Safety of toys — Part 6: Certain phthalate esters in toys and children's products

ISO 8124-6:2014 specifies a method for the determination of di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl phthalate (DINP), and di-iso-decyl phthalate (DIDP) (see Annex A) in toys and children's products. ISO 8124-6:2014 is applicable to toys and children's products which are made of plastics, textiles, and coatings, etc.

Sécurité des jouets — Partie 6: Jouets et produits pour enfants — Dosage de certains phtalates d'esters dans les jouets et produits pour enfants

General Information

Status
Withdrawn
Publication Date
07-Aug-2014
Withdrawal Date
07-Aug-2014
Technical Committee
Drafting Committee
Current Stage
9599 - Withdrawal of International Standard
Start Date
07-Nov-2018
Completion Date
07-Nov-2018
Ref Project

RELATIONS

Buy Standard

Standard
ISO 8124-6:2014 - Safety of toys
English language
27 pages
sale 15% off
Preview
sale 15% off
Preview
Standard
ISO 8124-6:2014 - Safety of toys
English language
27 pages
sale 15% off
Preview
sale 15% off
Preview

Standards Content (sample)

INTERNATIONAL ISO
STANDARD 8124-6
First edition
2014-08-15
Safety of toys —
Part 6:
Certain phthalate esters in toys and
children’s products
Sécurité des jouets —
Partie 6: Jouets et produits pour enfants — Dosage de certains
phtalates d’esters dans les jouets et produits pour enfants
Reference number
ISO 8124-6:2014(E)
ISO 2014
---------------------- Page: 1 ----------------------
ISO 8124-6:2014(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2014

All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form

or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior

written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of

the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2014 – All rights reserved
---------------------- Page: 2 ----------------------
ISO 8124-6:2014(E)
Contents Page

Foreword ........................................................................................................................................................................................................................................iv

Introduction ..................................................................................................................................................................................................................................v

1 Scope ................................................................................................................................................................................................................................. 1

2 Terms and definitions ..................................................................................................................................................................................... 1

3 Principle ........................................................................................................................................................................................................................ 2

4 Reagents ........................................................................................................................................................................................................................ 2

5 Apparatus ..................................................................................................................................................................................................................... 3

6 Selection of test portion ................................................................................................................................................................................ 4

7 Procedure..................................................................................................................................................................................................................... 4

7.1 Sample weighing ................................................................................................................................................................................... 4

7.2 Extraction .................................................................................................................................................................................................... 4

7.3 Sample solution for analysis ........................................................................................................................................................ 5

7.4 Determination ......................................................................................................................................................................................... 5

8 Calculation .................................................................................................................................................................................................................. 8

8.1 External Standard (ES) calculation ....................................................................................................................................... 8

8.2 Internal Standard (IS) calculation .......................................................................................................................................... 8

9 Quality control ........................................................................................................................................................................................................ 9

9.1 Limit of quantification (LOQ) ..................................................................................................................................................... 9

9.2 Method blank ............................................................................................................................................................................................ 9

9.3 Recovery ....................................................................................................................................................................................................... 9

9.4 Calibration check ................................................................................................................................................................................... 9

10 Precision ....................................................................................................................................................................................................................... 9

11 Test report ................................................................................................................................................................................................................... 9

Annex A (normative) Phthalate esters ............................................................................................................................................................10

Annex B (informative) Extraction apparatus ............................................................................................................................................11

Annex C (informative) Example of GC-MS conditions .......................................................................................................................13

Annex D (informative) Precision of the method ....................................................................................................................................16

Annex E (informative) Composite test .............................................................................................................................................................20

Annex F (informative) Background and rationale ...............................................................................................................................24

Bibliography .............................................................................................................................................................................................................................27

© ISO 2014 – All rights reserved iii
---------------------- Page: 3 ----------------------
ISO 8124-6:2014(E)
Foreword

ISO (the International Organization for Standardization) is a worldwide federation of national standards

bodies (ISO member bodies). The work of preparing International Standards is normally carried out

through ISO technical committees. Each member body interested in a subject for which a technical

committee has been established has the right to be represented on that committee. International

organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.

ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of

electrotechnical standardization.

The procedures used to develop this document and those intended for its further maintenance are

described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the

different types of ISO documents should be noted. This document was drafted in accordance with the

editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).

Attention is drawn to the possibility that some of the elements of this document may be the subject of

patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of

any patent rights identified during the development of the document will be in the Introduction and/or

on the ISO list of patent declarations received (see www.iso.org/patents).

Any trade name used in this document is information given for the convenience of users and does not

constitute an endorsement.

For an explanation on the meaning of ISO specific terms and expressions related to conformity

assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers

to Trade (TBT) see the following URL: Foreword - Supplementary information

The committee responsible for this document is Technical Committee ISO/TC 181, Safety of toys.

ISO 8124 consists of the following parts, under the general title Safety of toys:

— Part 1: Safety aspects related to mechanical and physical properties
— Part 2: Flammability
— Part 3: Migration of certain elements

— Part 4: Swings, slides and similar activity toys for indoor and outdoor family domestic use

— Part 6: Toys and children’s products — Determination of certain phthalate esters in toys and children’s

products
The following parts are under preparation:
— Part 5: Determination of total concentration of certain elements in toys
— Part 7: Finger paints — Requirements and test methods
— Part 8: Age determination guidelines
iv © ISO 2014 – All rights reserved
---------------------- Page: 4 ----------------------
ISO 8124-6:2014(E)
Introduction

This part of ISO 8124 is largely based upon the existing Chinese national standard GB/T 22048-2008.

Relevant standards of some countries and regions are referred to as well.

Considering the diversity of laws and regulations in different countries, this International Standard

has not set out limits for phthalate esters. It is intended to be used as a method standard in conformity

assessment. The user of this part of ISO 8124 is therefore advised to be aware of relevant national

requirements.

