Detail Information of GB 31604.30-2016; GB31604.30-2016
Description (Translated English): Determination of phthalate esters in food plastic packaging materials
Sector / Industry: National Standard
Classification of Chinese Standard: X09
Word Count Estimation: 12,151
Date of Issue: 2016-10-19
Date of Implementation: 2017-04-19
Older Standard (superseded by this standard): SN/T 2037-2007; GB/T 21928-2008
Regulation (derived from): State Health and Family Planning Commission Notice No.1516 of 2016
GB 31604.30-2016
Determination of phthalate esters in food plastic packaging materials
National Standards of People's Republic of China
National food safety standards
Food contact materials and products
Determination of phthalates and determination of migration
Published on.2016-10-19
2017-04-19 Implementation
China
National Health and Family Planning Commission released
Foreword
This standard replaces GB/T 21928-2008 "Determination of Phthalates in Food Plastic Packaging Materials" and SN/T 2037-2007
"Determination of migration of phthalate plasticizers in plastic molded articles in contact with foodstuffs - Gas chromatography-mass spectrometry".
Compared with GB/T 21928-2008 and SN/T 2037-2007, the main changes are as follows.
--- Revised the name of the standard "National Food Safety Standards Determination and Migration of Phthalates in Food Contact Materials and Articles
Amount of measurement";
--- Modify the scope of application;
--- Modified measurement method;
--- Modified detection limit.
National food safety standards
Food contact materials and products
Determination of phthalates and determination of migration
1 Scope
This standard specifies the determination of phthalate esters in food contact materials and products and the determination of migration.
This standard applies to the determination of phthalate esters in food plastic packaging materials and products, and to food contact materials and products.
Determination of migration of phthalate esters.
Phthalates Determination
2 principle
Food plastic packaging materials and products were crushed and extracted by ultrasonic extraction with n-hexane. The extracts were filtered and used for gas chromatography-mass spectrometry.
Method determination. The feature-selective ion monitoring scan mode (SIM) was used to quantify the retention time and the abundance ratio of fragments compared to qualitative and external standards.
3 Reagents and materials
Unless otherwise stated, the reagents used in this method are all chromatographic (or analytically pure and redistilled). Water is for all-glass installations
Redistilled water and stored in a glass container.
3.1 Reagents
3.1.1 n-Hexane (C6H14).
3.1.2 Acetone (CH3COCH3).
3.2 Phthalates Standards
Dimethyl Phthalate (DMP), Diethyl Phthalate (DEP), Diallyl Phthalate (DAP), Phthalate II
Isobutyl ester (DIBP), Di-n-butyl phthalate (DBP), Di(2-methoxy)ethyl phthalate (DMEP), Phthalic acid II
(4-Methyl-2-pentyl) ester (BMPP), bis(2-ethoxy)ethyl phthalate (DEEP), diamyl phthalate (DPP), o-phenylene
Dihexyl formate (DHXP), Butyl benzyl phthalate (BBP), Di(2-butoxy)ethyl phthalate (DBEP), Phthal
Dicyclohexyl acid ester (DCHP), Di(2-ethylhexyl) phthalate (DEHP), Diphenyl phthalate (DPhP), Phthalate II
n-Octyl ester (DNOP), diisodecyl phthalate (DINP), dinonyl phthalate (DNP). purity >95.0%.
3.3 Preparation of standard solution
3.3.1 18 standard phthalate stock solutions (1000μg/mL). 18 phthalate standards accurately weighed
25mg, dissolved in n-hexane and quasi-contained to 25mL, stored in a refrigerator at 4 °C protected from light.
3.3.2 17 kinds of phthalates standard use solution (10μg/mL). Accurate removal of 17 kinds of phthalates except diisodecyl phthalate
Place 1 mL of standard stock solution (1000 μg/mL) of acid ester into a 100 mL volumetric flask and add n-hexane to 100 mL in a refrigerator at 4°C.
Keep away from light.
3.3.3 Diisodecyl phthalate standard solution (100μg/mL). Accurately transfer standard diisodecyl phthalate stock solution
(1000 μg/mL) 10 mL to a 100 mL volumetric flask, adding n-hexane to 100 mL, and stored in a refrigerator at 4°C in the dark.
