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LAAN-A-MS-E027
Gas Chromatography Mass Spectrometry
No.M261
Analysis of Phthalate Esters in Polyvinyl Chloride Toys by GC/MS
Parts of the standard for foods and additives
(Notification No. 370 of Ministry of Health and Welfare,
1959) were revised in September, 2010; the restricted
phthalate esters were increased from 2 (Bis(2ethylhexyl) phthalate (hereafter, DEHP) and diisononyl
phthalate (DINP)) to 6 (including DEHP, DINP, dibutyl
phthalate (DBP), butyl benzyl phthalate (BBP),
diisodecyl phthalate (DIDP) and di-n-octyl phthalate
(DNOP)). Moreover, the restricted substances are not
limited to synthetic resins of which the principal
constituent is polyvinyl chloride, but have been expanded
to other materials that may include plasticizers.
The phthalate ester test method specifies extraction of
phthalate esters from plastic toys using an organic
solvent and measurement of phthalate esters in the
n Analytical Method
Pretreatment was conducted according to "Ministry of
Health, Labour and Welfare Notification No.336,
2010," which is presented as a flow chart in Fig. 1.
The sample consisted of two commercially available
polyvinyl toys (A and B) (The toy A sample was the
extract by GC-FID or GC/MS. The peak area of each
phthalate ester in the sample extract is not to exceed
the corresponding phthalate ester peak area in a
standard solution containing the maximum allowable
concentrations (maximum phthalate ester concentrations
of 0.1 % or less). In the event that the phthalate ester
concentration measured by GC-FID is non-compliant,
verification testing must be conducted by GC/MS.
This Application News introduces an example of GC/
MS analysis of 6 phthalate esters in toys. For an
example of GC-FID analysis of the same sample, refer
to Shimadzu Application News No. G275 "Analysis of
6 Phthalate Esters in Polyvinyl Chloride Toys by GCFID."
same one used in Application News No. 275).
The GC/MS analytical conditions are shown in Table 1.
It is required that the carrier gas flow rate be adjusted
so that DEHP is eluted in about 10 minutes.
Table 1 Analytical Conditions
Sample 1g
Acetone / hexane (3:7) 50mL
Extraction
Let stand overnight at 40°C
Filter
Acetone
Sample solution 100mL
Further dilute with
acetone to obtain
10:1 dilution
GC/MS
GC-FID
If results do not
complywith standard
requirement
Verification testing
Fig. 1 Preparation of Sample
Model
-GCColumn
Col.Temp.
Carrier Gas
Carrier Gas Mode
Inj.Temp.
Injection Method
Sampling Time
Injection Volume
-MSI. F. Temp.
Ionization
Scan Range
Scan Interval
: GCMS-QP2010 Ultra (230 V: High Power Oven Model)
: Rxi-5MS (30 m × 0.25 mmI.D., df = 0.25 μm)
: 100 °C - 20°C/min - 320 °C (10 min)
: He (44 cm/sec)
: Constant linear velocity mode
: 250 °C
: Splitless injection
: 1 min
: 1 μL
: 280 °C
: EI
: m/z 45 - 600
: 0.3 sec.
No.M261
n Analysis of Phthalate Ester Standard Solutions
m/z 149 (DBP, BBP, DEHP), m/z 279 (DNOP), m/z
293 (DINP), and m/z 307 (DIDP). The elution positions
of Peak #4-6 of DNOP, DINP and DIDP are adjacent
to one another, with the peaks partially overlapping.
Therefore, when conducting measurement by GC-FID,
it is necessary to prepare separate standard solutions
for these substances. However, when conducting
measurement by GC/MS, the mass chromatograms of
the 3 respective analytes can be separated for reliable
confirmation.
Standard solutions of 6 phthalate esters (DBP, BBP,
DEHP, DNOP, DINP, DIDP) were prepared by
dissolving 10 mg of each standard substance in
100 mL acetone (each 100 μg/mL). A standard
solution for GC/MS analysis containing a mixture of
these substances was prepared by mixing 1 mL of
each of the solutions, and adjusting the volume to
100 mL using acetone (each 1 μg/mL).
Chromatograms of the standard solution are shown in
Fig. 2. In addition to the TIC chromatogram,
characteristic ion mass chromatograms are shown for
1.3
(× 1,000,000)
TIC
1
1.2
2
3
1 DBP
2 BBP
3 DEHP
4 DNOP
5 DINP
6 DIDP
4
1.1
1.0
0.9
0.8
0.7
TICC
0.6
0.5
m/z 149
0.4
0.3
0.2
m/z 293
0.1
0.0
m/z 279
5
6
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
m/z 307
13.0
14.0
Fig. 2 TICC and Mass Chromatograms of Phthalate Esters in Standard Solution
15.0
16.0
17.0
No.M261
n Analysis of Sample Solutions
The chromatograms obtained from analysis of extracts
of toys A and B are shown in Fig. 3 and 4, respectively,
and the mass chromatograms of the standard
solutions and toy sample A and sample B test
solutions are shown in Fig. 5. The peak areas of the
various components are shown in Table 2.
