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National food safety standard - Food contact materials and products - Determination of phthalate esters and determination of migration
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| GB 31604.30-2016 | English | 85 |
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National food safety standard - Food Contact Materials and Articles - Determination of the Content and Migration of Phthalate Esters
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GB 31604.30-2025: PDF in English GB 31604.30-2025
GB
NATIONAL STANDARD OF THE
PEOPLE’S REPUBLIC OF CHINA
National Food Safety Standard - Food Contact Materials
and Products - Determination of Phthalate Esters and
Determination of Migration
ISSUED ON. MARCH 16, 2025
IMPLEMENTED ON. SEPTEMBER 16, 2025
Issued by. National Health Commission of the People’s Republic of China;
State Administration for Market Regulation.
Table of Contents
Foreword... 3
1 Scope... 4
Section I - Determination of Phthalate Esters... 4
2 Principle... 4
3 Reagents and Materials... 4
4 Instruments and Equipment... 6
5 Analytical Steps... 6
6 Expression of Analytical Results... 9
7 Precision... 9
8 Others... 9
Section II - Determination of Migration of Phthalate Esters... 10
9 Principle... 10
10 Reagents and Materials... 10
11 Instruments and Equipment... 11
12 Analytical Steps... 12
13 Expression of Analytical Results... 13
14 Precision... 15
15 Others... 16
Appendix A Information of 19 Phthalate Esters... 17
Appendix B Table of Quantitative and Qualitative Selected Ions of 19 Phthalate Esters
... 18
Appendix C Gas Chromatography - Mass Spectrometry Reference Spectrums of
Standard Solutions of Phthalate Esters... 19
National Food Safety Standard - Food Contact Materials
and Products - Determination of Phthalate Esters and
Determination of Migration
1 Scope
This Standard specifies the determination methods for 19 phthalate esters and the migration in
food contact materials and products. dimethyl phthalate (DMP), diethyl phthalate (DEP), diallyl
phthalate (DAP), diisobutyl phthalate (DIBP), di-n-butyl phthalate (DBP), bis(2-methoxyethyl)
phthalate (DMEP), bis(4-methyl-2-pentyl) phthalate (BMPP), bis(2-ethoxyethyl) phthalate
(DEEP), di-n-pentyl phthalate-D4 (DPP), di-n-hexyl phthalate (DHXP), benzyl butyl phthalate
(BBP), bis(2-n-butoxyethyl) phthalate (DBEP), dicyclohexyl phthalate (DCHP), bis(2-
ethylhexyl) phthalate (DEHP), diphenyl phthalate (DPhP), di-n-octyl phthalate (DNOP),
dinonyl phthalate (DNP), diisononyl phthalate (DINP-1), diisononyl phthalate - C8 ~ C10 (C9
enriched) (DINP-2), diisodecyl phthalate (DIDP-1), and diisononyl phthalate - C9 ~ C11 (C10
enriched) (DIDP-2).
Section I - Determination of Phthalate Esters is applicable to the determination of 19 phthalate
esters in food contact materials and products, such as. plastics, rubber, paint coatings and
adhesives, etc. Section II - Determination of Migration of Phthalate Esters is applicable to the
determination of the migration of 19 phthalate esters in food contact materials and products.
Section I - Determination of Phthalate Esters
2 Principle
Phthalate esters in food contact materials and products are extracted by ultrasonic method using
tetrahydrofuran as the solvent. For soluble specimens, polymers and other substances are
precipitated with n-hexane, and the extracting solution is centrifuged and concentrated, and
after reaching a constant volume, it is used for gas chromatography-mass spectrometry. The
insoluble specimens are repeatedly extracted using tetrahydrofuran, and the extracting solutions
are concentrated, and after reaching a constant volume, they are used for gas chromatography-
mass spectrometry. The retention times and characteristic ions are used for qualitative analysis,
and the external standard method for quantitative analysis.
3 Reagents and Materials
Unless otherwise specified, the reagents used in this Method are chromatographically pure
reagents, or analytically pure reagents, in which, no phthalate esters to be tested are detected by
blank test analysis, and the water is Grade-1 water specified in GB/T 6682.During the test,
avoid using plastic utensils, or use plastic utensils, in which, no phthalate esters to be tested are
detected by blank test analysis.
