Cleaning agents often

contain phthalates and may severely contaminate the laboratory air if in use regularly. Therefore, refrain from

using these agents during application of this procedure.
Using plastic gloves during pretreatment may increase the contamination.
4.4 Interferences in gas chromatography

Phthalates may bleed from the septa of the injector into the gas chromatograph, therefore use septa that are not

likely to contaminate the system.

Fittings, e. g. of syringes, or equipment and septa of the sampling bottles (see 6.5) may also contain

phthalates.
5 Reagents
5.1 General
All reagents shall be of recognized analytical grade.

Use only reagents with negligibly low concentration of phthalates and verify by blank determinations and, if

necessary, apply additional cleaning steps.

5.2 Nitrogen, N , of high purity, at least a volume fraction of 99,9 % for drying and, if necessary, for

concentration by evaporation.
5.3 Helium, He, of high purity, at least a volume fraction of 99,999 %.
5.4 Ethyl acetate, C H O , phthalate-free, high purity.
4 8 2
5.5 Methanol, CH OH.
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CEN/TS 16183:2012 (E)
5.6 Isooctane, C H (2,2,4-trimethylpentane).
8 18
5.7 Quartz wool, heated to 400 °C for at least 4 h.

5.8 Aluminium oxide, Al O , neutral, 50 µm to 200 µm particle size, heated to 400 °C for at least 4 h.

2 3
Store in covered flask or desiccator. Use within five days after heat-treatment.
1)

NOTE Alternative materials, like Florisil or silica may be used, provided their properties and capacity to separate

are similar to aluminium oxide and their properties are checked according to 8.6.

5.9 Internal standards
For example:
 deuterated di-n-butylphthalate, "D4-ring-DBP";
 deuterated D4-C H O ;
16 22 4
 deuterated di-(2-ethylhexyl)phthalate "D4-ring-DEHP";
 deuterated D4-C H O ; di-n-octylphthalate, "D4-ring-DOP";
24 38 4
 D4- C H O ;
24 38 4
 C-labelled standards can also be used, if available.
5.10 Reference substances

Table 2 gives a list of phthalates, with defined mass concentrations, for the preparation of reference solutions

for the gas chromatographic procedure.
5.11 Solutions of the single substances

In a 10 ml volumetric flask (6.13), transfer e. g. 10 mg of each of the reference substances (5.10) in ethyl

acetate (5.4) and bring to volume with ethyl acetate (5.4) (concentration: 1 g/l).

Store the solutions in glass bottles at –18 °C, protected from light, and check the concentration at least every

three months.
5.12 Stock solution

In a 10 ml volumetric flask (6.13), dissolve between 100 µl and 500 µl of the single substance solutions (5.11)

and bring to volume with ethyl acetate (5.4) (concentration: 10 mg/l to 50 mg/l).

Store the solution in a glass bottle at –18 °C, protected from light, and check the concentration at least every

three months.

1) Florisil is a trade name for a prepared diatomaceous substance, mainly consisting of anhydrous magnesium silicate.

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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5.13 Reference solutions for multipoint calibration (see Annex B).

Prepare solutions by adequate dilution of the stock solution (5.12) and internal standards (5.9) with ethyl

acetate (5.4).

Store the solutions in glass bottles at –18 °C, protected from light, and check the concentration at least every

three weeks.
5.14 Solution of the internal standards (see Annex B).
5.14.1 Internal standard solution of D4-phthalates

Weigh e. g. 0,1 g of an internal standard phthalate (D4) (5.9) in a 10 ml volumetric flask (6.13) filled with about

5 ml of ethyl acetate (5.4) and bring to volume with ethyl acetate (5.4). Store the solution in a glass bottle

at -18 °C.
5.14.2 Solution I internal standard mix

Combine the solutions of the single internal standard phthalates (5.9) e. g. by dilution 1:100 as follows:

Transfer with a syringe 0,1 ml (6.15) of each solution into a 10 ml volumetric flask (6.13) filled with about 5 ml

of ethyl acetate (5.4). Bring to volume with ethyl acetate. The final concentration of di-n-octylphthalate (D4)

di-n-butylphthalate (D4) and di-(2-ethylhexylphthalate) will be 100 mg/l in ethyl acetate (5.4).

5.14.3 Solution II internal standard mix

Take from this 1:100 dilution (5.14.2) e. g. 250 µl, transfer into a volumetric flask, 250 ml (6.13), filled with

250 ml of ethyl acetate (5.4).