Whereas in some countries, phthalate ester requirements for toys are also applicable to children

products and whereas children product materials are generally similar to those of toys, this part of

ISO 8124 whose scope covers various materials can be applicable to both toys and children products.

Annex A is normative and Annex B, Annex C, Annex D, Annex E, and Annex F are for information purposes

only, but they are crucial and helpful for the correct interpretation of this part of ISO 8124.

© ISO 2014 – All rights reserved v
---------------------- Page: 5 ----------------------
INTERNATIONAL STANDARD ISO 8124-6:2014(E)
Safety of toys —
Part 6:
Certain phthalate esters in toys and children’s products

WARNING — Persons using this International Standard should be familiar with normal laboratory

practice. This International Standard 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 in accordance with this International

Standard be carried out by suitably trained staff.
1 Scope

This part of ISO 8124 specifies a method for the determination of di-n-butyl phthalate (DBP), benzyl

butyl phthalate (BBP), bis-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl

phthalate (DINP), and di-iso-decyl phthalate (DIDP) (see Annex A) in toys and children’s products.

This part of ISO 8124 is applicable to toys and children’s products which are made of plastics, textiles,

and coatings, etc. This International Standard has been validated for polyvinylchloride (PVC) plastics,

polyurethane (PU) plastics, and some representative paint coatings (see Annex D). It might also be

applicable to other phthalate esters and other products materials provided that adequate validation is

demonstrated.
2 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
2.1
laboratory sample

toy or children’s product in the form in which it is marketed or intended to be marketed

2.2
base material
material upon which coatings can be formed or deposited
2.3
coating

all layers of material formed or deposited on the base material of toys or children’s products, including

paints, varnishes, lacquers, inks, polymers, or other substances of a similar nature, whether they contain

metallic particles or not, no matter how they have been applied to the toy or children’s product, and

which can be removed by scraping with a sharp blade
2.4
scraping
mechanical removal of coatings down to but not including the base material
2.5
test portion

portion of homogeneous material taken from a corresponding part of the laboratory sample for analysis

© ISO 2014 – All rights reserved 1
---------------------- Page: 6 ----------------------
ISO 8124-6:2014(E)
2.6
composite test portion

mixed test portion formed by physically mixing several test portions of similar material

Note 1 to entry: This term excludes the compositing of dissimilar materials, for example, compositing textiles and

paint coatings are not permitted.
2.7
composite test
test performed on the composite test portion
2.8
limit of quantification
LOQ

lowest amount of the analyte in the sample that can be quantitatively determined with defined precision

under the stated experimental conditions
2.9
method blank

aliquot of solvents that is treated exactly as a sample including exposure to glassware, apparatus, and

conditions used for a particular test, but with no added sample

Note 1 to entry: Method blank data are used to assess contamination from the laboratory environment.

3 Principle

The test portion of a toy or children’s product is mechanically cut into small pieces which are then

extracted through a Soxhlet extractor or solvent extractor (see Annex B) with dichloromethane; after

which, the phthalate esters in the extract are determined qualitatively and quantitatively by gas

chromatograph-mass spectrometer (GC-MS).
4 Reagents

4.1 Dichloromethane, CAS No. 75-09-2, analytical grade or higher, free of phthalate esters.

4.2 Phthalate reference substances, DBP, BBP, DEHP, DNOP, DINP, and DIDP (see Annex A), minimum

of 95 % purity.

4.3 Stock solution, 100 mg/l of DBP, BBP, DEHP, DNOP each, and 500 mg/l of DINP, DIDP each in

dichloromethane (4.1).

Stock solution should be properly stored at 0 °C to 4 °C to prevent change of concentration. It is

recommended to prepare the solution at least every three months.
4.4 External Standard (ES) calibration solutions.

A series of calibration standard solutions (of at least five equidistant calibrations in the range of

0,4 mg/l to 10 mg/l for DBP, BBP, DEHP, and DNOP, 2 mg/l to 50 mg/l for DINP and DIDP) is prepared by

transferring 0,2 ml to 5 ml of the stock solution (4.3) to a 50 ml volumetric flask and making up to the

mark with dichloromethane.

Calibration standard solutions should be properly stored at 0 °C to 4 °C to prevent change of concentration.

It is recommended to prepare the solution at least monthly.
2 © ISO 2014 – All rights reserved
---------------------- Page: 7 ----------------------
ISO 8124-6:2014(E)
4.5 Internal Standard (IS) calibration solutions.

4.5.1 Internal reference substances, benzyl benzoate (BB, CAS No.120-51-4) or di-n-amyl phthalate

(DAP, CAS No.131-18-0) [also known as di-n-pentyl phthalate (DPP)], minimum of 95 % purity.

The internal reference substances should not be present in the test portion matrix. Other compounds

such as isotopically labelled phthalates can be used as alternative internal reference substances.

4.5.2 Internal stock solution, 250 mg/l of BB or DAP or others, in dichloromethane.

IS solutions should be properly stored at 0 °C to 4 °C to prevent change of concentration. It is recommended

to prepare these solutions at least every three months.
4.5.3 Internal Standard calibration solutions.

A series of calibration standard solutions (of at least five equidistant calibrations in the range of

0,4 mg/l to 10 mg/l for DBP, BBP, DEHP and DNOP, 2 mg/l to 50 mg/l for DINP and DIDP) is prepared

by transferring 0,2 ml to 5 ml of the stock solution (4.3) to a 50 ml volumetric flask and adding 2 ml of

the IS stock solution (4.5.2) before making up to the mark with dichloromethane, each of the calibration

standards containing 10 mg/l IS.