3.1 Reagents
3.1.1 n-Hexane (C6H14).
3.1.2 Tetrahydrofuran (C4H8O).
3.2 Standard Substances
19 phthalate esters standard substances (see Appendix A). purity 95%, or standard substances
certified by the state and awarded with standard substance certificates.
3.3 Preparation of Standard Solutions
3.3.1 Single standard stock solutions of 19 phthalate esters (5,000 mg/L). respectively and
accurately weigh-take 50 mg of each of the 19 phthalate ester standard substances (in
accordance with NOTE a in Table A.1, select DINP-1 or DINP-2, DIDP-1 or DIDP-2 standard
substances), convert the actual weighed mass in accordance with the purity, accurate to 0.1 mg.
Use n-hexane to dissolve them and accurately reach a constant volume of 10 mL, and mix them
well. Transfer the solutions to brown glass containers and store them in a 20 C refrigerator
away from light. The shelf life is 6 months.
3.3.2 Mixed standard intermediate solution A of 19 phthalate esters. accurately transfer-take 10
mL of DINP-1 or DINP-2 standard stock solution (5,000 mg/L), 10 mL of DIDP-1 or DIDP-2
standard stock solution (5,000 mg/L), 1 mL of DNOP standard stock solution (5,000 mg/L), 1
mL of DNP standard stock solution (5,000 mg/L) and 0.5 mL of each of the other phthalate
esters standard stock solutions (5,000 mg/L) into a 100 mL volumetric flask, add n-hexane to
reach a constant volume of 100 mL, and mix it well. Among them, the mass concentration of
DINP-1 or DINP-2 is 500 mg/L, the mass concentration of DIDP-1 or DIDP-2 is 500 mg/L, the
mass concentration of DNOP is 50 mg/L, the mass concentration of DNP is 50 mg/L, and the
mass concentration of other phthalate esters is 25 mg/L. Transfer the solution to a brown glass
container and store it in a 20 C refrigerator away from light. The shelf life is 6 months.
3.3.3 Phthalate esters series mixed standard working solutions. into five 50 mL volumetric
flasks, respectively and accurately transfer-take 0.10 mL, 0.20 mL, 0.50 mL, 1.0 mL and 2.0
mL of 19 phthalate esters mixed standard intermediate solution A, use n-hexane to reach a
constant volume and mix them well. Thus, the phthalate esters series mixed standard working
solutions are obtained. Among them, the mass concentration of DINP-1 or DINP-2, DIDP-1 or
DIDP-2 is 1.0 mg/L, 2.0 mg/L, 5.0 mg/L, 10 mg/L and 20 mg/L; the mass concentration of
DNOP and DNP is 0.10 mg/L, 0.20 mg/L, 0.50 mg/L, 1.0 mg/L and 2.0 mg/L; the mass
concentration of the other phthalate esters is 0.050 mg/L, 0.10 mg/L, 0.25 mg/L, 0.50 mg/L and
1.0 mg/L. Prepare them right before use.
4 Instruments and Equipment
4.1 Gas chromatograph-mass spectrometer. equipped with electron impact ionization source
(EI).
4.2 Analytical balance. with a division value of 0.0001 g.
4.3 Glassware.
NOTE. after cleaning, use water to rinse it 3 times, soak in tetrahydrofuran for 1 hour and rinse 3
times, dry, and cool to room temperature for later use.
4.4 Ultrasonic generator.
4.5 Rotary evaporator.
4.6 Centrifuge. speed 4,000 r/min.
4.7 Vortex oscillator.
4.8 Cryogenic grinding instrument.
4.9 Glass filter membrane. organic phase, with a pore size of 0.45 m.
5 Analytical Steps
5.1 Sample Pre-treatment
5.1.1 Preparation of test solution
Take representative specimens. For solid specimens, such as. resin, plastic and rubber, etc., cut
them into fragments, or cut them into fragments and then, use liquid nitrogen to perform
cryogenic grinding, so as to control the size of the fragments to 0.1 cm, and evenly mix them.
For thin layer solid specimens, such as. coatings and adhesive layers, use a knife to scrape them,
or use a knife to scrape them and then, cut them into fragments or use liquid nitrogen to perform
cryogenic grinding, so as to control the size of the fragments to 0.3 cm, and evenly mix them.
