CN113030299A - Method for screening and evaluating safety of unintended or intended additive migration amount in recycled PET (polyethylene terephthalate) product for food contact - Google Patents
Method for screening and evaluating safety of unintended or intended additive migration amount in recycled PET (polyethylene terephthalate) product for food contact Download PDFInfo
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Abstract
The invention discloses a method for screening and evaluating safety of migration quantity of an unintended or intended additive in a regenerated PET product for food contact, which detects a food simulant of the regenerated PET product for food contact under different migration conditions by a non-targeted screening method, quantifies the detected substance by a semi-quantitative method, and evaluates safety according to relevant regulations such as GB9685-2016 and the like and based on a toxicological concern threshold method. Provides reference for the risk assessment, standard system revision and risk management assessment work of the recycled PET material for food contact.
Description
The technical field is as follows:
the invention relates to the field of food safety, in particular to a method for screening and evaluating safety of an unintended or intended additive migration amount in a regenerated PET product for food contact.
Background art:
food safety is more and more emphasized by consumers, and the safety of food packaging materials is a very important link. The food packaging material and the packaged food are mutually exchanged through absorption, dissolution, diffusion and other ways, which may affect the flavor of the food, generate toxicity and harm the health of consumers. Before being placed on the market, any material or article used for food packaging must be subjected to a migration test, and the substances released from the packaging material must be accurately identified and quantified. The detected substances and their migration are then compared with the list of substances and the limits permitted to be used in the relevant legislation and evaluated for safety. The migration test detects substances other than Intentional Additives (IAS) such as various additives and raw materials, and many unintentional additives (NIAS) mainly derived from degradation products of polymers, residual impurities of monomers, byproducts in the reaction process, and contaminants introduced in the production process. These unintended additions may be harmful, or lack toxicological information and risk assessment without being approved for use, and in order to ensure food safety, NIAS from food packaging must be accurately identified and quantified.
Polyethylene terephthalate (PET) is widely used in the fields of beverage bottles, fibers, films and the like, and most of the product packages of carbonated beverages, mineral water, edible oil and the like are PET bottles. Along with the increasingly serious plastic pollution problem and the implementation of 2020 new edition plastic token, the recycling is paid much attention as a core solution, especially for PET food packaging bottles with huge yield and consumption, if the PET food packaging bottles can be recycled after consumption and used for producing food contact materials, the recycling of the recycled PET with high value is realized, and the sustainable development of food plastic packaging is realized. However, recycled PET articles that do not meet safety standards are highly susceptible to safety risk issues once used to package food products. Research shows that the pollutant sources in the recycled PET material mainly comprise mixed small amounts of polyvinyl acetate and polyvinyl chloride, organic acids such as acetic acid generated by adhesives and the like, residual moisture, colored pollutants, aldehyde compounds, and foreign matters such as residual detergents and pesticides which are not used properly. In addition, there is a report in the literature that the recycled PET is affected by heat and light during washing, recycling and processing, which causes degradation of compounds such as additives in the material. When the recycled PET containing the above-mentioned substances is used for food contact materials, it may migrate into food, thereby threatening the physical health of consumers. Whereas european EC 2023/2006 specifies that from the source recycled PET must meet a range of safety standards before it can be used in the manufacture of food packaging. However, domestic research on the use of the recycled PET material for food contact materials is in the beginning, and in terms of safety standards and government regulations, the recycled PET is not allowed to be used for the production of food contact materials so far due to the worry about the food safety risk of the recycled PET. The analysis and detection of the IAS, the NIAS and other substances in the recycled PET material for food contact has not been reported, and the standard or method for measuring the NIAS/IAS in the recycled PET is not related. The lack of methods and monitoring data makes it difficult to perform risk assessment and risk management work on food contact PET, and therefore, research on the NIAS/IAS detection method in the recycled PET material for food contact is urgently needed.
Due to the complex sources of NIAS in the recycled PET food contact material, the low migration level and the unknown considerable amount of substances, the identification and quantitative determination of the substances are always great technical challenges for the safety analysis of the food contact material in the absence of complete chemical substance structure databases, mass spectrum databases, standards and the like.
