CN110514752B - Extraction method of additive in paper food packaging material and non-targeted screening method thereof - Google Patents
Extraction method of additive in paper food packaging material and non-targeted screening method thereof Download PDFInfo
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Abstract
The invention discloses a method for extracting an additive in a paper food packaging material, which comprises the following steps: (1) weighing modified polyphenyl ether, and spreading the modified polyphenyl ether at the bottom of a weighing dish; (2) cutting a part of food packaging area of the paper food packaging material as a sample, flatly paving the sample on the modified polyphenyl ether, and sealing by a gland; (3) placing the weighing vessel containing the sample and the modified polyphenyl ether in the step (2) in an oven for a migration test; (4) and transferring the modified polyphenyl ether in the weighing dish to a centrifuge tube, performing ultrasonic extraction, centrifuging, transferring the supernatant to a concentration bottle, performing nitrogen blowing concentration, and filtering through an organic filter membrane to obtain the additive extract of the sample. The invention further discloses a non-targeted screening method for the additives in the paper food packaging material, and the screening method has the advantages of strong specificity, simple operation, rapidness, accuracy and rich analysis types, and can provide a scientific method for the rapid analysis and quality control of the paper food packaging material.
Description
Technical Field
The invention belongs to the technical field of food packaging analysis and detection, and particularly relates to an extraction method and a non-targeted screening method of an additive in a paper food packaging material.
Background
In recent years, the emergence of toxic and harmful foods in large quantities causes extreme distrust of public on food safety, and meanwhile, food packaging materials closely related to food safety gradually enter the field of public vision. With the pressure of environmental protection, most food packaging materials in recent years are made of plastics and paper materials, among which paper packaging materials have good recyclability and fully satisfy the environmental requirements, and thus are widely used, and paper packaging materials also have excellent properties in terms of processability and mechanical strength. A series of processing can be carried out on the paper packaging material according to the packaging design of products in the using process, and some additives such as bactericides, curing agents, whitening agents and the like are required to be added in the processing process, and the additives have potential risks and are likely to migrate into food to cause harm to the health of consumers. In order to study the influence of these additives on food safety, a rapid, accurate, and simple analytical detection method must be established.
Currently reported non-targeted screening and measuring methods usually adopt gas chromatography and liquid chromatography/mass spectrometry, and in order to ensure the specificity of the detection method, a tandem mass spectrometry technology is mostly adopted. Although the organic matter quantitative analysis method based on the liquid chromatography-mass spectrometry (LC-MS) is high in sensitivity, the method is usually specific to a certain substance or a certain class of substances, so that many unknown organic matters cannot be discovered in time. Therefore, it is highly desirable to establish a rapid and simple method for screening organic substances. The gas chromatography-mass spectrometry GC-MS is one of analysis technologies commonly used for compound structure identification, can provide rich compound structure information and molecular weight information, is favorable for compound structure identification, and simultaneously has an NIST standard database for reference.
However, the components in the paper food packaging material are complex, and interfering impurities except the target substance (additive) not only interfere the analysis of the target substance, but also cause fatal damage to the chromatographic column in mass spectrum and gas chromatography, so how to effectively extract the additive in the paper food packaging material and purify and remove the interfering impurities in the paper food packaging material becomes a difficult problem to be solved urgently.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention provides a method for extracting an additive in a paper food packaging material, which comprises the following steps:
(1) weighing modified polyphenyl ether, and spreading the modified polyphenyl ether at the bottom of a weighing dish;
(2) cutting out partial food packaging area of paper food packaging material as sample with intercepting area of 0.385-0.435dm2Spreading a sample on modified polyphenyl ether, and sealing the sample by a gland, wherein the side of the sample, which contacts food, faces the modified polyphenyl ether;
(3) placing the weighing vessel containing the sample and the modified polyphenyl ether in the step (2) in an oven at 70-90 ℃ for a migration test, taking out after 2-4h, and naturally cooling to room temperature; more preferably, the weighing dish containing the sample and the modified polyphenylene ether in the step (2) is placed in an oven at 70 ℃ for a migration test, and is taken out after 2 hours;
(4) transferring all the modified polyphenyl ether in the weighing dish to a 50mL centrifuge tube, adding 10-20mL ethanol, performing ultrasonic extraction, centrifuging, transferring all supernatant to a concentration bottle, performing nitrogen blowing concentration to 1-2mL under the condition of water bath at 40-60 ℃, and filtering through a 0.45-micrometer organic filter membrane to obtain the additive extract of the sample. Wherein the organic filter membrane is a microporous filter membrane which is commonly used in laboratories and can resist organic solvents.