IS calibration solutions should be properly stored at 0 °C to 4 °C to prevent change of concentration. It is

recommended to prepare these solutions at least monthly.
5 Apparatus

Phthalate esters are common contaminants which can affect the test result even at a low level of

concentration. In order to prevent interference and cross-contamination, any type of plastic apparatus

that could affect the analysis should be avoided, and glassware and equipment should be scrupulously

cleaned before use.
5.1 Normal laboratory glassware.

5.2 Gas chromatography-mass spectrometer (GC-MS), with a capillary column coupled to a mass

spectrometric detector (electron ionization, EI) used for the analysis. See 7.4.1.

5.3 Soxhlet extractor, see Figure B.1.
5.4 Solvent extractor, see Figure B.2.
5.5 Extraction thimble, cellulose.
5.6 Cotton wool, for extraction thimble.
5.7 Analytical balance, capable of measuring to an accuracy of 0,001 g.
5.8 Concentration apparatus, for example, a rotary evaporator.

5.9 Solid phase extraction (SPE) cartridge, 1000 mg silica gel/6 ml tubes, or equivalent.

5.10 Volumetric flasks, of 5 ml, 10 ml, 25 ml, 50 ml, and 100 ml nominal capacity.

5.11 Pipettes, of 0,5 ml, 1 ml, 2 ml, 5 ml, and 10 ml nominal capacity.
© ISO 2014 – All rights reserved 3
---------------------- Page: 8 ----------------------
ISO 8124-6:2014(E)
5.12 Polytetrafluoroethylene (PTFE) membrane filter, of pore size 0,45 μm.
6 Selection of test portion

Use a scalpel or other appropriate cutting utensils to cut a representative portion from the laboratory

sample into small pieces. For coatings, remove each different coating from the laboratory sample by

scraping. Extra care shall be taken to minimize the inclusion of the base material. Each piece shall, in the

uncompressed condition, have no dimension greater than 5 mm and be mixed uniformly.

A test portion of less than 10 mg from a single laboratory sample shall not be tested.

NOTE Different countries or regions might have different legislation requirements for the minimum sample

mass.
Composite test can be used for screening. See Annex E.
7 Procedure
7.1 Sample weighing

Weigh, to the nearest 1 mg, approximately 1 g of the test portion into an extraction thimble (5.5). If 1 g

test portion cannot be obtained from a single laboratory sample, sampling as much as possible from

more than one laboratory samples, but 0,1 g should be a minimum test portion.
7.2 Extraction

Two optional extraction methods are described in the following, and the laboratory can select the most

suitable one at its discretion.
7.2.1 Method A

Place the thimble with test portion into the 150-ml Soxhlet extractor (5.3). In order to prevent the

sample from floating, add cotton wool (5.6) to the top of the thimble.

Add 120 ml of dichloromethane (4.1) into the 150-ml flask. Reflux for 6 h with no less than four reflux

cycles per hour.

After cooling, reduce the volume of the dichloromethane to about 10 ml using a suitable concentration

apparatus (5.8). Take care to avoid reduction to dryness.

When using a rotary evaporator, it is recommended that the temperature of the water bath is in the

range of 40°C to 50°C with a constant pressure between 30 kPa and 45 kPa.

NOTE During the refluxing and concentration steps, careful temperature control is necessary in order to

avoid loss of phthalate esters.
7.2.2 Method B

Place the thimble with test portion into the solvent extractor (5.4). In order to prevent the sample from

floating, add cotton wool (5.6) to the top of the thimble.

Add 80 ml of dichloromethane (4.1) into the receiver. Immerse for 1,5 h at about 80 °C and reflux for 1,5

h. At the end, concentrate the dichloromethane extract to about 10 ml.

NOTE During the refluxing and concentration steps, careful temperature control is necessary in order to

avoid loss of phthalate esters.
4 © ISO 2014 – All rights reserved
---------------------- Page: 9 ----------------------
ISO 8124-6:2014(E)
7.3 Sample solution for analysis

Filter the solution (7.2.1 or 7.2.2), which is obtained after the dichloromethane extract has been treated

according to the procedure specified in 7.3.1 or 7.3.2 where appropriate, with PTFE membrane filter

(5.12) for GC-MS (5.2) analysis.

If necessary, e.g. when the concentrated extract exhibits turbidity, before the filtering above, purify the

solution (7.2.1 or 7.2.2) with a pretreated SPE (5.9). Rinse the cartridge with 3 ml of dichloromethane

three times and collect the eluate.

NOTE Pretreat the SPE cartridge with approximate 10 ml of dichloromethane before purification. Discard

the effluent.
7.3.1 For quantification by External Standard calibration

Transfer the extract or the eluate into a 25-ml volumetric flask and make up to the mark with

dichloromethane.

NOTE The volume of the final solution can be adjusted according to the test specimen mass and concentration.

7.3.2 For quantification by Internal Standard calibration

Transfer the extract or the eluate and 1 ml of the IS stock solution (4.5.2) into a 25-ml volumetric flask

and make up to the mark with dichloromethane. The final solution contains 10 mg/l of IS.

NOTE The volume of both IS solution and the final solution can be adjusted according to the test specimen

mass and concentration. The concentration of IS in the final test solution should be the same as that of standard

calibration solutions (4.5.3).
7.4 Determination
7.4.1 GC-MS conditions

Due to the variation of instruments in different laboratories, no universal applicable instructions can

be provided for chromatographic analysis. The following general GC-MS operating conditions have been

found suitable, and an example of operating conditions is given in Annex C.

a) Column: capillary column, non-polar (phenylarylene polymer equivalent to 5 % phenylmethyl

polysiloxane), or equivalent.
b) Oven temperature program.
c) Carrier gas: helium or hydrogen, constant flow.
d) Injector system: split or splitless.
e) Ionization method: electron ionization (EI), 70 eV.

f) Determination: Identification by full scan mode, quantification by selected ion monitoring (SIM)

mode simultaneously.
7.4.2 Identification

Identify the compound by matching both retention times and relative intensities of the diagnostic ions

of test solution and standard solution.