The invention content is as follows:
the invention aims to provide a method for screening and evaluating safety of unintended or intentional additive migration quantity in recycled PET products for food contact, which detects food simulants of the recycled PET products for food contact under different migration conditions by a non-targeted screening method, quantifies detected substances by a semi-quantitative method, and evaluates safety according to relevant regulations such as GB9685-2016 and the like and based on a Threshold value of toxicological concern (TTC) method. Provides reference for the risk assessment, standard system revision and risk management assessment work of the recycled PET material for food contact.
The invention is realized by the following technical scheme:
a method for screening the migration amount of an unintended or intended additive in a recycled PET product for food contact selects finished cups, round boxes and square boxes prepared based on recycled PET as research objects, and identifies and quantitatively analyzes the migrated volatile substances, semi-volatile substances and nonvolatile substances by using a headspace-gas mass spectrometry (HS-GC/MS), a gas chromatography-mass spectrometry (GC-MS) and a liquid-quadrupole time-of-flight high-resolution mass spectrometry (LC-QTOF).
The method specifically comprises the following steps:
firstly, migration experiment: selecting 3 samples which are respectively a finished cup, a square box and a round box prepared based on the recycled PET, wherein the cup is subjected to a migration experiment under the conditions of 50% ethanol by volume fraction, 70 ℃ and 2 hours by volume fraction, 40 ℃ and 10 days by volume fraction, 95% ethanol by volume fraction, 40 ℃ and 10 days by volume fraction; the square box and the round box adopt the conditions of 95 percent ethanol by volume fraction, 60 ℃ and 2 hours by volume fraction, 40 ℃ and 10 days by volume fraction, and 95 percent ethanol by volume fraction and 40 ℃ and 10 days by volume fraction to carry out migration experiments;
secondly, identifying and quantitatively analyzing the volatile substances, the semi-volatile substances and the non-volatile substances migrated in the step one;
testing volatile substances by adopting a headspace mass spectrometer HS-GC/MS, wherein the headspace heating temperature is 85 ℃; heating for 1 h; the temperature of a sample injection needle is 100 ℃; the sample injection volume is 1 mu L; temperature programming is carried out, wherein the temperature of a sample inlet is 280 ℃; the sample injection mode is split sample injection, and the split ratio is 2: 1; the chromatographic column is DB-5MS 30m × 250 μm × 0.25 μm; the acquisition mode is a full scanning mode; the scanning range is 20-800 m/z; a threshold value 150; when the sample is 50% ethanol, taking a proper amount of the solution in the step one, and directly testing the solution on a headspace machine; when the sample is a 95% ethanol sample, the headspace on-machine test cannot be directly carried out due to safety problems, and the sample needs to be diluted into 50% ethanol by using distilled water and then is subjected to on-machine test;
testing the semi-volatile substances by a gas mass spectrometer (GC-MS) without shunting and sampling; sample introduction volume: 0.1 mu L; temperature programming: the sample inlet temperature is 280 ℃; chromatographic column DB-5MS 30m × 250 μm × 0.25 μm; a full scan acquisition mode; the scanning range is 20-800 m/z; a threshold value 150; when 50% ethanol sample: adding sodium chloride and dichloromethane, oscillating, standing, collecting the lower layer solution, blowing and concentrating to near dryness, diluting to constant volume with dichloromethane, centrifuging, collecting the supernatant, and testing on a machine; when 95% ethanol sample: weighing a proper amount of solution into a separating funnel, adding sodium chloride and dichloromethane, oscillating, standing, carrying out blowing concentration on the lower layer of dissolved liquid nitrogen until the solution is nearly dry, carrying out constant volume by using dichloromethane, centrifuging, and taking the supernatant and putting the supernatant on a machine;
for nonvolatile substances, a liquid quadrupole time-of-flight high-resolution mass spectrometer (LC-QTOF) DDA mode is adopted for testing: centrifuging the migrated solution obtained in the step one, and taking 1mL of the solution for on-machine testing; the conditions are as follows: mobile phase: phase A: 0.1% formic acid water, phase B: acetonitrile; elution gradient: 0-1.5 min, 5% B; 1.5-15 min, 5-40% B; 15-25 min, 40% -98% B; 25-32 min, 98% B; the column temperature is 40 ℃; 3 mu L of sample volume; all-first-stage ion scanning, all-second-stage ion scanning and a positive and negative ion mode; scanning the primary ions in the range of 50-1100 m/z; secondary ions, 20-800 m/z; secondary ion collision energies of 10, 20 and 40 eV;
