Plasticizers in toys: Method validation using toy

Transcription

Final Report
Plasticizers in toys:
Method validation using toy samples
and analysis of toys
2005-08-29
by
Franz Fiala
Consumer Council, Austrian Standards Institute
Ingrid Steiner
Institute of Chemical Engineering
Division Food Chemistry and Food Technology
Vienna University of Technology
General study data
Authors
Dr. Franz Fiala
Austrian Standards Institute
Consumer Council
Heinestraße 38
1020 Vienna
Austria
tel.: 0043 1 213 00 709
fax: 0043 1 213 00 328
e-mail: [email protected]
web: http://www.verbraucherrat.at
Prof. Dr. Ingrid Steiner
Institute of Chemical Engineering
Division Food Chemistry and Food Technology
Vienna University of Technology
Gertreidemarkt 9
1060 Vienna
Austria
tel.: 0043 1 58801 16002
fax: 0043 1 58801 16099
e-mail: [email protected]
Laboratory work
Chemcon GmbH
Zirkusgasse 23
1020 Vienna
Austria
Time schedule
June 2004 - August 2005
Context
Follow-up of a study finalised in 2003 on the determination of
plasticizers relating to EU Commission Mandate M/229
"Organic chemical compounds in toys other than chemical toys“
given to CEN to prepare European standards in this area
2
Contents
1
Introduction.............................................................................................................................. 5
2
Experimental ............................................................................................................................ 6
2.1
General............................................................................................................................... 6
2.2
Toys investigated................................................................................................................ 7
2.3
Analysis by infrared-spectroscopy...................................................................................... 9
2.3.1
Apparatus ...................................................................................................................... 9
2.3.2
Procedure:..................................................................................................................... 9
2.4
Analysis by solvent-extraction followed by GC/MS-analysis .............................................. 9
2.4.1
Chemicals.................................................................................................................... 10
2.4.2
Apparatus .................................................................................................................... 10
2.4.3
Procedure.................................................................................................................... 11
2.5
Validation of method using toy samples ........................................................................... 12
2.5.1
General........................................................................................................................ 12
2.5.2
Procedure.................................................................................................................... 12
2.5.3
Head-over- heel-extractor ........................................................................................... 13
2.5.4
Chemicals.................................................................................................................... 14
2.5.5
Apparatus .................................................................................................................... 15
2.5.6
Preparation of calibration standards............................................................................ 16
2.5.7
Results ........................................................................................................................ 17
2.5.7.1
2.5.7.1.1
Precision in the presence of sample 13 “Rubba Duck”................................... 17
2.5.7.1.2
Precision in the presence of sample 28 “Squirting Cube”............................... 21
2.5.7.2
Recovery ............................................................................................................. 25
2.5.7.2.1
Recovery of plasticizers in the presence of sample 13 “Rubba Duck” ........... 25
2.5.7.2.2
Recovery of plasticizers in the presence of sample 28 “Squirting Cube” ....... 26
2.5.7.3
Linearity ............................................................................................................... 27
2.5.7.3.1
Linearity of plasticizers in the presence of sample 13 “Rubba Duck” ............. 27
2.5.7.3.2
Linearity of plasticizers in the presence of sample 28 “Squirting Cube” ......... 28
2.5.7.4
2.6
Precision.............................................................................................................. 17
Limit of Detection (LOD) / Limit of Quantification (LOQ) ..................................... 29
2.5.7.4.1
LOD and LOQ in the presence of sample 13 “Rubba Duck” .......................... 29
2.5.7.4.2
LOD and LOQ in the presence of sample 28 “Squirting Cube” ...................... 30
2.5.7.5
Specificity ............................................................................................................ 30
2.5.7.6
Robustness/ruggedness...................................................................................... 31
2.5.7.7
Stability of standard solutions.............................................................................. 31
Analysis of real samples................................................................................................... 32
2.6.1
General........................................................................................................................ 32
3
3
2.6.2
Results migration tests ................................................................................................ 32
2.6.3
Determination of the total content of plasticizers in two toy samples .......................... 35
2.6.3.1
Chemicals............................................................................................................ 35
2.6.3.2
Procedure ............................................................................................................ 35
2.6.3.3
Results................................................................................................................. 35
Discussion of Results ........................................................................................................... 35
Annex A - Pictures of toys ........................................................................................................... 37
Annex B - fex-IKA 50 solvent extractor....................................................................................... 41
Annex C - Chromatograms of solvent extracts.......................................................................... 42
Annex D - Cut toy samples .......................................................................................................... 46
4
1 Introduction
The authors of this report acted as a lead laboratory in the preparation of European standards for
organic chemicals in toys and developed a method for the determination of 21 plasticizers
including citrates, adipates, azelates, sebacate, benzoates, phosphates and phthalates from an
aqueous solution. The substances involved in the study are shown below. The method satisfied the
validation criteria adopted by the CEN group in charge of the work (CEN/TC52/WG9/TG2 Safety of
toys – Organic chemical compounds – Method of analysis) and was adopted following a peer
review by 2 laboratories. It was incorporated in the European standard EN 71-11 “Safety of toys Part 11: Organic chemical compounds - Methods of analysis” adopted in 2005 for the
determination of those plasticizers for which a limit value was established (triphenyl phosphate,
tri-o-tolyl phosphate, tri-m-tolyl phosphate, tri-p-tolyl phosphate).
Plasticizers investigated in the study
Substance
CAS Number
Tributyl citrate
77-94-1
Tributyl O-acetyl citrate
77-90-7
Triethyl citrate
77-93-0
Triethyl O-acetyl citrate
77-89-4
Bis(2-ethylhexyl) adipate
103-23-1
Bis[2-(2-butoxyethoxy)ethyl] adipate
141-17-3
Bis(2-butoxyethyl) adipate
141-18-4
Dioctyl adipate
123-79-5
Diisodecyl adipate
27178-16-1
Bis(2-ethylhexyl) azelate
103-24-2
Bis(2-ethylhexyl) sebacate
122-62-3
Butyl benzoate
136-60-7
Di(ethylene glycol) dibenzoate
120-55-8
Di(propylene glycol) dibenzoate
94-51-9
Tributyl phosphate
126-73-8
Triphenyl phosphate
115-86-6
Tri-o-tolyl phosphate
78-30-8
Tri-m-tolyl phosphate
563-04-2
Tri-p-tolyl phosphate
78-32-0
Bis (2-ethylhexyl) phthalate
117-81-7
Diisononyl phthalate
68515-48-0
However, in this previous study possible matrix effects have not been taken into consideration
because the analyses were carried out with spiked water samples only and did not include toy
5
samples. Also the possible interferences caused by plasticizers present in higher concentrations
have not been investigated. These issues have been subject of the present study.