3.3.4 Phthalates series standard working solution. Accurately transfer proper amount of phthalic acid standard use solution, using n-hexane to prepare the concentration
0.02 mg/L, 0.05 mg/L, 0.10 mg/L, 0.20 mg/L, 0.50 mg/L, and 1.00 mg/L of 17 phthalate esters
The mixed standard uses liquids and concentrations of 0.5 mg/L, 1.0 mg/L, 2.0 mg/L, 5.0 mg/L, 10.0 mg/L, and 20.0 mg/L of o-benzene
Diisodecyl diformate (DINP) single-label use solution.
4 Instruments and Equipment
4.1 Gas chromatography-mass spectrometry (GC-MS).
4.2 Analytical balance. Sensitivity 0.0001g and 0.01g.
4.3 Ultrasonic generator.
4.4 Glassware.
Note. After the glassware is washed, it shall be rinsed 3 times with heavy distilled water, soaked in acetone for 1 hour, baked at.200°C for 2 hours, and then cooled to room temperature.
5 Analysis steps
5.1 sample preparation
Take 5g typical sample, cut the sample (without cling film) to a single piece diameter ≤ 0.2cm, cling film debris diameter ≤ 0.3cm, mixed
Evenly, accurately weigh 0.2g ~ 0.5g sample (accurate to 0.0001g) in a stoppered flask, add 20mL n-hexane, ultrasonic extraction
After 30 minutes, the residue was filtered and the residue was repeatedly extracted with 20 mL of n-hexane once. The filtrate was combined in a 50 mL volumetric flask, and the content was adjusted to volume with n-hexane.
Degree, depending on the content of phthalate esters in the sample for dilution, after mixing, the organic phase glass membrane is 0.45 μm, and the gas phase chromatograph-mass spectrometer
Instrument analysis.
5.2 Blank test
The reagent used in the test was treated as in 5.1 and subjected to GC-MS analysis.
5.3 Instrument Reference Conditions
5.3.1 Gas Chromatography Reference Conditions
a) Column. 5% Phenyl-Methyl Siloxane Quartz Capillary Column or analytical column with similar performance. Specifications. Column Length 30.0m, Inner Diameter
0.25mm, film thickness 0.25μm;
b) Inlet temperature. 260°C;
c) Temperature increase program. Initial column temperature is 60°C, hold for 1min, raise temperature to 220°C at 20°C/min, hold for 1min, then use 5°C/min
Warming to 250 ° C, hold 1min, and then heated to 20 ° C/min to 290 ° C, keep 7.5min;
d) carrier gas. helium (purity > 99.999%), flow rate. 1 mL/min;
e) Injection method. splitless injection;
f) Injection volume. 1 μL.
5.3.2 Mass Spectrometry Reference Conditions
a) Chromatography and mass spectrometry interface temperature. 280°C;
b) Ion source temperature. 230°C;
c) Ionisation. Electron Impact Ionization (EI);
d) Monitoring method. Select ion scan mode (SIM), monitoring ions see Appendix B;
e) Ionization energy. 70 eV;
f) Solvent delay. 7 min.
5.4 Making Standard Curves
Injection of a series of standard working solutions into a gas chromatograph-mass spectrometer to determine the peaks of the quantified ions of the corresponding phthalate compounds
Area, the concentration of the standard working solution is plotted on the abscissa, and the peak area of the quantified ions of each phthalate compound is plotted on the ordinate.
Quasi-curve.
5.5 Determination of sample solution
The sample solution is injected into the gas chromatograph-mass spectrometer to obtain the peak area of the quantified ions for each phthalate compound, according to the standard
The curve gives the concentration of each phthalate ester compound in the test solution.
5.6 Qualitative
The selected ions of the test sample solution and the standard product appear at the same retention time (±0.5%) and correspond to the mass charge of the mass spectrum fragment ions.
Consistent with the standard product, its abundance ratio should be in accordance with Table 1 compared to the standard product, which can qualitatively confirm the target analyte. Phthalate ester compound
Retention times, qualifier ions, and quantifier ions are listed in Appendix B. Gas Chromatography-Mass Spectrometry Selection of Reference Materials for Phthalates
See Appendix C for ion chromatograms.
Table 1 Ion Relative Abundance Ratio Maximum Allowable Deviation
Relative ion abundance
>50 >20~50 >10~20 ≤10
Allowed maximum deviation
±10 ±15 ±20 ±50
6 Expression of analysis results
The content of phthalate ester compound in the sample is calculated according to equation (1).
Xi=
(ρi-ρ0)×V×k
(1)
In the formula.