For liquid specimens, such as. coatings and adhesives, directly sample them.
Accurately weigh-take 0.2 g ~ 0.5 g of specimen (accurate to 0.0001 g) into a centrifuge tube,
add 10 mL of tetrahydrofuran, and extract by ultrasonic method for 30 min.
For specimens that are soluble or turbid during ultrasound, after extraction, slowly add 40 mL
of n-hexane and perform vortex oscillation. At 4,000 r/min, centrifuge for 20 min. Take the
supernatant, and at 45 C under reduced pressure, perform rotary evaporation to about 3 mL,
and use n-hexane to reach a constant volume of 10 mL. Filter it through a 0.45 m organic
phase glass filter membrane for the determination by gas chromatograph-mass spectrometer.
c) Ionization mode. electron impact ionization source (EI);
d) Monitoring mode. selected ion monitoring mode (SIM), and the monitored ions are
shown in Table B.1;
e) Ionization energy. 70 eV;
f) Solvent delay. 7 min.
5.3 Qualitative Determination
In accordance with the instrument reference conditions, the following conditions shall be
satisfied to determine the presence of the corresponding targets in the sample.
a) The difference between the chromatographic peak retention time of the phthalate
esters detected in the sample and the chromatographic peak retention time of the target
compound in the standard solution is within the range of 0.5%;
b) The selected ions appear in the sample mass spectrogram after background
subtraction and the signal-to-noise ratio is 3;
c) The deviation between the relative abundance of the qualitative ions and that of the
standard solution with equivalent concentration shall not exceed those specified in
Table 1.
Table 1 -- Maximum Allowable Deviation of Relative Abundance Ratio of Ions
5.4 Preparation of Standard Curve
Inject the series standard working solutions into the gas chromatograph-mass spectrometer to
determine the peak area of the quantitative ion of the corresponding phthalate ester. Take the
concentration of the standard working solutions as the horizontal axis and the peak area of the
quantitative ions of each phthalate ester as the vertical axis to draw the standard curve.
5.5 Determination of Specimen Solution
Inject the test solution into the gas chromatograph-mass spectrometer to obtain the peak area of
the quantitative ion of each phthalate ester. In accordance with the standard curve, obtain the
concentration of each phthalate ester in the solution to be tested.
The test solution can be diluted in accordance with the specific situation, so that its determined
value is within the linear range of the standard curve.
Relative Ion Abundance, K/%
Maximum Allowable Deviation/%
6 Expression of Analytical Results
The content of a single phthalate ester in the specimen is calculated in accordance with Formula
(1).
Where,
X---the content of a single phthalate ester in the specimen, expressed in (mg/kg);
c---the mass concentration of a single phthalate ester in the specimen extracting solution,
expressed in (mg/L);
c0---the mass concentration of a single phthalate ester in the blank extracting solution, expressed
in (mg/L);
V---the constant volume of the specimen, expressed in (mL);
N---the dilution factor, by which, the test solution is diluted to make the determined value within
the linear range of the standard curve;
m---the mass of the specimen, expressed in (g);
The result shall retain at least 2 significant figures.
7 Precision
The absolute difference between two independent determination results obtained under
repeatability conditions must not exceed 10% of the arithmetic mean.
8 Others
When the sampling size is 0.2 g and the constant volume is 10 mL, in this Method, the detection
limit of diisononyl phthalate and diisononyl phthalate - C8 ~ C10 (C9 enriched), diisodecyl
phthalate and diisononyl phthalate - C9 ~ C11 (C10 enriched) is 25 mg/kg, and the
quantification limit is 50 mg/kg; the detection limit of di-n-octyl phthalate and dinonyl phthalate
is 2.5 mg/kg, and the quantification limit is 5.0 mg/kg; the detection limit of other phthalate
esters is 1.0 mg/kg, and the quantification limit is 2.5 mg/kg.
and 1 mL of each of the other phthalate esters standard stock solutions (5,000 mg/L) into a 100
mL volumetric flask, add n-hexane to reach a constant volume of 100 mL, and mix it well.
Among them, the mass concentration of DINP-1 or DINP-2 is 500 mg/L, the mass
concentration of DIDP-1 or DIDP-2 is 500 mg/L, and the mass concentration of DBP is 25
mg/L, and the mass concentration of the other phthalate esters is 50 mg/L. Transfer the solution
to a brown glass container and store it in a 20 C refrigerator away from light. The shelf life
is 6 months.