The final concentration of di-n-octylphthalate (D4), di-n-butylphthalate (D4) and di-(2-ethylhexylphthalate) is

0,1 mg/l in ethyl acetate (5.4).
5.14.4 Solution III internal standard mix

Dilute the solution I internal standard (5.14.2.) 1:10: Pipette 1 ml of the solution (5.14.2.) in a 10 ml volumetric

flask (6.13) filled with about 5 ml of ethyl acetate (5.4). Bring to volume with ethyl acetate. The final

concentration of di-n-octylphthalate (D4), di-n-butylphthalate (D4) and di-(2-ethylhexylphthalate) is 10 mg/l in

ethyl acetate.
5.15 Sodium sulfate, Na SO , heated to 400 °C for at least 4 h.
2 4
6 Apparatus
6.1 General

Equipment or parts of it which are likely to come into contact with the sample or its extract shall be free from

phthalates. This may be achieved by thorough cleaning of all glass apparatus and checked by the blank

determination.

6.2 Wide-neck flat bottomed flasks with glass stoppers, preferably brown glass, volume 500 ml and

1 000 ml.
6.3 Drying oven, capable of maintaining at a temperature of (105 ± 5) °C.

6.4 Muffle furnace, adjustable, up to temperatures of (400 ± 10) °C, with capacity of e. g. at least 60 l.

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CEN/TS 16183:2012 (E)

6.5 Sampling vial, glass, with inert stopper, e. g. septum, lined with polytetrafluoroethylene (PTFE) for

storage of the extracts, and sampling bottles, glass, with inert septum, 2 ml, for storage of the extracts for auto

sampler operation.
6.6 Vacuum device for clean-up (vacubox, extraction box).

6.7 Stainless steel cock, with stainless steel cone or polytetrafluoroethylene (PTFE) cock with Luer

connection for separate vacuum connection.
6.8 Glass cartridges, with Luer cone.
6.9 Polytetrafluoroethylene (PTFE) frits for cartridges, 6 ml.
6.10 Aluminium foil, heated to 400 °C.
6.11 Stainless steel reservoir, for storage of smaller glass apparatus.
6.12 Measuring cylinders, volumes 50 ml and 100 ml.
6.13 Volumetric flasks, volumes 10 ml, 25 ml and 250 ml.
6.14 Pasteur pipettes, e. g. 2 ml.

6.15 Syringes, 2 µl, 5 µl, 10 µl 50 µl, 100 µl and 500 µl, maximum permitted error ± 2 %.

6.16 Gas chromatograph, with capillary column, temperature controlled, with mass spectrometric detection.

6.17 Operating gases for gas chromatography/mass spectrometer of high purity and in accordance with

manufacturer's specifications.

6.18 Fused silica columns, with non-polar stationary phase (see Annex C for examples).

Check the quality of the column e. g. by injecting the reference solution (5.13) and ensure that the separation

is satisfactory.
6.19 Glass tubes, graduated 5 ml or 10 ml.
6.20 Nitrogen device for drying the glass cartridges (6.8).
6.21 Beaker, volume 50 ml and 100 ml.
6.22 Erlenmeyer flask, volume 250 ml.
6.23 Shaking device, horizontal shaking movement.
6.24 Freeze drying apparatus
6.25 Metal spoon
6.26 Agate mortar
6.27 Metallic clamp, for stopper.
6.28 Balance, e. g.: range 0,001 g to 100 g.
6.29 Pipette, volume 20 ml, 25 ml and 50 ml.
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7 Sampling and sample storage

Collect, preserve and handle samples in accordance with EN ISO 5667-13, EN ISO 5667-15 and

ISO 10381-2.

Use for sampling pretreated sampling bottles (6.2) and make sure that the stoppers are pretreated as well.

In general, sampling should be carried out using stainless steel containers or glass vessels. In order to avoid

contaminations, do not use any plastics material (tubes and other).

Dry the sample as soon as possible after sample collection. If storage is unavoidable, store the samples in the

dark at 4 °C. Dried samples are found to be stable for a longer period.
Determine the dry matter content in accordance with EN 15934.
8 Procedure
8.1 Preparation of glass apparatus

Clean all glass apparatus, except the syringes, used during analysis in the dishwasher with water and

subsequently dry in the oven (6.3) at 105 °C.

Heat the pre-rinsed glass apparatus in the muffle furnace (6.4) for at least 4 h at 400 °C.

Subsequently let the apparatus cool to room temperature within 12 h.

NOTE Glassware for volumetric purposes may change its properties due to the heating process.

Close the cooled glass apparatus (bigger vessels) with the respective stoppers or with aluminium foil (6.10).

Store smaller glass apparatus in decontaminated (heated) and appropriately closed stainless steel containers

(6.11).

In order to avoid losses by adsorption on the walls, rinse the walls with isooctane (5.6) by using Pasteur

pipettes (6.14). Discard the solvent.
Let residual solvent evaporate under a fume hood.