In addition, 23 toy samples purchased in and around Vienna have been analysed for plasticizers
2 Experimental
General
2.1
In the context of the previous study target values (= limits) had been established for the plasticizers
involved as follows:
•
it is assumed that a toy sample of a size of 10 cm² is shaken for 1 hour in 100 ml water
following the procedure defined in EN 71-10 EN 71-10 “Safety of toys - Part 10: Organic
chemical compounds – Sample preparation and extraction”;
•
it is assumed that a child of 10 kg is sucking a toy with a contact area of 10 cm² for 3 hours
a day (which means that the water extract contains a third of the amount of substances a
child is assumed to ingest per day);
•
TDIs (Tolerable Daily Intakes) have been taken from literature or derived from NOELS (No
Observed Effect Levels);
•
an additional safety factor of 10 was used assuming that an exposure to a substance from
toys may only contribute to a tenth of the allowed total exposure from all sources
These target values are of practical use but are, of course, not officially recognised limits.
However, EN 71-10 “Safety of toys Part 9: Organic chemical compounds – Requirements”
established requirements for triphenyl phosphate, tri-o-tolyl phosphate, tri-m-tolyl phosphate and
tri-p-tolyl phosphate – these substances may not be detectable in the water extract.
The target values for the various plasticizers are shown in the table below.
6
Target values for the various plasticizers
Substance
Target value in 100ml H2O
Tributyl citrate
170µg
170µg
Triethyl citrate
170µg
170µg
100µg
170µg
170µg
Dioctyl adipate
170µg
Diisodecyl adipate
170µg
170µg
170µg
Butyl benzoate
1700µg (as benzoic acid)
1700µg
1700µg
Tributyl phosphate
170µg
Triphenyl phosphate
ND (= 1µg)
Tri-o-tolyl phosphate, tri-o-cresyl phosphate
ND (= 1µg)
Tri-m-tolyl phosphate, tri-m-cresyl phosphate
ND (= 1µg)
Tri-p-tolyl phosphate, tri-p-cresyl phosphate
ND (= 1µg)
12µg
50µg
Remark: the extraction time was changed in consecutive draft standards from 1 hour to 3 hours
and then back to one hour. In this study 3 hours were used, but the target values indicated above
were not adjusted for the sake of better comparison with the results of the previous study.
2.2 Toys investigated
32 different toys were screened for chlorine (PVC) using the Beilstein test and the 23 Beilstein
positive toys shown in the table below checked by IR for control.
7
Toy samples with positive result in Beilstein test
Nr.
Product
Purchased from
01
Baby doll in child seat, 3+, only doll tested
Toys R us
02
My first Baby Annabell, Zapf Creation, 1+
Toys R us
03
Pushhorn Winnie the Pooh, Disney
Toys R us
04
My little Pony, Hasbro, 3+
Toys R us
08
Tiger horn for children’s bicycles, Prophete
Toys R us
09
Memo Bubble, Funrise, Disney, 3+,only fish tested
Toys R us
10
Teletubby, Playskool/Hasbro, 1+
Toys R us
12
Friendly floatees, the first years, 0+
Toys R us
13
Gray duck, Rubba Ducks, Commonwealth, 10m+
Toys R us
14
Bath ducks, 0+
Toys R us
15
Splash pets, Simba, 3+
Toys R us
17
Tiny Baby, Simba
Gerngross
18
Tiny Chou Chou, Zapf Creation, 1+
Gerngross
19
2 animals, only red animal tested
Gerngross
20
Chou Chou, Zapf Creation
Gerngross
21
Bubbelix frog, Pustefix, 3+, only frog tested
Gerngross
23
Duck, Shelcore
Gerngross
26
Squeeze car, Lederaplastic
Bannert
27
Little People, Fisher Price, 1-5
Bannert
28
Squeeze cubes
Bannert
30
Plastic picture book – Little fish in the ocean, Coppenrath publishers,
Bannert
only bag tested
31
Squeeze animal, Babyline Schneiders
32
Lovely Doll, Beautiful Collection
Spielwaren F. Jank
Bestpreismarkt
Where an age indication was found on the package this was included in the table (e.g. 1+). In case
the toy consisted of several parts the one subject to analysis is reported.
Pictures of the toys are shown in Annex A.
8
2.3 Analysis by infrared-spectroscopy
Toys which showed a positive reaction in the Beilstein test (indicating the presence of chlorine,
originating from PVC containing plasticizers) were analyzed by attenuated total reflection (ATR) –
infrared spectroscopy.
2.3.1 Apparatus
Instrument: FT-IR-Spectrophotometer 210 DX, Nicolet Inc.
320 Grit Si-carbide-paper, Spectra-Tech Inc.
2.3.2 Procedure:
Surfaces of the samples were treated with ultra clean Siliciumcarbide abrasive paper holders at
positions were the toys were not painted, followed by analysis of the abrasive paper carrying the
sample (Siliciumcarbide gives no absorption between 400cm-1 and 4000cm-1).
The spectra of some toys showed the presence of PVC, some of alkyd resins, some of
polystyrene-PVC-copolymers, some of polyisobutylene. Some toys showed spectra, which made a
positive match with library spectra impossible. Most of the spectra showed a strong band at
approximately 1750cm-1, indicating ester groups. It was not possible to differentiate between ester
bands from polyesters of copolymers and from plasticizers. Hence, analysis by ATR – infrared
spectroscopy is not a reliable method to determine whether plasticizers are present or not.
2.4 Analysis by solvent-extraction followed by GC/MS-analysis
Eleven Toys – shown in the table below - were directly extracted with toluene and analyzed by
GC/MS to ensure the presence and nature of plasticizers in the samples.
These toys were chosen because IR-spectra of these samples showed strong absorption in the
region of 1700cm-1 to 1800cm-1 indicating the presence of esters which were supposed to originate
from plasticizers.
Extraction was performed on a fex-IKA 50 solvent extractor (see Annex B). This computer
controlled device is a modified Soxhlet-extractor, were the sample is extracted at boiling
temperature by a steam-liquid-mixture of the solvent. This method reduces extraction times by a
factor of ten to twenty.
9
Toys extracted with solvent
Nr.