10.3.3 Phthalate esters series standard working solutions of aqueous, acidic, ethanol-containing
food simulants and chemical alternative solvents. in five 50 mL volumetric flasks, respectively
and accurately transfer-take 0.10 mL, 0.20 mL, 0.50 mL, 1.0 mL and 2.0 mL of the mixed
standard intermediate solution B of 19 phthalate esters, use n-hexane to reach a constant volume
and mix them well. Among them, the mass concentration of DINP-1 or DINP-2, DIDP-1 or
DIDP-2 is 1.0 mg/L, 2.0 mg/L, 5.0 mg/L, 10 mg/L and 20 mg/L; the mass concentration of DBP
is 0.050 mg/L, 0.10 mg/L, 0.25 mg/L, 0.50 mg/L and 1.0 mg/L; and the mass concentration of
the other phthalate esters is 0.10 mg/L, 0.20 mg/L, 0.50 mg/L, 1.0 mg/L and 2.0 mg/L. Prepare
them right before use.
10.3.4 Phthalate esters series standard working solutions of oil-containing food simulants.
weigh-take 5 portions of 5 g (accurate to 0.01 g) of olive oil, respectively add 0.010 mL, 0.020
mL, 0.050 mL, 0.10 mL and 0.20 mL of the mixed standard intermediate solution B of 19
phthalate esters and mix them well by vortex. Among them, the mass concentration of DINP-1
or DINP-2, DIDP-1 or DIDP-2 is equivalent to 1.0 mg/kg, 2.0 mg/kg, 5.0 mg/kg, 10 mg/kg and
20 mg/kg, the mass concentration of DBP is equivalent to 0.050 mg/kg, 0.10 mg/kg, 0.25 mg/kg,
0.50 mg/kg and 1.0 mg/kg, and the mass concentration of the other phthalate esters is equivalent
to 0.10 mg/kg, 0.20 mg/kg, 0.50 mg/kg, 1.0 mg/kg and 2.0 mg/kg. In accordance with 12.2.4,
handle the standard working solutions. Prepare them before use.
11 Instruments and Equipment
11.1 Gas chromatograph-mass spectrometer. equipped with electron impact ionization source
(EI).
11.2 Analytical balance. with a division value of 0.0001 g and 0.01 g.
11.3 Centrifuge. speed 4,000 r/min.
11.4 Vortex oscillator.
11.5 Solid phase extraction device.
11.6 Rotary evaporator.
11.7 Glassware.
NOTE. after cleaning, use water to rinse it 3 times, soak in tetrahydrofuran for 1 hour and rinse 3
times, dry, and cool to room temperature for later use.
11.8 Solid phase extraction cartridge. PSA/Silica composite filler glass column (500 mg/500
mg, 6 mL) or others with equivalent performance.
12 Analytical Steps
12.1 Preparation of Soaking Solution
In accordance with the requirements of GB 5009.156 and GB 31604.1, carry out a migration
test on the sample to obtain the soaking solution.
12.2 Preparation of test solutions
12.2.1 Aqueous, acidic, and ethanol-containing food simulants (volume fraction of ethanol
< 50%)
Accurately transfer-take 10 mL of the soaking solution into a 25 mL centrifuge tube, add 4 mL
of n-hexane, perform vortex oscillation and extract for 10 min, at 4,000 r/min, centrifuge it for
5 min, and take the n-hexane layer. Then, repeat the extraction twice and combine the extracting
solutions. At 45 °C under reduced pressure, perform rotary evaporation on the extracting
solution to dryness. Add 1 mL of n-hexane, perform vortex oscillation to re-dissolve it, and take
the supernatant for instrument detection.
12.2.2 Ethanol-containing food simulants (50% volume fraction of ethanol < 95%)
Accurately transfer-take 10 mL of the soaking solution into a 50 mL centrifuge tube, add 10 mL
of water and 8 mL of n-hexane, perform vortex oscillation and extract for 10 min, at 4,000 r/min,
centrifuge for 5 min, and take the n-hexane layer. Then, repeat the extraction twice and combine
the extracting solutions. At 45 °C under reduced pressure, perform rotary evaporation on the
extracting solution to dryness. Add 1 mL of n-hexane, perform vortex oscillation to re-dissolve
it, and take the supernatant for instrument detection.