qualitative mass spectrometry is adopted, test data of a liquid quadrupole time-of-flight high-resolution mass spectrometer are analyzed, an unknown compound is analyzed through Agilent MassHunter Qualitative Analysis software, a candidate molecular formula is screened out through a non-targeted screening method through a laboratory self-built food contact material database according to the functions of 'compound discovery' and 'identification' of the software, comparative Analysis is carried out through test spectrogram information of the unknown compound, and the matching degree between theoretical fragments and experimental fragments is a key factor for confirming the unknown compound; for the test data of the gas mass spectrometer, testing and identifying through Agilent MassHunter and NIST databases;
the standard substance is selected from substances which have similar physical and chemical properties with the compounds to be determined and do not have chemical reaction with the compounds to be determined, ethyl oleate, butyl benzyl phthalate (BBP-D4), n-heptadecane and terephthalic acid are selected as internal standard substances, and one substance with similar structure or properties with the internal standard substance is selected for semi-quantification during semi-quantification.
The invention also provides a safety assessment method for the migration amount of the unintended or intentional additives in the recycled PET products for food contact, which is characterized in that after volatile substances, semi-volatile substances and nonvolatile substances which are migrated are identified and quantitatively analyzed to confirm the related information of the name and the migration amount of the unknown compound obtained by screening, the safety assessment is carried out on each compound, and the safety assessment method specifically comprises two types, namely compliance assessment based on the permission angle of the substances and exposure level safety assessment based on the TTC method.
Compliance assessment based on the substance acceptance angle is to search the detected compounds in GB9685-2016 food contact plastic materials and articles for permitted use of additive standards for whether they are listed in the list of substances permitted for use by national safety standards and, if not, for substances which are not permitted for use.
The invention has the following beneficial effects: the method comprises the steps of detecting food simulants of the recycled PET products for food contact under different migration conditions by a non-targeted screening method, quantifying the detected substances by a semi-quantitative method, and carrying out safety assessment according to related regulations and based on a toxicological concern threshold method. Finished samples such as cups, round boxes and square boxes prepared on the basis of recycled PET are selected as research objects, and analysis technologies such as headspace-gas mass spectrometry (HS-GC/MS), gas chromatography-mass spectrometry (GC-MS) and liquid phase-quadrupole time-of-flight high-resolution mass spectrometry (LC-QTOF) are used for identifying, quantitatively analyzing and safety evaluating migrated volatile substances, semi-volatile substances and nonvolatile substances. The result is reliable, and the reference is provided for the risk assessment, standard system revision and risk management assessment work of the recycled PET material for food contact. Solves the great technical problems that the origin of NIAS in the regenerated PET food contact material is complex, the migration level is low, and a considerable amount of substances are unknown, and the identification and quantitative determination of the substances are always the safety analysis of the food contact material.
Description of the drawings:
FIG. 1 is a GC-MS diagram of three compounds, methyl linoleate (a), methyl oleate (b) and methyl palmitate (c);
FIG. 2 is a TIC graph showing the migration amount of nonvolatile substances of the cup, square box and round box samples (95% ethanol (v/v), 40 ℃ C., 10 days);
FIG. 3 is an EIC diagram of three compounds, triethylene glycol diisooctanoate (a), triethylene glycol decanoate (b), and 1, 2-bis- (4-carboxy-benzoyl) -ethane (c);
fig. 4 is a mass spectrum of three compounds, triethylene glycol diisooctanoate (a), triethylene glycol octanoate decanoate (b), and 1, 2-bis- (4-carboxy-benzoyl) -ethane (c).
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Examples the samples used for the tests were finished samples of recycled PET cups (bottom diameter 6.2cm x height 12.0cm x mouth diameter 12.0cm), round boxes (bottom diameter 13.5cm x height 9.0cm x mouth diameter 16.5cm) and square boxes (length 15.5cm x width 11.2cm x height 5.2cm), which were the same lot and were provided by guano renewable resources development ltd, guangxi parasol. The solid standard substance is required to be prepared into standard stock solution and standard working standard solution.