Xi --- The content of some kind of phthalates in the sample, in milligrams per kilogram (mg/kg);
Ρi --- The concentration corresponding to the area of a phthalate ester in the sample extract, in milligrams per liter (mg/L);
Ρ0 --- The concentration of a phthalate ester in a blank sample in milligrams per liter (mg/L);
V --- constant volume of the sample, in milliliters (mL);
k --- dilution factor;
m --- sample mass in grams (g).
The calculation results retain three significant figures.
7 Precision
The absolute difference between two independent determinations obtained under repeatability conditions must not exceed 20% of the arithmetic mean.
8 Others
The method has a quantitative limit of 50.0 mg/kg for diisodecyl phthalate and a quantification limit of 5.00 mg/kg for the remaining 17 phthalates.
Measurement of migration
9 Principle
Food plastic packaging materials and products are soaked with food simulants. The plasticizer migrates to the soaking liquid and takes a certain amount of simulated soaking liquid.
Concentrate, hexane was dissolved and centrifuged. The supernatant was determined by gas chromatography-mass spectrometry to determine the plasticizer in the sample within a certain concentration range.
The amount of migration was quantitatively tested by external standards and confirmed.
10 Reagents and Materials
Unless otherwise stated, the reagents used in this method are all chromatographic (or analytically pure and redistilled). Water is a full glass device
The redistilled water was stored and stored in a glass container.
10.1 Reagents
10.1.1 Hexane (C6H14).
10.1.2 Anhydrous ethanol (C2H5OH).
10.1.3 Acetic acid (CH3COOH).
10.1.4 Reagents for preparing acidic and alcoholic food simulants. According to the provisions of GB 31604.1.
10.1.5 Isooctane. Oil-based food simulant.
10.2 Standards
18 kinds of phthalate standard products, with 3.2.
10.3 Preparation of Standard Solution
10.3.1 Standard stock solution. Same as 3.3.1.
10.3.2 17 kinds of phthalates standard use liquid. the same with 3.3.2.
10.3.3 Diisodecyl phthalate standard solution. Same as 3.3.3.
10.3.4 Phthalates Standard Series Working Solutions. Accurate removal of suitable amount of phthalic acid standard use solution, using n-hexane to prepare the concentration
0.1 mg/L, 0.2 mg/L, 0.5 mg/L, 1.0 mg/L, 3.0 mg/L, 8.0 mg/L, and 10.0 mg/L of 17 phthalates
Mixture standard substance use solution and concentration of 0.5mg/L, 1.0mg/L, 3.0mg/L, 8.0mg/L, 10.0mg/L phthalate II
Isononyl ester (DINP) single-standby.
11 Instruments and Equipment
11.1 Gas Chromatography-Mass Spectrometer. With Electron Impact Source (EI).
11.2 Centrifuge.
11.3 Oscillator.
11.4 Solid phase extraction device.
11.5 Constant temperature oven.
11.6 Cryogenic Incubator.
11.7 Centrifuge tube. 10 mL.
11.8 Volumetric flask. 10 mL.
11.9 Glassware.
Note. After the glassware is washed, it is rinsed 3 times with heavy distilled water, soaked in acetone for 1 hour, baked at.200°C for 2 hours, and cooled to room temperature for later use.
12 Analysis steps
12.1 Preparation of Food Simulator Test Solution
According to the requirements of GB 5009.156 and GB 31604.1, the samples were subjected to a migration test to obtain a food simulant test solution.
12.2 Soaking Solution Treatment
Place the soaking solution at room temperature. Accurately take it for isooctane and 95% ethanol solution (≥50% alcoholic food) mimic soak solution.
10g±0.01g soaking solution in a pear-shaped distillation flask, evaporating to near dryness in a water bath at 45°C under reduced pressure, and then adding 1mL of n-hexane to the solution.
Solution, vortex 3min, 4000r/min centrifugation 5min, collect supernatant for instrument detection.
For other simulated soaking solutions (including water-based, acidic foods, and <50% alcoholic food simulants), weigh 10g ± 0.01g of the simulation
Soak solution in 25mL centrifuge tube, add 4mL n-hexane, shaking extraction 10min, 4000r/min centrifuge speed 5min, take
Extract the upper layer of n-hexane and repeat the extraction twice. Combine the n-hexane phases in a pear-shaped distillation flask and evaporate to dryness in a 45°C water bath under reduced pressure.