12.2.3 95% (volume fraction) ethanol and isooctane chemical alternative solvents
Accurately transfer-take 10 mL of the soaking solution into a flask, and at 45 °C under reduced
pressure, perform rotary evaporation to dryness. Add 1 mL of n-hexane, perform vortex
oscillation to re-dissolve it, and take the supernatant for instrument detection.
12.2.4 Oil-containing food simulants
Weigh-take 5 g (accurate to 0.01 g) of the soaking solution into a 50 mL centrifuge tube, add
20 mL of acetonitrile, perform vortex oscillation and extract for 10 min, at 4,000 r/min,
centrifuge for 10 min, and take the acetonitrile layer. Repeat the extraction once and combine
the extracting solutions in a flask. At 45 °C under reduced pressure, perform rotary evaporation
on the combined acetonitrile extracting solution to about 3 mL as the solution to be purified.
Add 10 mL of acetonitrile to the solid phase extraction cartridge for activation, and discard the
c0---the mass concentration of a single phthalate ester in the blank soaking solution, expressed
in (mg/L);
V---the constant volume, expressed in (mL);
N---the dilution factor, by which, the test solution is diluted to make the determined value within
the linear range of the standard curve;
V0---the sampling size, expressed in (mL).
13.1.2 Oil-containing food simulants
The content of a single phthalate ester in oil-containing food simulants is calculated in
accordance with Formula (3).
Where,
X1---the content of a single phthalate ester in food simulants, expressed in (mg/kg);
M---the mass concentration of a single phthalate ester in the specimen soaking solution,
expressed in (mg/kg);
M0---the mass concentration of a single phthalate ester in the blank soaking solution, expressed
in (mg/kg);
N---the dilution factor, by which, the specimen solution is diluted to make the determined value
within the linear range of the standard curve.
13.2 Calculation of Specific Migration of Phthalate Esters in Food Contact
Materials and Products
13.2.1 Calculation of specific migration of phthalate esters in food contact materials and
products for non-sealed and sealed products (expressed in mg/kg)
For food contact materials and products for non-sealed products and sealed products, such as.
lids, sealing rings and connectors, etc., the specific migration of a single phthalate ester, when
expressed in mg/kg, is calculated in accordance with Formula (4).
Where,
X2---the specific migration of a single phthalate ester in food contact materials and products,
expressed in (mg/kg);
V1---the volume or mass of the specimen soaking solution in the migration test, expressed in (L)
or (kg);
S0---the area of food contact materials and products that are in contact with food during actual
use, expressed in (dm2);
S1---the area of contact between the specimen and the soaking solution in the migration test,
expressed in (dm2);
m0---for non-sealed products, it refers to the mass corresponding to the mass of solid food or
the volume of liquid food that the food contact materials and products come into contact with
during actual use, expressed in (kg); for sealed products, it refers to the mass corresponding to
the mass of solid food or the volume of liquid food in the actual supporting containers of food
contact materials and products, expressed in (kg). The volume of various liquid foods is
converted into the corresponding mass based on the density of 1 kg/L.
When the area / volume of the sample in contact with food during actual use is unknown, “S0/m0”
in Formula (4) is taken as 6 dm2/kg.
The result shall retain at least 2 significant figures.
13.2.2 Calculation of specific migration of phthalate esters in food contact materials and
products for sealed products (expressed in mg/piece)
When the intended use is unknown, for food contact materials and products for sealed products,
the specific migration of a single phthalate ester is expressed in mg/piece and calculated in
accordance with Formula (5). The migration test method used and the contact area between a
single sealed product and the food simulant in the migration test need to be indicated.
Where,
X3---the specific migration of a single phthalate ester in food contact materials and products,
expressed in (mg/piece);
V1---the volume or mass of the specimen soaking solution, expressed in (L) or (kg);
n---the quantity of sealed products for soaking, expressed in pieces.
The result shall retain at least 2 significant figures.
14 Precision
The absolute difference between two independent determination results obtained under
repeatability conditions must not exceed 15% of the arithmetic mean.
......
Source: Above contents are excerpted from the PDF -- translated/reviewed by: www.chinesestandard.net / Wayne Zheng et al.
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