Carry out this deactivation of the surface after heating and cooling or immediately prior to use.

8.2 Drying of the sample
8.2.1 General
Pretreat the samples according to EN 16179, if not otherwise specified.

Depending on the water content and the matrix, dry the sample either with sodium sulfate (5.15) or by freeze

drying (see also Annex D).

Samples (i. e. soil, waste) with a dry matter > 80 % can be dried with sodium sulfate (see 8.2.3).

Sludge with high water content shall be dried by freeze drying (see 8.2.2).
8.2.2 Freeze drying

Freeze a part of the homogenized sample or a representative part of the sample at –18 °C. Afterwards

lyophilise at about 5 kPa until the constant mass is achieved.
Homogenize the freeze-dried sample with the aid of an agate mortar (6.26).
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CEN/TS 16183:2012 (E)
8.2.3 Drying with sodium sulfate (Na SO )
2 4

Depending on the expected phthalate content of the sample, weigh between 1 g to 10 g of the wet sample into

a beaker (6.21) and give as much sodium sulfate (5.15) into the wet sample until a trickle mixture is achieved.

Mortar the mixture in an agate mortar (6.26). When a free-flowing mixture is obtained, the humidity is bound.

In parallel, determine the dry matter content of the sample (see Clause 7).
8.3 Extraction

Transfer between 1 g to 10 g, referred to the dry matter content and the expected phthalate concentration, of

the mixture of the sample and sodium sulfate (prepared according to 8.2.3) or the freeze dried sample

(prepared according to 8.2.2) into a 250 ml Erlenmeyer flask (6.22) and give e. g. 20 ml ethyl acetate (5.4)

with internal standard (5.9) to the sample. If a high amount of phthalates is expected, the extraction solvent

can be doubled or multiplied (see Table 3). Since the concentration of phthalate in a blank is unknown,

dilutions of the sample extract shall be avoided. Close the Erlenmeyer flask (6.22) with a stopper and fix the

stopper with a metallic clamp (6.27).

Extract the sample for at least 30 min on the shaking device (6.23). Make sure that a good thorough mixing of

the sample and the solvent is obtained. After the extraction, take approximately 1 ml with a pipette (6.14) and

transfer the extract into a GC vial (6.5), or approximately 3 ml are required if a clean-up (see 8.4) is

necessary. Place the heated aluminium foil (6.10) between vial and caps in order to avoid a contamination by

phthalates from the septa. The extract can be analysed by GC-MS directly.

If a clean-up is necessary, e. g. due to interferences of the target analyte in the GC-MS chromatography, see

8.4.
Table 3 — Examples of sample intake and ratio dry matter/solvent volume
Matrix Sample intake Ratio dry matter:solvent Remark
Sludge (sewage) 1 to 10 < 1:80 A high amount of DEHP is expected
Sediment / suspended solid 2 to 10 < 2:20 DEHP is expected
Compost 2 to 10 < 2:20 Low to high concentration of DEHP
Soil 2 to 10 < 2:20 Low to high concentration of DEHP

Take care that the amount of solvent is sufficient for collecting the extract (at least 3 ml).

NOTE The described method of extraction (shaking) is recommended due to the small contamination potential. Using

Soxhlet extraction or accelerated solvent extraction (ASE), comparable amount of phthalates can be achieved, but the

contamination risk is higher. Moreover, the extraction relation (solvent and sample intake) should be adjusted to the

respective extraction method. For blank criteria see 8.6.
8.4 Clean-up

A clean-up is only necessary if interferences in the GC-MS chromatogram, originating from matrices, are

expected, otherwise it should be avoided due to the additional risk of contamination. After the extraction take

approximately 3 ml of the extract with a pipette (6.14) and clean the extract with aluminium oxide (5.8).

Clean the extracts as follows:

 place 1 g of activated aluminium oxide (5.8) in the cartridges (6.8) between two PTFE frits (6.9);

 clean the aluminium oxide (5.8) with one cartridge volume of ethyl acetate (5.4);

 dry with nitrogen (5.2) for 1 min;
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SIST-TS CEN/TS 16183:2012
CEN/TS 16183:2012 (E)

 fix the cleaned cartridge with stainless steel cock (6.7) and place it on the vacuum device (6.6);

 let the extract run through the cartridge and collect it in a glass tube (6.19);

 transfer the extract to GC vials (6.5). Attach heated aluminium foil (6.10) between vial and cap in order to

avoid a contamination by phthalates from the septa.
8.5 Gas chromatography

Optimise the GC-apparatus (6.16) according to the instrument manufacturer's manual.

Use capillary columns (6.18 see also Annex C) for separation.
In order to clean the inlet system free from p
...

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