ISO 8124-6:2014
(Main)Safety of toys — Part 6: Certain phthalate esters in toys and children's products
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
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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
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ISO 8124-6:2014(E)
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ii © ISO 2014 – All rights reserved
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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
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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
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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.
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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
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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.
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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.
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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.
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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 %;
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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.
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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;
1
C is the concentration of the individual phthalate in the calibration solution, in mg/l;
b is the ordinate intercept of the calibration curve.
1
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
22
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;
IS
a is the slope of the calibration curve;
2
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;
IS
b is the ordinate intercept of the calibration curve.
2
NOTE It is common practice to set the IS concentration (C ) to 1 mg/l for the IS methods when the amount
IS
and concentration of IS added to the test portion and calibrants prior to injection are the same.
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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
1
w = ××D× (3)
S
a m 10000
1
where
w is the concentration of the individual phthalate found in the test portion, in %;
S
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);
1
a is the slope of the calibration curve, obtained from Formula (1);
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
IS
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 %;
S
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;
IS
b is the ordinate intercept of the calibration curve, obtained from Formula (2);
2
C is the concentration of the IS, in the calibration solution, in mg/l;
IS
a is the slope of the calibration curve, obtained from Formula (2);
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
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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.
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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
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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
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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
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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
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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)
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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
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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
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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
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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.
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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 %)
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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
2
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;
1
c is the concentration of the individual phthalate in the calibration solution in mg/l;
b is the ordinate intercept of the calibration curve.
1
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
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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;
IS
a is the slope of the calibration curve;
2
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;
IS
b is the ordinate intercept of the calibration curve.
2
NOTE It is common practice to set the IS concentration (c ) to 1 for the IS methods when the amount and
IS
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):
(Ab ) V 1
1
w D （3）
S
a m 10000
1
where
w is the concentration of the individual phthalate found in the test portion, in %;
S
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);
1
a is the slope of the calibration curve, obtained from Equation (1);
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
...
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