1290-6546 liquid chromatography-tandem high resolution time-of-flight mass spectrometer, Agilent, USA; 5975C-7890B GC, Agilent, USA; 5975C-7890B GC (equipped with G6500-CTC headspace sampling device), Agilent Inc., USA; ME204 electronic analytical balance, METTLER TOLEDO, Switzerland; Milli-Q ultra pure water generators, Millipore, USA; AS-7240BT ultrasonic generator, Tianjin Oseins.
Example 1:
first, migration experiment
Migration experiments were carried out according to GB31604.1, the specific conditions being shown in table 1. The foods that the sample cups are expected to contact are mainly water and wine, the most stringent of 50% (v/v, the same below) ethanol and 95% (v/v) ethanol are selected as food simulants; selecting conditions of 70 ℃ and 2h for experiment according to the total migration experiment condition selection principle; since no substance could be detected, slightly severe conditions of 40 ℃ and 10 days were selected for the experiment. The most strict using conditions of the square box and the round box are to contain hot cooked food containing grease, according to the selection principle of total migration experiment conditions, the experiment conditions of 95% (v/v) ethanol, 100 ℃ or reflux temperature and 2 hours are selected, in the practical experiment, the maximum experiment temperature of the 95% (v/v) ethanol is 60 ℃ from the safety point of view, so the initial conditions are adjusted to 95% (v/v) ethanol as a food simulant to carry out the experiment under the conditions of 60 ℃ and 2 hours; since no substance was detected, the experiment was continued under relatively severe experimental conditions. For comparison with sample cups, experiments were also performed using 50% (v/v) ethanol as a food simulant at 40 ℃ and 10 days.
Table 1 migration test conditions
Calculation of migration amount:
in the formula: x represents the migration amount in mg/kg; c represents the concentration of the detected substance in the sample, and the unit is mg/L; v1Represents the sample soaking volume in units of L; v2Represents the volume of the soak solution for sample measurement in unit L; v3The volume of the soaking solution for sample measurement is expressed as a constant volume, and the unit L is expressed; v4Represents the mass of contact in kg, expected or in actual use; s1Area of contact between the sample and the immersion liquid, unit dm2；S2Area of expected contact with food of sample, unit dm2。
Secondly, identifying and quantitatively analyzing the volatile substances, the semi-volatile substances and the non-volatile substances migrated in the step one;
the sample pretreatment method comprises the following steps:
volatile substance(s): for 50% ethanol samples, 5mL of the solution was taken and directly loaded into a headspace; for a 95% ethanol sample, the headspace on-machine test cannot be directly carried out due to safety problems, and the sample needs to be diluted into 50% ethanol by using distilled water and then subjected to the on-machine test. Semi-volatile materials: for 50% ethanol samples: adding sodium chloride and dichloromethane, shaking, and standing for 5 min. Taking the lower organic phase to a test tube, blowing nitrogen to concentrate the lower organic phase to be nearly dry, redissolving the lower organic phase by using dichloromethane, centrifuging the lower organic phase, taking supernatant liquid, fixing the volume to 1.0mL, and testing the upper organic phase on a machine; for the 95% ethanol sample: an appropriate amount of the solution was weighed into a separatory funnel, added with sodium chloride and dichloromethane, shaken and then allowed to stand for 5 min. And taking the lower-layer organic phase to a test tube, concentrating the lower-layer organic phase to be nearly dry by nitrogen blowing, redissolving the lower-layer organic phase by using dichloromethane, centrifuging the lower-layer organic phase, taking supernatant liquid to be constant volume to 1.0mL, and testing the supernatant liquid on a machine. Non-volatile substances: and centrifuging the solution after migration, diluting the supernatant to 1.0mL, and testing on a machine.