Product
03
Pushhorn Winnie The Pooh, Disney
10
Teletubby, Playskool/Hasbro
13
Grey duck, Rubba Ducks
15
Splash pets, Simba
19
Red animal
23
Duck, Shelcore
26
27
Little People, Fisher Price
28
Squeeze cubes
30
Plastic picture book – Little fish in the ocean, Coppenrath
publishers, only bag tested
31
2.4.1 Chemicals
Toluene pestanal®, Art.no.: 34494, Lot 4228A, Riedel de Haën
2.4.2 Apparatus
Fex-IKA 50 Solvent extractor, IKA Janke & Kunkel GmbH
Gas chromatograph: HP 5890 A Series II, Hewlett-Packard
Column: Macherey & Nagel Optima δ-3 30m*0,25mm*0,5µm
Carrier gas: Helium
Column head pressure: 70kPa constant pressure
Split-Modus, split flow: 20ml/min
Injector temperature: 260°C
Interface temperature: 270°C
Oven program:
50°C/4min
15°C/min
80°C/0min
25°C/min
300°C/30min
Mass selective Detector: HP 5972MSD, Hewlett-Packard
Scan-Modus: 40-350 amu
Software G1701AA Rel. A03.00 with Wiley-Spectra-Library (containing 133.000 data sets),
Hewlett-Packard
10
2.4.3 Procedure
Approximately 0,5grams of a sample were put in the extraction vessel and extracted for one hour
with toluene. The extract was analyzed by GC/MS. The mass spectra of the measured peaks were
electronically compared to those in the spectra library of the software.
Plasticizers found in the solvent extract are shown below (see Annex C: Chromatograms of solvent
extracts):
Plasticizers found in the solvent extract
Nr.
Toy
Plasticizer
03
Pushhorn Winnie The Pooh, Disney
Phthalate esters *)
10
Teletubby, Playskool/Hasbro
Citroflex (Citrate esters)
13
Grey duck, Rubba Ducks
Adipates, Citroflex
15
Splash pets, Simba
Phthalate esters*)
19
Red animal
Phthalate esters*)
23
Duck, Shelcore
Citroflex
26
Phthalate esters*)
27
Little People, Fisher Price
Citroflex
28
Squeeze cubes
Phthalate esters*)
30
Plastic picture book – Little fish in the ocean, Coppenrath
Phthalate esters*)
publishers, only bag tested
31
*) Phthalate esters means different types and mixtures.
11
Phthalate esters*)
2.5 Validation of method using toy samples
2.5.1 General
To observe possible matrix effects over the whole concentration range of the validation two
different toys, sample 13 – Rubba Duck (containing adipates and citrates) and sample 28 squeezing cubes (containing phthalate esters) were five times extracted with water, the watery
extract spiked with all plasticizers at the 25%, 50%, 100%, 150%, 200% level of the proposed
target values, extracted with toluene:ethyl acetate=95:5 and analyzed by GC/MS.
The samples were chosen because of their content of different plasticizer types:
sample 28 contains phthalate esters and sample 13 contains adipates and citrate esters. This
allowed to validate all plasticizers without interference from the same plasticizers present in the
samples.
2.5.2 Procedure
According to draft standard EN 71-10 “Safety of toys Part 10: Organic chemical compounds –
Sample preparation and extraction” (edition December 2003) the samples were cut into pieces of
10cm2 (see Annex D) and each piece put in a 250ml Duran-Schott flask. 100ml of ultra pure water
were added and the flask closed with a screw cap equipped with a Teflon coated silicone sealing.
The flasks were fixed in the rotator. The bottles were rotated at a speed of 60 +/- 1 turns per
minute for 3 hours exactly.
Note: As already indicated in clause 2.1 the extraction time was altered in subsequent editions of
the (draft) standard to one hour.
Afterwards the sample of the toy was removed from the water using tweezers. Stock-solutions of
the plasticizers in acetone plus a stock solution of benzylbutyl phthalate in acetone (as internal
standard) were added to the water extract and homogenized. Differing from the Standard draft
mentioned above the watery extract was not filtered, because of the absence of small particles and
to reduce the possibility of contamination. Extraction took place within the used flask where 10ml of
the solvent toluene:ethyl acetate=95:5 was used. To facilitate removal of organic layer after
extraction water was added, so that the level of the solvent rose up to the neck of the bottle, where
the solvent was removed by use of Pasteur’s pipettes.
12
Extraction and analysis with GC/MS were performed five times per level (including blank – i.e.
water extract of toy without addition of plasticizers) using an internal standard method.
2.5.3 Head-over- heel-extractor
The extractor (see picture below) is an apparatus for extracting samples at a speed of 60 turns per
minute and complies with EN 71-10 “Safety of toys Part 10: Organic chemical compounds –
Sample preparation and extraction”. The sample holders are able to carry eight sample vessels
with a volume up to two litres, or up to 24 sample vessels with a volume of 250ml. For safety
purposes the axle with the sample holders is V-belt driven allowing to disengage from the 12Vmotor. The grounded power supply is mounted beneath the sample holders. The rotation speed is
infinitely variable and can be fixed at a desired value.
Picture: Head-over-heel-extractor
13
2.5.4 Chemicals
Ethyl acetate for Pesticide Residue Analysis, Art.no.: 3427, Lot LECD-B, Promochem
Acetone pestanal®, Art.no.: 34480, Lot 30910, Riedel de Haën
Water puriss. from water treating apparatus, Easypure
Standards
Name
Purity
CAS-Nr.
Manufacturer
Order-Nr.
Ch.Nr.
( supplier data)
Tributyl citrate
>99%
77-94-1
Merck
8.203.500.100
S23527 102
>99.0%
77-90-7
Fluka
42858
415938/1
20502
Triethyl citrate
>98%
77-93-0
Fluka
27500
423804/1
32201
>99.0%
77-89-4
Fluka
68536
416283/1
13801
>99%
103-23-1
Fluka
WA17455
308606/1
53900
Bis[2-(2-butoxyethoxy)ethyl]
?
141-17-3
Aldrich
42,101-4
11901PU
Techn.
141-18-4
Aldrich
46,023-0
05224HQ
Di-n-octyl adipate
?
123-79-5
Chem Service
Pz-325
55-121L
Diisodecyl adipate
Techn.
27178-16-1
Aldrich
46,021-4
04224HQ
Ca. 80%
103-24-2
Merck
8.013.170.100
S25705 005
>97%
122-62-3
Fluka
WA12729
48396/1
adipate
43901
Butyl benzoate
>98%
136-60-7
Fluka
12410
367947/1
54200
96%
120-55-8
Aldrich
36,936-5
05027ES
?
94-51-9
Chem Service
Pz-96
61-55D
Tributyl phosphate
p.A. >99%
126-73-8
Merck
1.083.540.500
K28998154
117
Triphenyl phosphate
>98%
115-86-6
Fluka
93080
361606/1
22301
98%
78-30-8
Chem Service
O-918
273-43A
97%
563-04-2
Acros
422280100
A010989901
>98%
78-32-0
Acros
422300250
A010354501
Bis-(2-ethylhexyl) phthalate
> 97%
117-81-7
Fluka
80032
420656/1
40201
techn.