The target compound is considered to be identified in the test solution if the following criteria are

fulfilled:

a) the ratio of the retention time of the analyte to that of the IS, i.e. the relative retention time of the

analyte, corresponds to that of the calibration solution at a tolerance of ±0,5 %;

© ISO 2014 – All rights reserved 5
---------------------- Page: 10 ----------------------
ISO 8124-6:2014(E)

b) the diagnostic ions (see Table C.1) are present at the substance-specific retention time;

c) the relative intensities of the diagnostic ions (refer to Table C.1) in full scan, expressed as a percentage

of the intensity of the most intense ion, shall correspond to those of the calibration standard at

comparable concentrations, measured under the same conditions, within the tolerances in Table 1.

Table 1 — Maximum permitted tolerances for relative ion intensities using a range of mass

spectrometric techniques
Relative intensity Maximum permitted tolerances
(% of base peak) (relative intensity)
>50 % ±10 %
>20 % to 50 % ±15 %
>10 % to 20 % ±20 %
≤10 % ±50 %

NOTE Some isomers of DINP or DIDP can interfere with the identification of DINP or DIDP. For example, Di-

propylheptyl phthalate (DPHP, CAS No. 53306–54–0) is one of the isomers of DIDP, it is theoretically difficult to

separate DPHP from DIDP, but they can be recognized through the feature of peak, retention time, and abundance

ratio.
7.4.3 Calibration
7.4.3.1 General

Two optional calibration methods, External Standard (ES) (7.4.3.2) and Internal Standard (IS) (7.4.3.3),

are described in the following. Either ES or IS can be used for calibration. Laboratories can choose the

suitable calibration method according to their best practice (see Annex F).

A calibration curve shall be established for either method. A minimum of five equidistant calibration

standard solutions (4.4 or 4.5.3) shall be prepared. Quantification is based on the measurement of the

peak area. The correlation coefficient (r), of each calibration curve shall be at least 0,995.

The isomers of DINP and DIDP shall be quantified using baseline integration.

NOTE 1 DINP and DIDP are available as different isomeric mixtures under different CAS numbers. Since the

chromatogram of the GC-MS is different for each mixture, the laboratory should choose the reference substance

that matches as closely as possible the isomeric ratio to the phthalates in the test portion and report the CAS No.

of the reference material used in accordance with 11 f).

NOTE 2 Due to the existence of inseparable isomers, the peaks of DNOP, DINP and DIDP are partially overlapped.

The interference of this can be minimized effectively when m/z = 279 (DNOP), m/z = 293 (DINP), and m/z = 307

(DIDP) are selected as quantification ions respectively.
7.4.3.2 External Standard (ES) calibration

Integrate the peak areas of the target quantification ions (see Table C.1) in the chromatograph by ES

calibration.
6 © ISO 2014 – All rights reserved
---------------------- Page: 11 ----------------------
ISO 8124-6:2014(E)

To establish the calibration curve, the response A is plotted against the concentration C in accordance

with Formula (1):
A = (a × C)+ b (1)
1 1
where

A is the peak area or sum of peak areas of the individual phthalate in the calibration solution;

a is the slope of the calibration curve;

C is the concentration of the individual phthalate in the calibration solution, in mg/l;

b is the ordinate intercept of the calibration curve.
7.4.3.3 Internal Standard (IS) calibration

Integrate the peak areas of the target quantification ions (see Table C.1) in the chromatograph by IS

calibration.

To establish the calibration curve, the response A/A is plotted against the concentration ratio C/C in

IS IS
accordance with Formula (2):
 
A C
=×a +b
 
A C
IS  IS 
(2)
where

A is the peak area or sum of peak areas of the individual phthalate in the calibration solution;

A is the peak area of the IS in the calibration solution;
a is the slope of the calibration curve;

C is the concentration of the individual phthalate in the calibration solution, in mg/l;

C is the concentration of the IS in the calibration solution in mg/l;
b is the ordinate intercept of the calibration curve.

NOTE It is common practice to set the IS concentration (C ) to 1 mg/l for the IS methods when the amount

and concentration of IS added to the test portion and calibrants prior to injection are the same.

© ISO 2014 – All rights reserved 7
---------------------- Page: 12 ----------------------
ISO 8124-6:2014(E)
8 Calculation
8.1 External Standard (ES) calculation

Calculate the mass fraction of the individual phthalate in the test portion by using Formula (3) after

solving Formula (1):
()Ab− V 1
w = ××D× (3)
a m 10000
where

w is the concentration of the individual phthalate found in the test portion, in %;

A is the peak area or sum of peak areas of the individual phthalate in the test solution;

b is the ordinate intercept of the calibration curve, obtained from Formula (1);

a is the slope of the calibration curve, obtained from Formula (1);
V is the volume of the final solution, in ml;
m is the mass of the test portion, in g;
D is the dilution factor.

The result shall be expressed in percentage by weight (%) and reported to three significant figures.

The response value of the tested phthalate in the calibration solution and test solution should be within

the instrument detection linear range. If necessary, further diluted solution with dichloromethane

should be prepared.
8.2 Internal Standard (IS) calculation

Calculate the mass fraction of the individual phthalate in the test portion by using Formula (4) after

solving Formula (2):
A C V 1
w =−()b ×× ××D (4)
S 2
A a m 10000
IS 2
where

w is the concentration of the individual phthalate found in the test portion, in %;

A is the peak area or sum of peak areas of the individual phthalate in the test solution;

A is the peak area of the IS in the test solution;

b is the ordinate intercept of the calibration curve, obtained from Formula (2);

C is the concentration of the IS, in the calibration solution, in mg/l;
a is the slope of the calibration curve, obtained from Formula (2);
V is the volume of the final solution, in ml;
m is the mass of the test portion, in g;
D is the dilution factor.
8 © ISO 2014 – All rights reserv
...