After evaporation, add 1 mL of n-hexane to dissolve, vortex for 3 minutes, centrifuge at 4000r/min for 5 minutes, and collect the supernatant for instrument detection.
The sample solution can be diluted according to the specific conditions so that the measured value is within the linear range of the standard curve.
12.3 Blank Experiment
The reagents used in the test were processed according to 12.2 and subjected to GC-MS analysis.
12.4 Instrument Reference Conditions
Same as 5.3.
12.5 Making Standard Curves
With 5.4.
12.6 Determination of sample solution
Same as 5.5.
12.7 Qualitative
Same as 5.6.
13 Expression of Analysis Results
13.1 Calculation of Phthalate Esters Concentration in Food Simulators
The content of phthalate ester compounds in food simulants is calculated according to formula (2).
Xi=
(ρi-ρ0)×V×k
(2)
In the formula.
Xi --- the content of a certain kind of phthalates in the food simulant test solution, in milligrams per kilogram (mg/kg);
Ρi --- The mass concentration of a certain phthalate peak in the sample extract, in milligrams per liter (mg/L);
Ρ0 --- The mass concentration of a phthalate in the blank sample, in milligrams per liter (mg/L);
V --- constant volume of the sample, in milliliters (mL);
k --- dilution factor;
m --- The quality of the food simulant tester in grams (g).
The calculation results retain three significant figures.
13.2 Calculation of phthalate migration
The phthalate ester concentration in the sample solution obtained from 13.1 was calculated according to GB 5009.156 and the food was obtained.
Simulated products and products in a certain amount of phthalate migration. As a result, three significant figures are retained.
14 Precision
The absolute difference between two independent determinations obtained under repeatability conditions must not exceed 15% of the arithmetic mean.
15 other
The limit of quantification of diallyl phthalate in water-based, acidic foods, and alcoholic food simulants was 0.01 mg/kg.
The limit of quantitation of phthalates was 0.1 mg/kg.
Appendix A
18 commonly used phthalate ester plasticizer information
18 kinds of commonly used phthalate ester plasticizer name, abbreviation, CAS number, molecular formula, purity in Table A.1.
Table A.1 18 commonly used phthalate plasticizer information
No. Chinese Name English Name Abbreviation CAS No. Molecular Formula Purity/%
1 Dimethylphthalate Dimethylphthalate DMP 131-11-3 C10H10O4 99.5
2 Diethylphthalate DEP 84-66-2 C12H14O4 99.0
3 diallyl phthalate Diallphthalate DAP 131-17-9 C14H14O4 97.0
4 Diisobutylphthalate DIBP 84-69-5 C16H22O4 99.0
5 Dibutylphthalate DBP 84-74-2 C16H22O4 99.0
Phthalate di(2-methoxy)
Ethyl ester
Bis(2-methoxyethyl)phthalate DMEP 117-82-8 C14H18O6 94.0
Phthalate di(4-methyl-2-)
Amyl ester
Bis(4-methyl-2-pentyl)phthalate BMPP 146-50-9 C20H30O4 98.0
Phthalate di(2-ethoxy)
Ethyl ester
Bis(2-ethoxyethyl)phthalate DEEP 605-54-9 C16H22O6 99.5
9 Dipentylphthalate DPP 131-18-0 C18H26O4 99.2
10 Dihexylphthalate DHXP 84-75-3 C20H30O4 99.0
11 Butyl phthalate Benzylbutylphthalate BBP 85-68-7 C19H20O4 97.0
Phthalate di(2-butoxy)
Ethyl ester
Bis(2-n-butoxyethyl)phthalate DBEP 117-83-9 C20H30O6 98.5
13 Dicyclohexylphthalate DCHP 84-61-7 C20H26O4 99.5
Phthalate di(2-ethyl)
Hexyl ester
Bis(2-ethylhexyl)phthalate DEHP 117-81-7 C24H38O4 99.0
15 Diphenyl phthalate Diphenylphthalate DPhP 84-62-8 C20H14O4 99.5
16 di-n-octylphthalate phthalate DNOP 117-84-0 C24H38O4 97.5
17 Diisononyl phthalate DINP 28553-12-0 C26H42O4 98.5
18 Dinonylphthalate DNP 84-76-4 C26H42O4 99.5
Appendix B
Phthalates Quantitative and Qualitative Selective Ion Tables
The retention time, qualitative and quantitative ion parameters of 18 phthalates are given in Table B.1.