68515-48-0
14
Fluka
80072
24260/1 1295
2.5.5 Apparatus
Gas Chromatograph Agilent 6890N
Column: Macherey & Nagel Optima δ-3 30m*0,25mm*0,5µm
Carrier gas: Helium
Column head pressure: 120kPa constant pressure
Splitless-Mode, 1min, total flow: 40ml/min
Injector temperature: 275°C
Interface temperature: 290°C
Oven program:
100°C/1min - 7°C/min - 300°C/5min
Mass-selective Detector: Agilent 5973 inert
MS Quadrupole Temperature: 150°C
MS Ion Source Temperature: 230°C
SIM-Modus:
Group 1 (0-20min): 99amu, 105amu, 115amu, 123amu, 155amu, 157amu, 203amu
Group 2 (20min – end of run): 85amu, 99amu, 105amu, 111amu, 112amu, 129amu, 149amu,
163amu, 165amu, 167amu, 169amu, 171amu, 179amu, 185amu, 206amu, 241amu,
293amu,325amu, 368amu
List of target and qualifier ions for plasticizers
Substance
CAS Number
Target
Qualifier
Ion
Tributyl citrate
77-94-1
129
185
77-90-7
185
129
Triethyl citrate
77-93-0
157
115
77-89-4
157
203
103-23-1
129
111
141-17-3
099
085
141-18-4
085
111
Dioctyl adipate
123-79-5
129
241
Diisodecyl adipate
27178-16-1
129
111
103-24-2
171
112
122-62-3
185
112
Butyl benzoate
136-60-7
105
123
120-55-8
105
149
94-51-9
105
163
15
Substance
CAS Number
Target
Qualifier
Ion
Tributyl phosphate
126-73-8
099
155
Triphenyl phosphate
115-86-6
325
169
78-30-8
165
179
563-04-2
368
165
78-32-0
368
165
117-81-7
149
167
68515-48-0
149
293
Substance
CAS Number
Target
Qualifier
Ion
Benzylbutyl phthalate (Internal Standard)
85-68-7
149
206
2.5.6 Preparation of calibration standards
Of the different plasticizers two stock solutions were prepared by dissolving the substances in
acetone. Working standard solutions containing all substances in appropriate concentration ratios
to each other were prepared by dissolving the stock solutions in acetone using glass pipettes and
glass volumetric flasks. Storage of the stock and the working standard solution was performed at
room temperature.
16
2.5.7
Results
2.5.7.1
Precision
The repeatability was measured at 25%, 50%, 100% 150% and 200% of the proposed limits
respectively in the presence of plasticizers extracted from two different toys sample 13 “Rubba
Duck” and sample 28 “Squirting Cube”. The last column indicates the migration into the water of
plasticizers contained in the toy sample.
2.5.7.1.1
Precision in the presence of sample 13 “Rubba Duck”
from sample
Sample 13 Rubba duck
25 % of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
3,50
Tributyl citrate
42,89
1,19
2,76
127,26
5,99
4,71
103
Triethyl citrate
34,35
0,59
5,25
-
38,91
1,02
2,63
-
39,57
1,59
6,84
-
38,62
0,68
2,35
-
39,59
0,65
2,15
-
Di-n-octyl adipate
40,66
0,95
3,95
2,10
Diisodecyl adipate
218,17
14,47
6,63
180
41,06
1,01
2,45
2,10
37,55
1,51
5,68
-
Butyl benzoate
52,33
0,97
1,55
-
41,39
1,00
2,41
-
37,27
1,29
3,47
-
Tributyl phosphate
35,87
0,75
2,09
-
Triphenyl phosphate
2,98
0,07
2,20
-
2,66
0,17
6,47
-
2,63
0,19
7,40
-
2,55
0,11
4,50
-
Bis(2-ethylhexyl) phthalate
3,82
0,22
5,87
1,20
12,04
0,41
7,17
-
17
from sample
Sample 13 Rubba Duck
50% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
Tributyl citrate
81,1
2,0
2,5
3,50
178,8
6,1
3,4
103
Triethyl citrate
68,9
0,9
3,9
-
82,1
0,7
0,9
-
80,8
1,9
3,0
-
78,1
3,8
6,3
-
73,4
1,2
1,6
-
Di-n-octyl adipate
82,5
2,5
4,7
2,10
Diisodecyl adipate
255,9
14,8
5,8
180
80,5
2,0
3,2
2,10
76,0
3,8
6,5
-
Butyl benzoate
119,2
2,4
2,0
-
84,6
3,3
3,9
-
80,1
2,4
3,1
-
Tributyl phosphate
79,0
0,8
1,0
-
Triphenyl phosphate
5,7
0,4
6,2
-
5,4
0,4
7,0
-
5,4
0,3
5,3
-
5,9
0,3
5,7
-
6,4
0,4
6,4
1,20
22,4
0,7
5,4
-
from sample
Sample 13 Rubber Duck
100% limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
Tributyl citrate
168,8
3,6
2,1
3,50
265,8
4,8
1,8
103
Triethyl citrate
134,5
0,9
1,8
-
174,4
13,0
7,4
-
149,2
7,6
5,1
-
150,1
5,0
3,6
-
156,6
7,2
4,6
-
Di-n-octyl adipate
167,7
5,3
3,8
2,10
Diisodecyl adipate
346,3
11,7
3,4
180
162,8
7,5
4,9
2,10
162,3
3,6
2,2
-
Butyl benzoate
231,1
11,9
5,2
-
18
from sample
Sample 13 Rubber Duck
100% limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
165,8
4,5
2,7
-
164,7
4,3
2,6
-
Tributyl phosphate
154,4
10,8
7,0
-
Triphenyl phosphate
10,2
0,4
3,7
-
11,5
0,5
4,6
-
10,2
0,4
3,7
-
11,0
0,5
5,0
-
12,4
0,1
1,0
1,20
45,1
1,4
4,6
-
from sample
150% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
246,8
7,3
2,9
3,50
355,4
3,8
1,1
103
Triethyl citrate
215,7
0,3
0,4
-
253,9
3,5
1,4
-
241,1
2,9
1,2
-
239,7
6,1
2,5
-
248,0
4,9
1,9
-
Di-n-octyl adipate
250,0
9,9
4,0
2,10
Diisodecyl adipate
432,0
25,7
6,0
180
256,6
8,7
3,4
2,10
259,7
2,5
0,9
-
Butyl benzoate
361,1
9,8
2,6
-
247,9
13,8
5,5
-
240,5
6,2
2,6
-
Tributyl phosphate
260,2
15,8
6,1
-
Triphenyl phosphate
16,5
0,7
4,9
-
16,6
0,9
5,0
-
16,3
0,6
3,6
-
16,7
0,8
4,5
-
17,0
0,5
4,2
1,20
64,5
1,2
2,1
-
Tributyl citrate
19
from sample
200% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
Tributyl citrate
335,2
8,7
2,6
3,50
433,0
10,9
2,5
103
Triethyl citrate
267,2
5,0
4,5
-
335,5
8,0
2,4
-
325,7
9,7
3,0
-
319,0
14,8
4,7
-
318,5
10,7
3,3
-
Di-n-octyl adipate
326,8
12,4
3,8
2,10
Diisodecyl adipate
511,6
18,2
3,6
180
329,7
22,4
6,8
2,10
325,4
6,0
1,9
-
Butyl benzoate
470,9
9,7
2,1
-
318,5
9,4
3,0
-
331,9
13,1
4,0
-
Tributyl phosphate
340,8
15,2
4,4
-
Triphenyl phosphate
21,4
0,8
4,3
-
22,5
0,3
1,5
-
21,3
0,4
1,8
-
21,9
0,5
2,5
-
23,3
0,4
2,3
1,20
90,8
3,6
5,0
-
According to the validation criteria contained in document CEN/TC 52/WG 9/TG 2 N68 Rev.4 the
relative standard deviation should be below the limits of Annex A of this document, which is 7,3%
for 10µg/g and 11% for 1µg/g. All RSD-values comply with these limits. Where plasticizers were
contained in the sample these values are also indicated in the table, but were discounted in the
validation.