DRAFT INTERNATIONAL STANDARD ISO/DIS 8124-6
ISO/TC 181 Secretariat: DS
Voting begins on Voting terminates on
2013-03-18 2013-06-18

INTERNATIONAL ORGANIZATION FOR STANDARDIZATION • МЕЖДУНАРОДНАЯ ОРГАНИЗАЦИЯ ПО СТАНДАРТИЗАЦИИ • ORGANISATION INTERNATIONALE DE NORMALISATION

Safety of toys —
Part 6:
Toys and children's products — Determination of phthalate
plasticizers in polyvinyl chloride plastics
Sécurité des jouets —

Partie 6: Jouets et produits pour enfants — Dosage des plastifiants à base de phtalate dans les plastiques en

chlorure de polyvinyl
ICS 97.200.50

To expedite distribution, this document is circulated as received from the committee

secretariat. ISO Central Secretariat work of editing and text composition will be undertaken at

publication stage.

Pour accélérer la distribution, le présent document est distribué tel qu'il est parvenu du

secrétariat du comité. Le travail de rédaction et de composition de texte sera effectué au

Secrétariat central de l'ISO au stade de publication.

THIS DOCUMENT IS A DRAFT CIRCULATED FOR COMMENT AND APPROVAL. IT IS THEREFORE SUBJECT TO CHANGE AND MAY NOT BE

REFERRED TO AS AN INTERNATIONAL STANDARD UNTIL PUBLISHED AS SUCH.

IN ADDITION TO THEIR EVALUATION AS BEING ACCEPTABLE FOR INDUSTRIAL, TECHNOLOGICAL, COMMERCIAL AND USER PURPOSES, DRAFT

INTERNATIONAL STANDARDS MAY ON OCCASION HAVE TO BE CONSIDERED IN THE LIGHT OF THEIR POTENTIAL TO BECOME STANDARDS TO

WHICH REFERENCE MAY BE MADE IN NATIONAL REGULATIONS.

RECIPIENTS OF THIS DRAFT ARE INVITED TO SUBMIT, WITH THEIR COMMENTS, NOTIFICATION OF ANY RELEVANT PATENT RIGHTS OF WHICH

THEY ARE AWARE AND TO PROVIDE SUPPORTING DOCUMENTATION.
© International Organization for Standardization, 2013
---------------------- Page: 1 ----------------------
ISO/DIS 8124-6
Copyright notice

This ISO document is a Draft International Standard and is copyright-protected by ISO. Except as permitted

under the applicable laws of the user’s country, neither this ISO draft nor any extract from it may be

reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic,

photocopying, recording or otherwise, without prior written permission being secured.

Requests for permission to reproduce should be addressed to either ISO at the address below or ISO’s

member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Reproduction may be subject to royalty payments or a licensing agreement.
Violators may be prosecuted.
ii © ISO 2013 – All rights reserved
---------------------- Page: 2 ----------------------
ISO/DIS 8124-6
Contents Page
Foreword………………………………………………………………..…………………………….………….............iv

1 Scope ...................................................................................................................................................... 1

2 Normative references ............................................................................................................................ 1

3 Terms and definitions ........................................................................................................................... 1

4 Principle.................................................................................................................................................. 2

5 Standards and reagents ........................................................................................................................ 2

6 Apparatus ............................................................................................................................................... 3

7 Selection of test portions ..................................................................................................................... 3

8 Procedure ............................................................................................................................................... 4

8.1 Sample weighing ................................................................................................................................... 4

8.2 Extraction ............................................................................................................................................... 4

8.2.1 Method A ................................................................................................................................................ 4

8.2.2 Method B ................................................................................................................................................ 4

8.3 Sample solution for analysis ................................................................................................................ 4

8.3.1 For quantification by external standard calibration .......................................................................... 5

8.3.2 For quantification by internal standard calibration ........................................................................... 5

8.4 Determination ........................................................................................................................................ 5

8.4.1 GC-MS conditions ................................................................................................................................. 5

8.4.2 Identification .......................................................................................................................................... 5

8.4.3 Calibration .............................................................................................................................................. 6

9 Calculation ............................................................................................................................................. 7

9.1 ES calculation ........................................................................................................................................ 7

9.2 IS calculation ......................................................................................................................................... 7

10 Quality control ....................................................................................................................................... 8

10.1 Limit of Quantification (LOQ) ............................................................................................................... 8

10.2 Method blank test .................................................................................................................................. 8

10.3 Recovery................................................................................................................................................. 8

10.4 Calibration check ................................................................................................................................... 8

11 Precision................................................................................................................................................. 9

12 Test report .............................................................................................................................................. 9

Annex A (normative) Phthalates esters ........................................................................................................ 10

Annex B (informative) Extraction apparatus ................................................................................................ 11

Annex C (informative) Example of GC-MS conditions ................................................................................ 13

Annex D (informative) Precision of the method ........................................................................................... 15

Annex E (informative) Composite test .......................................................................................................... 18

E.1 Introduction .......................................................................................................................................... 18

E.2 Preparation of composite test portion .............................................................................................. 18

E.3 Testing procedure ............................................................................................................................... 18

E.4 Calculation ........................................................................................................................................... 18

E.5 Judgment for next action.................................................................................................................... 19

E.6 Test report ............................................................................................................................................ 19

E.7 Example ................................................................................................................................................ 20

Annex F (informative) Background and rationale ........................................................................................ 21

© ISO 2013 — All rights reserved iii
---------------------- Page: 3 ----------------------
ISO/DIS 8124-6

F.1 Introduction ......................................................................................................................................... 21

F.2 Other phthalate esters in toys and children’s products ................................................................. 21

F.3 Sample preparation, extraction and determination methods ........................................................ 21

F.4 ES and IS Calibration ......................................................................................................................... 22

F.5 Materials that may contain phthalate esters .................................................................................... 22

Bibliography ..................................................................................................................................................... 24

iv © ISO 2013 — All rights reserved
---------------------- Page: 4 ----------------------
ISO/DIS 8124-6
Foreword

ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies

(ISO member bodies). The work of preparing International Standards is normally carried out through ISO

technical committees. Each member body interested in a subject for which a technical committee has been

established has the right to be represented on that committee. International organizations, governmental and

non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the

International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.