The chromatographic conditions include three:
headspace mass spectrometer (HS-GC/MS) conditions: testing volatile substances by adopting HS-GC/MS, wherein the specific instrument condition is that the headspace heating temperature is 85 ℃; heating for 1 h; the temperature of a sample injection needle is 100 ℃; the sample injection volume is 1 mu L; the initial temperature of the programmed temperature rise is kept for 12min at 35 ℃, and the temperature rise rate of 10 ℃/min is kept for 0min when reaching 100 ℃; then the temperature rise rate of 20 ℃/min is increased to 250 ℃ and kept for 2 min; the sample inlet temperature is 280 ℃; the sample injection mode is split sample injection, and the split ratio is 2: 1; the chromatographic column is DB-5MS 30m × 250 μm × 0.25 μm; the acquisition mode is a full scanning mode; the scanning range is 20-800 m/z; a threshold value 150.
Gas mass spectrometer (GC-MS) conditions: testing the semi-volatile substances by a gas mass spectrometer (GC-MS), wherein the specific instrument condition is non-flow-dividing sample injection; sample introduction volume: 0.1 mu L; temperature programming: keeping the initial temperature at 40 ℃ for 1min, and keeping the temperature rising rate at 5 ℃/min to 315 ℃ for 8 min; the sample inlet temperature is 280 ℃; chromatographic column DB-5MS 30m × 250 μm × 0.25 μm; a full scan acquisition mode; the scanning range is 20-800 m/z; a threshold value 150.
Liquid quadrupole time-of-flight high-resolution mass spectrometer (LC-QTOF) conditions: for the non-volatile substance, the DDA mode test of LC-QTOF is adopted, and the specific instrument conditions are as follows: phase A: 0.1% formic acid water, phase B: acetonitrile; elution gradient: 0-1.5 min, 5% B; 1.5-15 min, 5-40% B; 15-25 min, 40% -98% B; 25-32 min, 98% B; the column temperature is 40 ℃; 3 mu L of sample volume; all-first-stage ion scanning, all-second-stage ion scanning and a positive and negative ion mode; scanning the primary ions in the range of 50-1100 m/z; secondary ions, 20-800 m/z; the secondary ion collision energies were 10, 20 and 40 eV.
The mass spectrum qualitative method comprises the following steps:
all samples were assayed in triplicate under each migration assay condition and the compounds present in all triplicate assays were taken for analysis. For test data of LC-QTOF, unknown compounds were analyzed by Agilent MassHunter qualativeanalysis software. Candidate molecular formulas are screened out by using a non-targeted screening method through a laboratory self-built food contact material database according to the 'compound discovery' and 'identification' functions of software, and the matching degree between theoretical fragments and experimental fragments is a key factor for confirming the unknown compounds through comparative analysis with test spectrogram information of the unknown compounds. For the GC-MS test data, testing and identification were performed by Agilent MassHunter and NIST databases.
Selection of standard substances:
the standard substance is selected to have similar physical and chemical properties with the compound to be determined and not to have chemical reaction with the compound to be determined as far as possible. The semi-quantitative test selects ethyl oleate, butyl benzyl phthalate (BBP-D4), n-heptadecane and terephthalic acid as internal standard substances, and selects a substance with similar structure or property to the internal standard substance for semi-quantitative determination.
Thirdly, safety assessment: after identifying and quantitatively analyzing the volatile substances, semi-volatile substances and non-volatile substances which are migrated to confirm the related information of the names and the migration amounts of the unknown compounds obtained by screening, performing safety assessment on each compound, wherein the safety assessment specifically comprises compliance assessment based on the substance permission angle and exposure level safety assessment based on a TTC method.
And (3) evaluating compliance:
compliance assessments were made in view of substance approval, and the compounds detected were searched in GB9685-2016 food contact plastic materials and articles for approved use with additive standards, and listed in the list of substances approved for use by national safety standards.
Safety evaluation of exposure level:
the evaluation of a limited number of standard compounds is performed according to a limited number of standards. The evaluation of the compounds without limiting standards is based on the exposure evaluation conditions of the food contact material specified by the European Union to calculate the exposure of the crowd to the target; that is, assuming an adult of 60kg in weight, 1kg of food packed in the food contact material containing the object is ingested daily (exposure 1kg × maximum migration mg/kg).