20
2.5.7.1.2
Precision in the presence of sample 28 “Squirting Cube”
from sample
Sample 28 Squirting Cubes
25% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
28,92
0,50
1,72
-
39,66
1,08
3,87
-
Triethyl citrate
33,54
0,24
1,68
-
39,80
1,68
4,22
-
34,89
0,88
4,77
-
42,99
2,04
6,71
-
36,52
0,22
0,75
-
Di-n-octyl adipate
38,40
0,83
4,59
-
Diisodecyl adipate
39,41
2,01
5,43
-
39,70
1,46
7,82
-
41,27
1,19
6,12
-
Butyl benzoate
54,44
0,70
1,14
-
39,53
1,84
4,65
-
35,89
1,04
2,88
1,40
Tributyl phosphate
37,32
0,23
0,61
-
Triphenyl phosphate
2,90
0,17
5,87
-
2,73
0,12
4,35
-
2,63
0,13
4,79
-
2,55
0,11
4,47
-
2,49
0,20
7,19
-
16,40
0,36
2,19
4,0
Tributyl citrate
from sample
Sample 28 (Squirting Cubes)
50% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
78,9
2,8
4,1
-
77,2
3,0
5,0
-
Triethyl citrate
68,9
0,9
2,9
-
81,9
1,8
2,2
-
76,5
1,8
3,6
-
77,5
1,3
2,1
-
77,1
2,3
3,6
-
Di-n-octyl adipate
75,9
2,5
5,7
-
Diisodecyl adipate
82,1
3,2
3,9
-
76,9
3,1
5,7
-
Tributyl citrate
21
from sample
Sample 28 (Squirting Cubes)
50% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
79,6
3,9
6,6
-
Butyl benzoate
127,9
5,3
4,1
-
84,4
3,7
4,4
-
79,9
2,3
2,9
1,40
Tributyl phosphate
80,7
1,3
1,6
-
Triphenyl phosphate
5,4
0,1
2,5
-
5,7
0,4
8,4
-
5,4
0,4
8,8
-
4,9
0,2
4,0
-
5,5
0,3
6,7
-
30,0
0,7
2,4
4,0
from sample
100% of limit
Substance
µg/100ml water
Sr µg/100ml
RSD %
µg/100ml water
158,4
15,0
9,4
-
139,9
3,7
2,8
-
Triethyl citrate
141,3
3,0
4,3
-
161,8
14,4
8,9
-
156,2
7,3
6,1
-
162,4
6,5
4,3
-
169,6
5,4
3,9
-
Di-n-octyl adipate
156,5
7,1
6,4
-
Diisodecyl adipate
151,9
3,3
3,3
-
153,1
7,2
6,1
-
169,3
5,2
4,0
-
Butyl benzoate
242,1
9,3
3,8
-
161,3
4,7
2,9
-
166,3
4,2
2,5
1,40
Tributyl phosphate
169,1
6,1
3,6
-
Triphenyl phosphate
10,4
0,3
2,9
-
11,9
0,2
1,8
-
10,6
0,2
2,1
-
11,0
0,2
2,2
-
11,5
0,3
3,3
-
54,7
0,7
1,5
4,0
Tributyl citrate
22
from sample
150% of limit
Substance
µg/100ml water
Sr µg/ 100ml
RSD %
µg/100ml water
249,1
9,3
3,7
-
225,9
12,1
5,4
-
Triethyl citrate
197,6
4,6
4,2
-
229,5
10,4
4,5
-
237,5
4,7
2,0
-
254,5
15,2
6,0
-
228,4
12,2
5,4
-
Di-n-octyl adipate
220,7
7,4
3,6
-
Diisodecyl adipate
224,0
11,4
5,1
-
244,8
7,9
3,2
-
236,2
12,5
5,3
-
Butyl benzoate
359,9
19,5
5,4
-
249,5
4,9
2,0
-
241,1
7,5
3,1
1,40
Tributyl phosphate
227,3
13,9
6,1
-
Triphenyl phosphate
15,2
0,6
4,2
-
15,9
0,4
2,7
-
15,1
0,4
2,6
-
15,2
0,8
5,6
-
16,3
0,3
2,2
-
66,1
2,0
2,9
4,0
Tributyl citrate
from sample
200% of limit
Substance
µg/100mlwater
Sr µg/100ml
RSD %
µg/100ml water
345,2
14,5
4,2
-
308,2
5,9
1,9
-
Triethyl citrate
273,4
9,7
5,7
-
287,9
6,2
2,2
-
307,1
9,2
3,0
-
340,4
9,4
2,8
-
319,0
13,4
4,4
-
Di-n-octyl adipate
297,4
9,5
3,6
-
Diisodecyl adipate
296,4
13,5
4,6
-
328,0
6,6
2,3
-
300,7
9,2
3,1
-
Butyl benzoate
515,4
6,0
2,4
-
340,0
8,8
4,4
-
Tributyl citrate
23
from sample
200% of limit
Substance
µg/100mlwater
Sr µg/100ml
RSD %
µg/100ml water
327,9
6,8
2,1
1,40
Tributyl phosphate
321,5
16,1
5,7
-
Triphenyl phosphate
20,9
0,6
2,8
-
22,0
0,7
3,4
-
20,8
0,8
4,0
-
20,9
0,8
4,0
-
22,0
0,6
3,7
-
91,1
2,5
2,8
4,0
relative standard deviation should be below the limits of Annex A of this document, which is 7,3%
for 10µg/g and 11% for 1µg/g. Except for bis(2-ethylhexyl)-azelate at the 25% level all RSd-values
comply with these limits. Where plasticizers were contained in the sample these values are also
indicated in the table, but were discounted in the validation.
24
2.5.7.2
Recovery
The recovery was calculated from the data obtained from the precision experiments.