International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.

The main task of technical committees is to prepare International Standards. Draft International Standards

adopted by the technical committees are circulated to the member bodies for voting. Publication as an

International Standard requires approval by at least 75 % of the member bodies casting a vote.

Attention is drawn to the possibility that some of the elements of this document may be the subject of patent

rights. ISO shall not be held responsible for identifying any or all such patent rights.

ISO 8124-6 was prepared by Technical Committee ISO/TC 181, Safety of toys.

ISO 8124 consists of the following parts, under the general title Safety of toys.

— Part 1: Safety aspects related to mechanical and physical properties
— Part 2: Flammability
— Part 3: Migration of certain elements

— Part 4: Swings, slides and similar activity toys for indoor and outdoor family domestic use

— Part 5: Total concentration of certain elements of toys (in preparation)

— Part 6: Determination of certain phthalate esters in toys and children’s products

— Part 7: Finger paints (in preparation)
— Part 8: Age determination guidelines (in preparation)
© ISO 2013 — All rights reserved v
---------------------- Page: 5 ----------------------
DRAFT INTERNATIONAL STADARD ISO/DIS 8124-6
Safety of toys – Part 6: Determination of certain phthalate
esters in toys and children’s products

WARNING — Persons using this International Standard should be familiar with normal laboratory

practice. This International Standard 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 in accordance to this International

Standard be carried out by suitably trained staff.
1 Scope

This part of ISO 8124 specifies a method for the determination of di-n-butyl phthalate (DBP), benzyl butyl

phthalate (BBP), bis (2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl phthalate

(DINP) and di-iso-decyl phthalate (DIDP) (see Annex A) in toys and children’s products.

This part of ISO 8124 is applicable to toys and children’s products which are made of plastics, textiles, coating.

This standard has been validated for polyvinylchloride (PVC) plastics, polyurethane (PU) plastics and some

representative paint coatings (see Annex D). It may also be applicable to other phthalate esters and other

products materials provided that adequate validation is demonstrated.
2 Normative references
There are no normative references in this document.
3 Terms and definitions

For the purposes of this part of ISO 8124, the following terms and definitions apply.

3.1
laboratory sample

toys or children’s products in the form in which it is marketed or intended to be marketed.

3.2
base material
material upon which coatings may be formed or deposited
3.3
coating

all layers of material formed or deposited on the base material of a toy, including paints, varnishes, lacquers,

inks, polymers or other substances of a similar nature, whether they contain metallic particles or not, no

matter how they have been applied to the toy, and which can be removed by scraping with a sharp blade

3.4
scraping

mechanical removal of coatings down to the base material without damaging the substrate material

© ISO 2013 — All rights reserved 1
---------------------- Page: 6 ----------------------
ISO/DIS 8124-6
3.5
test portion

homogeneous material taken from corresponding part of the laboratory sample for analysis

3.6
composite test portion

a mixed test portion formed by physically mixing several test portions of similar material

NOTE This term precludes the compositing of dissimilar materials e.g. compositing textiles and paint coatings is not

permitted.
3.7
composite test
test performed on the composite test portions
3.8
limit of quantification (LOQ)

the lowest amount of the analyte in the sample that can be quantitatively determined with defined precision

under the stated experimental conditions
3.9
method blank

an aliquot of solvents that is treated exactly as a sample including exposure to glassware, apparatus and

conditions used for a particular test, but with no added sample. Method blank data are used to assess

contamination from the laboratory environment.
4 Principle

The test portion of toys and children’s products is mechanically cut into small pieces which are then extracted

through a Soxhlet extractor or solvent extractor (see Annex B) with dichloromethane, after which the phthalate

esters in the extract are determined qualitatively and quantitatively by gas chromatograph-mass spectrometer

(GC-MS).
5 Standards and reagents

5.1 Dichloromethane, CAS No. 75-09-2, analytical grade or higher, free of phthalate esters.

5.2 Phthalate reference substances, DBP, BBP, DEHP, DNOP, DINP and DIDP, minimum 95 % purity,

see Annex A.

5.3 Stock solution, 0,1 g/l of DBP, BBP, DEHP, DNOP each and 0,5 g/l of DINP, DIDP each in

dichloromethane (5.1).

NOTE Stock solution should be properly stored at 0°C to 4°C to prevent change of concentration. It is recommended

to prepare the solution at least every three months.
5.4 External standard (ES) calibration solutions

A series of calibration standard solutions (of at least five equidistant calibrations in the range 0.4 mg/l to 10

mg/l for DBP, BBP, DEHP and DNOP, 2 mg/l to 50 mg/l for DINP and DIDP) are prepared by transferring 0.2

ml to 5 ml of the stock solution (5.3) to a 50 ml volumetric flask and making up to the mark with

dichloromethane.

NOTE Calibration standard solutions should be properly stored at 0°C to 4°C to prevent change of concentration. It is

recommended to prepare the solution at least monthly.
5.5 Internal standard (IS) calibration solutions
2 © ISO 2013 — All rights reserved
---------------------- Page: 7 ----------------------
ISO/DIS 8124-6

5.5.1 Internal reference substances, benzyl benzoate (BB, CAS No.120-51-4) or di-n-amyl phthalate (DAP,

CAS No.131-18-0) (also known as di-n-pentyl phthalate (DPP)), minimum 95 % purity.