For chemicals with low concentrations and lacking clear toxicological data, an evaluation method was established for the target substance according to the general TTC method. For the evaluation of the TTC method, according to the rules and methods for evaluating the risk of chemicals in food (compiled by the national health publishing agency, 2012), issued by the jet food and agriculture organization (JECFA), for chemicals with low concentrations and lacking clear toxicological data, they are classified into Cramer class i, ii and iii according to the structure of the compound by using the Toxtree software established by the european chemical agency, and are assigned corresponding safety exposure thresholds, and the chemicals do not need to raise safety concerns as long as the human exposure is below the corresponding thresholds. Cramer class i: chemical compounds with simple chemical structure, clear metabolic pathway and low oral toxicity; the corresponding safe exposure threshold was 1.8 mg/person/day. Cramer class ii: the chemical structure is between I and III, belonging to medium toxicity material; the corresponding safe exposure threshold was 0.54 mg/person/day. Cramer III family[32]: chemicals with complex chemical structures, possibly with significant toxic or reactive functional groups; the corresponding safe exposure threshold was 0.09 mg/person/day. If the safe exposure threshold is exceeded, further toxicological assessments or case assessments of the chemical are required.
The results are as follows:
for volatile substances, three samples were tested under experimental conditions using 50% (v/v) ethanol as food simulant at 70 ℃ and 2h and 40 ℃ and 10 days, and no compound to be considered was found after blank subtraction; when 95% (v/v) ethanol was used as a food simulant, no compounds of interest were found after blank subtraction when the test was performed at 60 ℃ and 2h and 40 ℃ and 10 days.
For semi-volatile substances, we first performed experiments using 50% (v/v) ethanol as a food simulant at 70 ℃ and 2h migration conditions, with samples pre-treated and then tested, and no compounds to be noticed were found except for the blank; we then performed migration experiments using slightly harsh test conditions (95% (v/v) ethanol as a food simulant, migrating at 60 ℃ for 2h), and no compounds to be of interest were found, minus the blank; using 50% (v/v) ethanol as a simulant, prolonging the migration experiment time to 10 days at 40 ℃, processing according to the same method, and then testing on a computer, wherein the blank is deducted from three samples, and then no compound needing attention is still found; when 95% (v/v) ethanol was used as a simulant, and the experimental time was extended to 10 days at 40 ℃, methyl oleate and methyl linoleate (see table 2) were detected in all three samples, wherein the methyl oleate compound was used as a surface active base material, a plastic plasticizer, a water repellent agent and a toughening agent for resin, which is an intentional additive IAS; methyl linoleate, which may be a contaminant introduced during production or regeneration, is an unintended additive NIAS. Where methyl palmitate is also detected in the sample cube, this compound is often used as an intermediate for emulsifiers, wetting agents, stabilizers and plasticizers, and is also a deliberate additive IAS.
From the mass spectra of the three compounds, the three compounds are prone to form corresponding molecular ion peaks (FIG. 1) for the loss of-CH3or-OCH3Formed [ M-15 ]]Or [ M-31]The fragmentation peaks of oleic acid methyl ester and linoleic acid methyl ester were not formed (FIGS. 1a and 1b), whereas palmitic acid methyl ester was lost-OCH3Form [ M-31]Fragment peak of (1 c). Methyl linoleate and methyl palmitate form more fragment peaks of M28, M41, M55 and M81, which are mainlyDue to the double bond contained in the compound; methyl oleate forms mainly the fragment peaks of alkyl groups such as M29, M43, M55, and M74. And comparing the three compounds with the standard spectrogram, wherein the main fragment peaks are basically consistent, and the relative abundance of the main fragment peaks is basically consistent with that of the fragment peaks of the substance in the standard spectrogram library, so that the qualitative result is reliable.