2.5.7.2.1
Recovery of plasticizers in the presence of sample 13 “Rubba Duck”
Substance
25 % of limit
50% of limit
100 % of limit 150 % of limit 200% of limit
%
%
%
%
%
Tributyl citrate *)
100,9
95,4
99,3
96,8
98,6
Tributyl O-acetyl citrate *)
299,4
210,4
156,4
139,4
127,3
Triethyl citrate
80,8
81,0
79,1
84,6
78,6
91,6
96,6
102,6
99,6
98,7
93,1
95,0
87,8
94,5
95,8
90,9
91,9
88,3
94,0
93,8
93,2
86,3
92,1
97,2
93,7
Di-n-octyl adipate *)
95,7
97,1
98,6
98,0
96,1
Diisodecyl adipate *)
513,4
301,1
203,7
169,4
150,5
Bis(2-ethylhexyl) azelate *)
96,6
94,7
95,7
100,6
97,0
88,3
89,4
95,5
101,9
95,7
Butyl benzoate
84,4
96,1
93,2
97,6
94,9
97,4
99,5
97,5
97,2
93,7
87,7
94,2
96,9
94,3
97,6
Tributyl phosphate
84,4
93,0
90,8
102,0
100,2
Triphenyl phosphate
99,2
94,3
85,4
91,9
89,2
88,7
90,8
95,6
92,1
93,9
87,7
89,6
85,3
90,3
88,2
84,9
97,6
91,5
93,0
91,2
Bis-(2-ethylhexyl) phthalate *)
127,2
107,2
103,3
94,4
97,0
96,3
89,4
90,3
86,1
90,8
*) component present in sample
recovery should fall in the range of 80-110% for 0,1µg/g to 10µg/g. Except for triethyl citrate at the
100% level (recovery: 79,1%) all recovery values comply with these limits. Where plasticizers were
validation.
25
2.5.7.2.2
Recovery of plasticizers in the presence of sample 28 “Squirting Cube”
Substance
25 % of limit
50% of limit
100 % of limit 150 % of limit 200% of limit
%
%
%
%
%
Tributyl citrate
68,1
92,9
93,2
97,7
101,5
93,3
90,8
82,3
88,6
90,6
Triethyl citrate
78,9
81,0
83,1
77,5
80,4
93,6
96,3
95,2
90,0
89,8
82,1
90,0
92,0
93,9
90,3
101,1
91,1
95,5
99,8
100,4
85,9
90,7
99,8
89,6
93,8
Di-n-octyl adipate
90,4
89,3
92,1
86,6
87,3
Diisodecyl adipate
92,7
96,6
89,3
87,8
87,2
93,4
90,5
90,1
96,0
96,5
97,1
90,5
99,6
92,6
88,4
Butyl benzoate
99,3
103,2
97,6
96,8
103,9
93,0
99,3
94,9
97,8
100,0
Di(propylene glycol) dibenzoate *)
84,4
94,1
97,8
94,6
96,5
Tributyl phosphate
87,8
95,0
99,5
94,7
94,6
Triphenyl phosphate
96,6
89,8
86,4
84,6
86,9
91,0
94,4
99,3
88,1
91,6
87,7
90,3
88,5
83,9
85,9
85,1
80,9
91,7
84,6
87,1
91,6
91,4
95,5
90,3
91,6
Diisononyl phthalate *)
131,9
118,8
109,3
97,6
91,1
recovery should fall in the range of 80-110% for 0,1µg/g to 10µg/g. Except for triethyl citrate at the
25% and the 150% level (recovery: 78,9% and 77,5% respectively) and tributyl citrate at the 25%
level (recovery: 68,1%) all recovery values comply with these limits. Where plasticizers were
validation.
26
2.5.7.3
Linearity
All of the concentration levels mentioned above (10%-500% of limit) were analyzed five times.
According to document CEN/TC 52/WG 9/TG 2 N68 Rev.4 the minimum coefficient of correlation
by using a straight line fit should be 0,995. Linearity is calculated using the peak area ratio (PAR)
and benzylbutyl phthalate as internal standard.
2.5.7.3.1
Linearity of plasticizers in the presence of sample 13 “Rubba Duck”
Sres
slope (b)
Intercept (a)
R2
R
Tributyl citrate *)
209567
3797
-381038,00
0,9980
0,9990
309175
4132,8
3362131,00
0,9957
0,9978
Triethyl citrate
348421
3901,8
-93905,00
0,9948
0,9974
16928
216,75
-8443,00
0,9961
0,9980
15985
218
-496,00
0,9965
0,9982
2528
30,05
-1351,00
0,9954
0,9977
7830
96,11
-7988,00
0,9957
0,9978
14941
220,58
-12069,00
0,9970
0,9985
29133
179
285390,00
0,9801
0,9900
10208,7
170,5
-10332,00
0,9975
0,9987
16490
207,4
-16254,00
0,9959
0,9979
Butyl benzoate
2728
24,258
-5509,00
0,9961
0,9980
23909
305,87
-3277,00
0,9960
0,9980
5672
83,7
-2526,00
0,9970
0,9985
Tributyl phosphate
35937,8
423,7
-47258,00
0,9953
0,9976
Triphenyl phosphate
507,87
81,896
-1188,00
0,9950
0,9975
523,9
113,6
-1539,00
0,9972
0,9986
461,5
92,27
-1326,00
0,9967
0,9983
420,46
80,34
-1175,00
0,9964
0,9982
2150
394
2278,00
0,9954
0,9977
20817
888
432,00
0,9959
0,9979
Substance
It is shown, that the correlation coefficient R is better than 0,995 for all components. Where
plasticizers were contained in the sample these values are also indicated in the table, but were
discounted in the validation.
27
2.5.7.3.2
Linearity of plasticizers in the presence of sample 28 “Squirting Cube”
Substance
Intercept (a)
R2
Sres
slope (b)
R
Tributyl citrate
357063
3929
-695927,00
0,9946
0,9973
311501
3595
-244035,00
0,9951
0,9975
Triethyl citrate
296832
3801
-46314,00
0,9960
0,9980
16797
197
-448,00
0,9953
0,9976
14702
210,3
2546,00
0,9968
0,9984
2657
32,17
-1670,00
0,9956
0,9978
7979
94
-7142,00
0,9954
0,9977
Di-n-octyl adipate
16656
198,26
-8849,00
0,9954
0,9977
Diisodecyl adipate
13500
156
-22735,00
0,9951
0,9975
11916
164,15
-11496,00
0,9966
0,9983
20430
189,14
-1628,00
0,9924
0,9962
Butyl benzoate
2106
25,776
-6208,00
0,9980
0,9990
22967
322,454
-19012,00
0,9967
0,9983
4250
83,239
-2316,00
0,9983
0,9991
Tributyl phosphate
27052
398,479
-24822,00
0,9969
0,9984
Triphenyl phosphate
352,889
78,627
-1163,00
0,9974
0,9987
723
105
-1243,00
0,9943
0,9971
473,3
88,38
-1144,00
0,9963
0,9981
426,266
76,71
-1252,00
0,9960
0,9980
1947
392
-1892,00
0,9968
0,9984
29045
878,7
77951,00
0,9903
0,9951
* component present in sample
It is shown, that the correlation coefficient R is better than 0,995 for all components. Where
plasticizers were contained in the sample these values are also indicated in the table, but were
discounted in the validation.