NOTE The internal reference substances should not be present in the test portion matrix. Other compounds such as

isotopically labelled phthalates can be used as alternative internal reference substances.

5.5.2 Internal stock solution, 0,25 g/l of BB or DAP or others, in dichloromethane.

NOTE IS solutions should be properly stored at 0°C to 4°C to prevent change of concentration. It is recommended to

prepare these solutions at least every three months.
5.5.3 Internal standard calibration solutions

A series of calibration standard solutions (of at least five equidistant calibrations in the range 0.4 mg/l to 10

mg/l for DBP, BBP, DEHP and DNOP, 2 mg/l to 50 mg/l for DINP and DIDP) are prepared by transferring 0.2

ml to 5 ml of the stock solution (5.3) to a 50 ml volumetric flask and adding 2 ml of the IS stock solution (5.5.2)

before making up to the mark with dichloromethane, each of the calibration standards containing 10 mg/l IS.

NOTE IS calibration solutions should be properly stored at 0°C to 4°C to prevent change of concentration. It is

recommended to prepare these solutions at least monthly.
6 Apparatus

NOTE Phthalate ester is a common contaminant which may affect the test result even just at a low level of

concentration. In order to prevent interference and cross-contamination, any type of plastic apparatus that could affect the

analysis should be avoided, and glassware and equipment should be scrupulously cleaned before use.

6.1 Normal laboratory glassware

6.2 Gas chromatography-mass spectrometer (GC-MS), with a capillary column coupled to a mass

spectrometric detector (electron ionization, EI) used for the analysis. See 8.4.1.

6.3 Soxhlet extractor, see figure B.1.
6.4 Solvent extractor, see figure B.2.
6.5 Extraction thimble, cellulose.
6.6 Cotton wool, for extraction thimble.
6.7 Analytical balance, capable of measuring to an accuracy of 0,001 g.
6.8 Concentration apparatus, for example a rotary evaporator.

6.9 Solid phase extraction (SPE) cartridge, 1000 mg silica gel / 6 ml tubes, or equivalent.

6.10 Volumetric flasks, of 5 ml, 10 ml, 25 ml, 50 ml and 100 ml nominal capacity.

6.11 Pipettes, of 0,5 ml, 1 ml, 2 ml, 5 ml and 10 ml nominal capacity.
6.12 Polytetrafluoroethylene (PTFE) membrane filter, of pore size 0,45 μm.
7 Selection of test portions

Use a scalpel or other appropriate cutting utensils to cut a representative portion from the laboratory sample

into small pieces. For coatings, remove each different coating of the laboratory sample by scraping from the

base material. Extra care shall be taken to minimize the inclusion of the base material. Each piece shall, in the

© ISO 2013 — All rights reserved 3
---------------------- Page: 8 ----------------------
ISO/DIS 8124-6

uncompressed condition, have no dimension greater than 5 mm and be mixed uniformly.

A test portion of less than 10 mg from a single laboratory sample shall not be tested.

NOTE Different countries or regions may have different legislation requirements for the minimum sample mass.

Composite test may be used for a screen test. (see Annex E).
8 Procedure
8.1 Sample weighing

Weigh, to the nearest 1 mg, approximately 1,0 g of the test portion into an extraction thimble (6.5). If 1,0 g test

portion cannot be obtained, sampling as much as possible from more than one laboratory samples, but 0,1g

test portion should be a minimum weight.
8.2 Extraction

Two alternative extraction method A (8.2.1) and method B (8.2.2) are described in the following.

8.2.1 Method A

Place the thimble with test portion into 150ml soxhlet extractor (6.3). In order to prevent the sample from

floating, add cotton wool (6.6) to the top of the thimble.

Add 120 ml of dichloromethane (5.1) into the 150 ml flask. Reflux for 6 h with no less than four reflux cycles

per hour.

After cooling, reduce the volume of the dichloromethane to about 10 ml using a suitable concentration

apparatus (6.8), take care to avoid reduction to dryness.

When using a rotary evaporator, it is recommended that the temperature of water bath is in the range of 40°C

to 50°C with a constant pressure between 30 kPa and 45 kPa.

NOTE Care should be taken to condensate temperature on refluxing or concentrating procedures to preventing lose

of phthalate esters.
8.2.2 Method B

Place the thimble with test portion into solvent extractor (6.4). In order to prevent the sample from floating, add

cotton wool (6.6) to the top of the thimble.

Add 80 ml of dichloromethane (5.1) into the receiver. Immerse for 1,5 h at about 80 °C and reflux for 1,5 h. At

the end, concentrate the dichloromethane extract to about 10 ml.

NOTE Care should be taken to condensate temperature on refluxing or concentrating procedures to preventing lose

of phthalate esters.
8.3 Sample solution for analysis

Filter the solution (8.2.1 or 8.2.2), which is obtained after the dichloromethane extract has been treated

according to the following procedure as specified in clause 8.3.1 or 8.3.2 where appropriate, with PTFE

membrane filter (6.12) for GC-MS (6.2) analysis.

If necessary, e.g. when the concentrated extract exhibits turbidity, before the filtering above, purify the solution

(8.2.1 or 8.2.2) with a pretreated SPE (6.9), Rinse the cartridge with 3 × 3 ml of dichloromethane and collect

the eluate.
4 © ISO 2013 — All rights reserved
---------------------- Page: 9 ----------------------
ISO/DIS 8124-6

NOTE Pretreated the SPE cartridge with approximate 10 ml of dichloromethane before purification, discard the

effluent.
8.3.1 For quantification by external standard calibration

Transfer the extract or the eluate into a 25 ml volumetric flask and make up to the mark by dichloromethane.

NOTE The volume of the final solution can be adjusted according to the test specimen mass and concentration.