Comparing the mass chromatograms of Fig. 5, the
peak elution times and peak shapes of the 3
constituents (DBP, DEHP, DINP) of toy sample A test
solution, and the 2 constituents (DBP, DEHP) of toy B
test solution clearly match the corresponding peaks in
the standard solutions.
Although the peak area of DBP in the toy sample A
test solution is smaller than that of the corresponding
peak in the standard solution, the peak areas of DEHP
and DINP are larger than those of the corresponding
peaks in the standard solution, indicating that toy A is
"non-compliant."
The peak areas of both DBP and DEHP of toy sample
B test solution are smaller than those of
corresponding peaks in the standard solution,
indicating that toy B is "compliant."
(×10,000,000)
1 DBP
2 DEHP
3 DINP
2
1.0
0.9
TOTM
0.8
0.7
0.6
0.5
TICC
0.4
m/z 149
1
0.3
m/z 279
0.2
3
m/z 293
0.1
0.0
m/z 307
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
Fig. 3 TICC and Mass Chromatograms of Phthalate Esters in Toy Sample A
(×1,000,000)
1 DBP
2 DEHP
4.0
ATBC
3.5
3.0
2.5
2.0
TICC
1.5
1
2
m/z 149
1.0
m/z 279
0.5
m/z 293
0.0
m/z 307
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
Fig. 4 TICC and Mass Chromatograms of Phthalate Esters in Toy Sample B
15.0
16.0
17.0
No.M261
DBP
BBP
3.0
Standard solution
DEHP
1.0
7.0
(×100,000)
149
7.5
9.0
(×100,000)
1.5 149
9.5
4.0
7.0
(×100,000)
149
7.5
1.0
1.5
1.5
9.5
1.5
11.0
10.0
(×1,000)
7.0
7.5
9.0
9.5
11.0
10.0
12.0
12.5
(×100)
307
293
5.0
10.5
(×10,000)
279
9.5
10.0
(×100,000)
149
0.0
0.0
10.0
(×1,000)
2.0
293
11.0
1.00
1.5
0.75
1.0
0.50
0.5
11.0
12.0
5.0
10.0
(×100)
307
12.5
10.0
12.5
2.5
0.0
0.0
0.25
-0.5
0.00
9.5
2.5
2.5
0.5
0.5
0.5
0.5
0.0
0.0
10.5
(×10,000)
279
5.0
1.0
1.0
1.0
2.5
0.5
1.0
1.0
9.0
(×100,000)
149
5.0
1.5
2.0
0.5
0.5
Toy sample B
1.5
3.0
1.0
1.0
2.0
0.00
DIDP
(×100)
307
7.5
2.0
0.25
9.5
10.0
(×100,000)
149
DINP
293
0.75
0.5
2.0
1.5
(×1,000)
0.50
0.5
0.0
(×10,000)
279
1.00
1.0
1.0
Toy sample A
1.25
1.5
2.0
2.5
DNOP
(×100,000)
2.0 149
(×100,000)
149
(×100,000)
149
10.5
10.0
11.0
10.0
11.0
12.0
Fig. 5 Mass Chromatograms of Phthalate Esters in Standard and Toy Sample (A and B)
Table 2 Phthalate Ester Peak Areas in Standard and Toy Sample (A and B)
DBP (m/z 149)
BBP (m/z 149)
DEHP (m/z 149) DNOP (m/z 279)
Standard solution
429950
167370
228814
16377
20610
15873
Toy sample A
22368
n.d.
14414977
n.d.
101614
6967
NG
Toy sample B
8201
n.d.
11576
n.d.
n.d.
n.d.
OK
In addition, plasticizers other than phthalate esters
were also detected, namely TOTM (trioctyl trimellitate)
in toy sample A, and ATBC (acetyl tributyl citrate) in
toy sample B (Fig. 3 and 4). The structures of TOTM
and ATBC are shown in Fig. 6, and their mass spectra
are shown in Fig. 7.
O
O
O
O
O
O
O
O
O
O
O
TOTM
ATBC
%
100
75
50
25
0
%
100
75
50
25
0
Fig. 6 Structures of TOTM and ATBC
[Reference]
Ministry of Health, Labour and Welfare Notification No.336, September 6, 2010
SHIMADZU CORPORATION. International Marketing Division
DIDP (m/z 307)
Remarks
These compounds are considered to be alternatives to
phthalate ester plasticizers, and their use is
expanding.TOTM is used in medical and automotive
applications, and ATBC is used in food wrap and soft
polyvinyl chloride toys, etc. Thus, GC/MS can be used
to verify the presence of plasticizers other than
restricted phthalate ester plasticizers.
O
O
O
DINP (m/z 293)
3. Kanda-Nishikicho 1-chome, Chiyoda-ku, Tokyo 101-8448, Japan Phone: 81(3)3219-5641 Fax. 81(3)3219-5710
305
57 71
50
113
100
193
211
148
150
200
50
112
100
250
300
350
435
417
400
450
500
185
129
57
TOTM
ATBC
259
139 157
150
213
200
329
273
250
550
300
350
Fig. 7 Mass Spectra of TOTM and ATBC
400