TABLE 2 migration test results of semi-volatile substances in the samples
For nonvolatile substances, when 50% (v/v) ethanol or 95% (v/v) ethanol is used as a food simulant, at the temperature of 60 ℃ or 70 ℃ and under the migration experiment condition of 2h, after the migration solution is centrifuged, 1mL of the solution is taken for on-machine test, and no compound needing attention is found after blank deduction. When 50% (v/v) or 95% (v/v) ethanol was used as the simulant, triethylene glycol diisooctanoate was detected in all three samples at 40 ℃ for 10 days as shown in FIG. 2a and Table 3, and the amount of substance transferred was larger in the 95% (v/v) ethanol than in the 50% (v/v) ethanol. The above results are probably due to the better solubility of triethylene glycol diisooctanoate in 95% (v/v) ethanol solution. The substance is a solvent type cold-resistant environment-friendly plasticizer, has excellent low temperature, durability, oil resistance, ultraviolet irradiation resistance and antistatic property, and is an IAS. Both triethylene glycol caprylic acid decanoate (fig. 3b) and 1, 2-bis- (4-carboxy-benzoyl) -ethane (fig. 3c), both of which are surfactants commonly used in the plastics industry and IAS, were also detected in all three samples at 40 ℃ and 10 days using 95% (v/v) ethanol as a mimic; the latter is the starting material for PET, an oligomer of terephthalic acid and ethylene glycol, and is NIAS. The mass spectra of the three compounds are shown in FIG. 4, and triethylene glycol diisocaprylate is formedIs [ M + H]+Ion Peak, [ M + NH ] formed by triethylene glycol caprylic acid decanoate4]+Ion peak, and 1, 2-bis- (4-carboxy-benzoyl) -ethane forms [ M-H]-Negative ion peak of (2). The three compounds obtained by data processing software are well matched with corresponding compound fragment peaks in a spectrum library, and the results show the reliability of detecting the three compounds in the sample.
TABLE 3 migration amount of nonvolatile substance in sample
And selecting the test result with the highest migration quantity for evaluation.
Firstly, from the perspective of compliance, the detected compounds were searched in GB9685-2016 food contact plastic materials and products allowing the use of additive standards, and none of the 6 detected compounds, such as methyl oleate, methyl linoleate, methyl palmitate, triethylene glycol caprylic decanoate, 1, 2-bis- (4-carboxy-benzoyl) -ethane, triethylene glycol diisocaprylate, and the like, were listed in the national safety standards and are substances that were not allowed to be used.
TTC evaluation is carried out on the compounds, and Cramer classification shows that the detected substances have structures of fatty acid esters or aromatic acid esters, do not have toxic functional groups and belong to oxygen-containing ester compounds. 6 esters were analyzed using a Toxtree classification decision tree, all Cramer class I with a threshold of 1.8 mg/person/day. The range of the migration amount of the detected substance is as follows: 0.00456-0.300 mg/kg; their exposure is well below the safe exposure threshold of 1.8 mg/person/day. Therefore, these 6 substances are less harmful to human health and do not need to raise safety concerns.
TABLE 3 safety assessment of the TTC method for the test substances
Note that the migration test conditions of all the substances detected were 95% ethanol, 40 ℃ for 10 days.
Claims (4)
1. A screening method for the migration amount of an unintended or intended additive in a recycled PET product for food contact is characterized in that finished cups, round boxes and square boxes prepared based on recycled PET are selected as research objects, and volatile substances, semi-volatile substances and nonvolatile substances which migrate out are identified and quantitatively analyzed by using a headspace-gas mass spectrometry, a gas chromatography-mass spectrometry and a liquid-quadrupole time-of-flight high-resolution mass spectrometry.