28
2.5.7.4
Limit of Detection (LOD) / Limit of Quantification (LOQ)
Limit of detection and limit of quantification are calculated using the data from the calibration
functions LOD is expressed as 3*Sres/B, where Sres is the residual standard deviation and B the
slope of the calibration function. LOQ is expressed as LOD*2. LOD and LOQ based on peak/noise
was not determined, because of the low noise of the used new Mass-selective Detector Agilent
5973.
2.5.7.4.1
LOD and LOQ in the presence of sample 13 “Rubba Duck”
Substance
Sres
b
LOD ng/ml LOQ ng/ml
LOD
LOQ
µg/100ml
µg/100ml
Tributyl citrate *)
209567
3797
165,58
331,16
1,66
3,31
309175
4132,8
224,43
448,86
2,24
4,49
Triethyl citrate
348421
3901,8
267,89
535,79
2,68
5,36
16928
216,75
234,30
468,60
2,34
4,69
15985
218
219,98
439,95
2,20
4,40
2528
30,05
252,38
504,76
2,52
5,05
7830
96,11
244,41
488,81
2,44
4,89
14941
220,58
203,21
406,41
2,03
4,06
29133
179
488,26
976,53
4,88
9,77
10208,7
170,5
179,63
359,25
1,80
3,59
16490
207,4
238,52
477,05
2,39
4,77
Butyl benzoate
2728
24,258
337,37
674,75
3,37
6,75
23909
305,87
234,50
469,00
2,35
4,69
5672
83,7
203,30
406,59
2,03
4,07
Tributyl phosphate
35937,8
423,7
254,46
508,91
2,54
5,09
Triphenyl phosphate
507,87
81,896
18,60
37,21
0,19
0,37
523,9
113,6
13,84
27,67
0,14
0,28
461,5
92,27
15,00
30,01
0,15
0,30
420,46
80,34
15,70
31,40
0,16
0,31
2150
394
16,37
32,74
0,16
0,33
20817
888
70,33
140,66
0,70
1,41
29
2.5.7.4.2
LOD and LOQ in the presence of sample 28 “Squirting Cube”
Substance
Sres
b
LOD ng/ml LOQ ng/ml
LOD
LOQ
µg/100ml
µg/100ml
Tributyl citrate
357063
3929
272,64
545,27
2,73
5,45
311501
3595
259,95
519,89
2,60
5,20
Triethyl citrate
296832
3801
234,28
468,56
2,34
4,69
16797
197
255,79
511,58
2,56
5,12
14702
210,3
209,73
419,46
2,10
4,19
2657
32,17
247,78
495,55
2,48
4,96
7979
94
254,65
509,30
2,55
5,09
Di-n-octyl adipate
16656
198,26
252,03
504,07
2,52
5,04
Diisodecyl adipate
13500
156
259,62
519,23
2,60
5,19
11916
164,15
217,78
435,55
2,18
4,36
20430
189,14
324,05
648,09
3,24
6,48
Butyl benzoate
2106
25,776
245,11
490,22
2,45
4,90
22967
322,454
213,68
427,35
2,14
4,27
4250
83,239
153,17
306,35
1,53
3,06
Tributyl phosphate
27052
398,479
203,66
407,33
2,04
4,07
Triphenyl phosphate
352,889
78,627
13,46
26,93
0,13
0,27
723
105
20,66
41,31
0,21
0,41
473,3
88,38
16,07
32,13
0,16
0,32
426,266
76,71
16,67
33,34
0,17
0,33
1947
392
14,90
29,80
0,15
0,30
29045
878,7
99,16
198,33
0,99
1,98
2.5.7.5
Specificity
In the case of trace analysis of organic chemicals the possibility of false positive results by
interfering substances is always subject to be considered. To minimize this possibility GC/MS with
target and qualifier ions is used. This means that a signal of a target ion at a specific retention time
is quantified only if the signal of the qualifier ion at the same retention time is within a fixed ratio to
the target ion. This ratio is specific for each substance.
30
2.5.7.6
Robustness/ruggedness
All analysis were performed at room temperature in November and December respectively with a
change in room temperature of about 5 degrees Celsius (depending on working rhythm of gas
chromatographs installed in the same room). No significant impact on the test results were
observed.
2.5.7.7
Stability of standard solutions
There were no observable effects on the stock solutions in acetone at concentrations in the range
of mg/ml when stored at room temperature for 3 months. In addition no degradation products could
be found after this time of storage.
In addition, there were no observable effects on the calibration standard solutions in toluene:ethyl
acetate=95:5 at concentrations of µg/ml when stored at room temperature for 4 weeks.
31
2.6 Analysis of real samples
2.6.1 General
Twenty toy samples shown below were selected from the list given in 2.2 and analyzed with the
method described in 2.5.2 – 2.5.6. Pieces of 10cm2 were cut out from the toy out and extracted
with water. The water extract was extracted with organic solvent (toluene:ethyl acetate=95:5) and
analyzed by GC/MS.
Nr.
Product
03
Pushhorn Winnie the Pooh, Disney
04
My little Pony, Hasbro, 3+
08
Tiger horn for children’s bicycles, Prophete
09
Memo Bubble, Funrise, Disney, 3+, only fish tested
10
Teletubby, Playskool/Hasbro, 1+
12
Friendly floatees, the first years, 0+
13
Gray duck, Rubba Ducks, Commonwealth, 10m+
14
Bath ducks, 0+
15
Splash pets, Simba, 3+
17
Tiny Baby, Simba
18
Tiny Chou Chou, Zapf Creation, 1+
19
2 animals, only red animal tested
21
Bubbelix frog, Pustefix, 3+, only frog tested
23
Duck, Shelcore
26
27
Little People, Fisher Price, 1-5
28
Squeeze cubes
30
Plastic picture book – Little fish in the ocean, Coppenrath publishers,
only bag tested
31
32
Lovely Doll, Beautiful Collection
2.6.2 Results migration tests
The results stated in the tables below are mean values from duplicate analysis. The results of the
samples 13, 27 and 28 are mean values of fivefold analysis. “<” means result is below LOD. LODs
are stated below.