8.3.2 For quantification by internal standard calibration

Transfer the extract or the eluate and 1 ml of the IS stock solution (5.5.2) into a 25 ml volumetric flask and

make up to the mark by dichloromethane. The final solution contains 10 mg/l of IS.

NOTE The volume of both IS solution and the final solution can be adjusted according to the test specimen mass and

concentration,but the concentration of IS in the final solution should be the same with that of standard calibration

solutions (5.5.3).
8.4 Determination
8.4.1 GC-MS conditions

Due to the variation of instruments in different laboratories, no universal applicable instructions can be

provided for chromatographic analysis. The following general GC-MS operating conditions have been found

suitable, and an example of operating conditions is given in Annex C.

a) Column: capillary column, non-polar (phenyl-arylene-polymer equivalent to 5 % phenyl-methylpoly-

siloxane), or equivalent.
b) Oven temperature program.
c) Carrier gas: helium or hydrogen, constant flow.
d) Injector system: split or splitless.
e) Ionization method: electron ionization (EI), 70 eV.

f) Determination: Identification by full scan mode, quantification by Selected Ion Monitoring (SIM) mode

simultaneously.
8.4.2 Identification

Identify the compound by matching both retention times and relative intensities of the diagnostic ions of test

portion and standard solution.
The target compound is identified in the test portion if:

1) The ratio of the retention time of the analyte to that of the IS, i.e. the relative retention time of the

analyte, corresponds to that of the calibration solution at a tolerance of ± 0,5 %.

2) The diagnostic ions (see Table C.1) are present at the substance-specific retention time.

3) The relative intensities of the diagnostic ions (refer to table C.1) in full scan correspond to those of

the calibration standard. (Relative intensity > 50 %, the maximum permitted tolerance being 10 %;

relative intensity within 20 % to 50 %, the maximum permitted tolerance being 15 %; relative intensity

within 10 % to 20 %, the maximum permitted tolerance being 20 %; relative intensity ≤ 10 %, the

maximum permitted tolerance being 50 %)
© ISO 2013 — All rights reserved 5
---------------------- Page: 10 ----------------------
ISO/DIS 8124-6

NOTE Some isomers of DINP or DIDP can interfere the identification of DINP or DIDP, just like Di-propyl-heptyl-

phthalate (DPHP, CAS No. 53306-54-0) is one of the isomers of DIDP, it is difficult to separate theoretically from DIDP,

but they can be recognized through the feature of peak, retention time and abundance ratio.

8.4.3 Calibration
8.4.3.1 General

Two alternative calibration methods, ES (8.4.3.2) and IS (8.4.3.3), are described in the following. Either ES or

IS can be used for calibration. Laboratories can choose the suitable calibration method according to their best

practise (see Annex F).

A calibration curve shall be constructed for either method. A minimum of five equidistant calibration standard

solutions (5.4 or 5.5.3) shall be prepared. Quantification is based on the measurement of the peak area. The

correlation coefficient, r , of each calibration curves should be at least 0,995.

The isomers of DINP and DIDP shall be quantified using baseline integration.

NOTE 1 DINP and DIDP are available as different isomeric mixtures under different CAS numbers. Since the response

of the GC-MS is different for each mixture, the laboratory should choose the reference substance that matches as closely

as possible the isomeric ratio to the phthalates in the test portion and report the CAS No. of the reference material used in

accordance with 12 f).

NOTE 2 Due to the existence of inseparable isomers, the peaks of DINP, DNOP and DIDP are partially overlapped.

The interference of this can be minimized effectively when m/z = 279 (DNOP), m/z = 293 (DINP) and m/z = 307 (DIDP)

are selected as quantification ions respectively.
8.4.3.2 ES calibration

Determine the peak areas of the target quantification ions (see Table C.1) in the chromatograph by ES

calibration.

To construct the calibration curve, the response A is plotted against the concentration c in accordance with

Equation (1):
A = a× c + b (1)
1 1
where

A is the peak area or sum of peak areas of the individual phthalates in the calibration solution;

a is the slope of the calibration curve;

c is the concentration of the individual phthalate in the calibration solution in mg/l;

b is the ordinate intercept of the calibration curve.
8.4.3.3 IS calibration

Determine the peak areas of the target quantification ions (see Table C.1) in the chromatograph by IS

calibration.

To produce the calibration curve, the response A/A is plotted against the concentration ratio c/c in

IS IS
accordance with Equation (2):
A c
(2)
a  b
2 2
A c
IS IS
6 © ISO 2013 — All rights reserved
---------------------- Page: 11 ----------------------
ISO/DIS 8124-6
where

A is the peak area or sum of peak areas of the individual phthalate in the calibration solution;

A is the peak area of the IS in the calibration solution;
a is the slope of the calibration curve;

c is the concentration of the individual phthalate in the calibration solution in mg/l;

c is the concentration of the IS in mg/l;
b is the ordinate intercept of the calibration curve.

NOTE It is common practice to set the IS concentration (c ) to 1 for the IS methods when the amount and

concentration of IS added to the test portion and calibrants prior to injection are the same.

9 Calculation
9.1 ES calculation

Calculate the mass fraction of the individual phthalate from the calibration by using Equation (3) after solving

Equation (1):
(Ab ) V 1
w   D (3)
a m 10000
where

w is the concentration of the individual phthalate found in the test portion, in %;

A is the peak area or sum of peak areas of the individual phthalate in the test solution;

b is the ordinate intercept of the calibration curve, obtained from Equation (1);

a is the slope of the calibration curve, obtained from Equation (1);
V is the volume of the final solution, in ml;
m is the mass of the test portion, in gram;
D is the dilution factor.

The result shall be expressed in percentage by weight (%) and reported to three significant figures.

NOTE The response value of the tested phthalate in the calibration
...

Questions, Comments and Discussion

Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.