2. The method for screening the migration amount of the unintended or intended additives in the recycled PET articles for food contact according to claim 1, comprising the steps of:
firstly, migration experiment: selecting 3 samples which are respectively a finished cup, a square box and a round box prepared based on the recycled PET, wherein the cup is subjected to a migration experiment under the conditions of 50% ethanol by volume fraction, 70 ℃ and 2 hours by volume fraction, 40 ℃ and 10 days by volume fraction, 95% ethanol by volume fraction, 40 ℃ and 10 days by volume fraction; the square box and the round box adopt the conditions of 95 percent ethanol by volume fraction, 60 ℃ and 2 hours by volume fraction, 40 ℃ and 10 days by volume fraction, and 95 percent ethanol by volume fraction, 40 ℃ and 10 days by volume fraction to carry out the migration experiment;
secondly, identifying and quantitatively analyzing the volatile substances, the semi-volatile substances and the non-volatile substances migrated in the step one;
testing volatile substances by adopting a headspace mass spectrometer, wherein the headspace heating temperature is 85 ℃; heating for 1 h; the temperature of a sample injection needle is 100 ℃; the sample injection volume is 1 mu L; temperature programming is carried out, wherein the temperature of a sample inlet is 280 ℃; the sample injection mode is split sample injection, and the split ratio is 2: 1; the chromatographic column is DB-5MS 30m × 250 μm × 0.25 μm; the acquisition mode is a full scanning mode; the scanning range is 20-800 m/z; a threshold value 150; when the sample is 50% ethanol, taking a proper amount of the solution in the step one, and directly testing the solution on a headspace machine; when the sample is a 95% ethanol sample, the sample needs to be diluted into 50% ethanol by using distilled water and then is tested on the machine;
testing the semi-volatile substances by adopting a gas-mass spectrometer without shunting and sampling; sample introduction volume: 0.1 mu L; temperature programming: the sample inlet temperature is 280 ℃; chromatographic column DB-5MS 30m × 250 μm × 0.25 μm; a full scan acquisition mode; the scanning range is 20-800 m/z; a threshold value 150; when 50% ethanol sample: adding sodium chloride and dichloromethane, oscillating, standing, collecting the lower layer solution, blowing and concentrating to near dryness, diluting to constant volume with dichloromethane, centrifuging, collecting the supernatant, and testing on a machine; when 95% ethanol sample: weighing a proper amount of solution into a separating funnel, adding sodium chloride and dichloromethane, oscillating, standing, carrying out blowing concentration on the lower layer of dissolved liquid nitrogen until the solution is nearly dry, carrying out constant volume by using dichloromethane, centrifuging, and taking the supernatant and putting the supernatant on a machine;
for non-volatile substances, a liquid quadrupole time-of-flight high resolution mass spectrometer DDA mode is adopted for testing: centrifuging the migrated solution obtained in the step one, and taking 1mL of the solution for on-machine testing; the conditions are as follows: mobile phase: phase A: 0.1% formic acid water, phase B: acetonitrile; elution gradient: 0-1.5 min, 5% B; 1.5-15 min, 5-40% B; 15-25 min, 40% -98% B; 25-32 min, 98% B; the column temperature is 40 ℃; 3 mu L of sample volume; all-first-stage ion scanning, all-second-stage ion scanning and a positive and negative ion mode; scanning the primary ions in the range of 50-1100 m/z; secondary ions, 20-800 m/z; secondary ion collision energies of 10, 20 and 40 eV;
qualitative mass spectrometry is adopted, test data of a liquid quadrupole time-of-flight high-resolution mass spectrometer are analyzed, an unknown compound is analyzed through Agilent MassHunter Qualitative Analysis software, a candidate molecular formula is screened out through a non-targeted screening method through a laboratory self-built food contact material database according to the functions of 'compound discovery' and 'identification' of the software, comparative Analysis is carried out through test spectrogram information of the unknown compound, and the matching degree between theoretical fragments and experimental fragments is a key factor for confirming the unknown compound; for the test data of the gas mass spectrometer, testing and identifying through Agilent MassHunter and NIST databases;
according to the method, ethyl oleate, butyl benzyl phthalate, n-heptadecane and terephthalic acid are selected as internal standard substances, and one substance with a structure or property similar to that of the internal standard substance is selected for semi-quantification during semi-quantification.
3. A safety assessment method for the migration amount of an unintended or intended additive in a recycled PET product for food contact, characterized in that, by using the method for screening the migration amount of an unintended or intended additive in a recycled PET product for food contact according to claim 2, after identifying and quantitatively analyzing the migrated volatile substances, semi-volatile substances and nonvolatile substances and confirming the information related to the name and the migration amount of an unknown compound obtained by screening, the safety assessment is performed on each compound, specifically including two types, namely compliance assessment based on the allowable angle of the substances and exposure level safety assessment based on the TTC method.
4. The method of claim 3, wherein the compliance assessment based on substance approval is to search the detected compounds in GB9685-2016 food contact plastic material and product approved additive standard for use if they are listed in the list of substances approved for use by national safety standards, and if they are not listed, they are substances that are not approved for use.
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