32
Results migration tests, samples 3-17, µg/100ml water
Substance
Sample 3
Sample 4
Sample 8
Sample 9
Sample 10
Sample 12
Sample 13
Sample 14
Sample 15
Sample 17
(used for
validation)
Tributyl citrate
<
<
<
19,0
10,7
7,81
3,5
7,04
<
<
2,20
<
<
62,4
584
379
103
399
<
<
Triethyl citrate
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
Di-n-octyl adipate
<
<
<
1,90
<
<
2,1
<
<
<
Diisodecyl adipate
7,93
<
<
55,8
<
<
180
<
<
<
<
<
<
<
<
<
2,1
<
<
<
<
<
<
<
<
<
<
<
<
<
Butyl benzoate
<
<
<
<
<
<
<
<
<
<
<
<
<
<
1,59
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
Tributyl phosphate
<
<
<
<
<
<
<
<
<
2,14
Triphenyl phosphate
1,87
1,775
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
1,2
<
<
<
22,5
11,78
7,615
<
<
<
<
<
8,36
<
33
Results migration tests, samples 18-32, µg/100ml water
Substance
Sample 18
Sample 19
Sample 21
Sample 23
Sample 26
Sample 27
Sample 28
Sample 30
Sample 31
Sample 32
(used for
validation)
Tributyl citrate
<
<
<
11,5
<
3,7
<
<
<
<
<
3,29
2,43
1336
<
199
<
<
<
2,55
Triethyl citrate
<
<
<
1,305
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
2,775
Di-n-octyl adipate
<
<
<
<
<
<
<
<
<
<
Diisodecyl adipate
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
Butyl benzoate
<
<
<
<
<
<
<
<
<
<
<
1,58
<
<
<
<
<
<
<
<
<
1,89
<
<
<
4,5<
1,4
<
<
<
Tributyl phosphate
<
<
<
<
<
<
<
<
<
2,53
Triphenyl phosphate
<
<
<
<
<
1,6<
<
<
<
4,56
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
1,32
4,61
<
<
<
<
<
1,92
<
13488
<
6,66
36,85
<
16
<
4
<
1930,5
18,5
34
2.6.3 Determination of the total content of plasticizers in two toy samples
For this test the samples 31 (Squeeze animal, Babyline Schneiders) and 32 (Lovely Doll,
Beautiful Collection) were chosen because of the high phthalate concentration in the water
extract and because of the fact that the future European legislation will limit the content
rather than the migration of phthalates in toys. The two toys were directly extracted with
toluene/ethyl acetate and analyzed by GC/MS. Extraction was performed on a fex-IKA 50
solvent extractor (see Annex B). Extraction and analysis with GC/MS were performed in
duplicate using an internal standard method.
2.6.3.1
Chemicals
Ethyl acetate for Pesticide Residue Analysis, Art.no .: 3427, Lot LECD-B, Promochem
2.6.3.2
Procedure
Approximately 0,5grams of a sample were put in the extraction vessel and extracted for one
hour with toluene:ethyl acetate=95:5. The Internal standard was added after the extraction.
2.6.3.3
Results
Sample 31 contains 18,5 % by mass diisononyl phthalate.
Sample 32 contains 34,0 % by mass bis(2-ethylhexyl) phthalate.
3 Discussion of Results
The validation of the method for the determination of plasticizers in aqueous solution after
extraction of a toy sample with water showed that the quality criteria mentioned in document
CEN/TC52/WG9/TG2 N68 (Protocol for method validation of the analysis of the simulant or
the extraction limit by lead laboratory) are achieved for all plasticizers even in the presence
of other plasticizers or other compounds contained in toys. Extraction and analysis within the
given working range do not seem to be affected by added or included plasticizers and other
substances present in toys. From that follows that one should normally not encounter
difficulties in the practical application of the method for the monitoring of plasticizers in toys.
Only two of the toy samples investigated showed plasticizer concentrations of concern:
35
both sample 31 (18,5 % by mass diisononyl phthalate) and sample 32 (34,0 % by mass
bis(2-ethylhexyl) phthalate) would not comply with the agreed limits included in the draft
European legislation on phthalates in toys and childcare articles which will enter into force in
2005. The text agreed by the Council and the Parliament foresees a limit of 0,1 % by mass of
diisononyl phthalate (DINP) in toys or childcare articles which can be put in the mouth by
children and a limit of 0,1 % by mass of bis(2-ethylhexyl) phthalate (DEHP) for all toys and
childcare articles.
36
Annex A - Pictures of toys
Sample 1
Sample 2
Sample 3
Sample 4
Sample 8
Sample 9
37
Annex A - Pictures of toys (continued)
Sample 10
Sample 12
Sample 13
Sample 14
Sample 15
Sample 17
38
Sample 18
Sample 19
Sample 20
Sample 21
Sample 23
Sample 26
39
Sample 27
Sample 28
Sample 30
Sample 31
Sample 32
40
Annex B - fex-IKA 50 solvent extractor
41
Annex C - Chromatograms of solvent extracts
Abundance
TIC: 2101001.D
1.3e+07
1.2e+07
1.1e+07
1e+07
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 03 - Disney Pushhorn Winnie The Pooh
Abundance
TIC: 2201002.D
4.8e+07
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
Time-->
Chromatogramm of extract from sample 10 - Teletubby
42
35.00
40.00
Abundance
TIC: 3301001.D
5500000
5000000
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 13 - Rubba Ducks
Abundance
TIC: 2301003.D
1.6e+07
1.5e+07
1.4e+07
1.3e+07
1.2e+07
1.1e+07
1e+07
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
10.00
15.00
20.00
25.00
30.00
Time-->
Chromatogramm of extract from sample 15 - Wasserspritzer (water squirt)
Abundance
TIC: 2401004.D
5e+07
4.8e+07
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 19 - Spritztier rot (Squeezing animal red)
43
Abundance
TIC: 2501005.D
5e+07
4.8e+07
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 23 - Wasserspritztier (water squirt)
Abundance
TIC: 2601006.D
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 26 - Squeezing car Lederaplastic
Abundance
TIC: 3401002.D
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
Time-->
Chromatogramm of extract from sample 27 - Little People
44
35.00
40.00
Abundance
TIC: 2701007.D
2.4e+07
2.3e+07
2.2e+07
2.1e+07
2e+07
1.9e+07
1.8e+07
1.7e+07
1.6e+07
1.5e+07
1.4e+07
1.3e+07
1.2e+07
1.1e+07
1e+07
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 28 - Quietschwürfel (Squeezing cubes)
Abundance
TIC: 2801008.D
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07
3e+07
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 30 - Kleiner Fisch im Meer (bag only)
Abundance
TIC: 2901009.D
2.8e+07
2.6e+07
2.4e+07
2.2e+07
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000
2000000
0
10.00
15.00
20.00
25.00
30.00
35.00
40.00
Time-->
Chromatogramm of extract from sample 31 - Quietschhund (Squeezing dog)
45
Annex D - Cut toy samples
Sample 12
Sample 12
Sample 15
Sample 15
Sample 21
Sample 21
46

Plasticizers in toys: Method validation using toy

Transcription

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