In the step (2) and the step (3), modified polyphenylene oxide (MPPO) is solid particles, a sample is laid on the modified polyphenylene oxide, the sample is sealed by a pressing cover, one side of the sample, which is in contact with food, faces to the modified polyphenylene oxide, the modified polyphenylene oxide can adsorb additives in the paper food packaging material, so that the step of transferring the additives in the paper food packaging material to the modified polyphenylene oxide is completed, and then the ethanol solution is used for carrying out solvent extraction on the modified polyphenylene oxide, so that the extract is free from interfering impurities in the paper food packaging material, and the problem that the ethanol solution is directly used for carrying out solvent extraction on the paper food packaging material in the prior art is avoided, so that the extract not only comprises the additives to be detected, but also comprises a large amount of interfering impurities in the paper food packaging material is solved.
Preferably, the ultrasonic frequency in the step (4) is 2000-4000Hz, and the ultrasonic time is 10-20 min; the centrifugal speed is 2000-4000rpm, and the centrifugal time is 5 min.
The invention provides a non-targeted screening method for additives in a paper food packaging material, which comprises the following steps:
(1) taking an additive extract of a sample obtained by the extraction method provided by the first aspect of the invention as an object to be detected, and taking an additive in the object to be detected as a target object;
(2) gas chromatography-mass spectrometry detection: detecting the object to be detected in a full-scanning mode with a monitoring mass number range of 29-550amu by taking an HP-5MS chromatographic column as a separation means;
(3) qualitative and quantitative analysis of substances: after background subtraction is carried out on a chromatographic peak of an object to be detected, NIST spectral library retrieval is adopted, a qualitative result that the matching degree of the spectral library is higher than 70% is reserved and recorded, and when an unlicensed additive is found in the qualitative result, qualitative confirmation is carried out by adopting a standard product of the unlicensed additive; the quantitative method is an internal standard method;
(4) calculating the relative content of the target in the sample: the relative content X of the target object in the sample is calculated by the formula (1):
X＝(As-A0)*Ci*V*f/(Ai*S)……………………………………(1)
in the formula:
x-relative content of target in mg/m2；
Peak area of As-target
A0 peak area of blank control sample
Peak area of Ai-internal standard
Ci-concentration of internal standard in ug/mL
V-volume of internal standard in mL
f-number of times of concentration in step (1)
S-intercepting area of the paper food packaging material in the step (1), wherein the unit is m2。
Wherein the blank control sample is an ethanol solvent sample which is not added with the paper food packaging material sample and the modified polyphenyl ether in the extraction process of the additive in the paper food packaging material in the step (1), namely the ethanol solvent sample which is not extracted with the additive in the paper food packaging material sample.
Preferably, the internal standard substance used in the internal standard method is deuterated anthracene, and 100 μ L of acetonitrile internal standard solution of deuterated anthracene is added into the substance to be detected in the step (1). The preparation method of the acetonitrile internal standard solution of the deuterated anthracene comprises the following steps: accurately weighing 10mg of deuterated anthracene, accurately measuring to 0.1mg, dissolving with acetonitrile, fixing the volume in a 100mL volumetric flask, preparing a deuterated anthracene internal standard solution with the concentration of 100 mu g/mL, storing in a sealed and light-proof manner at 0-4 ℃, and keeping the effective period for 3 months.
Preferably, in the step (2), the chromatographic conditions in the gas chromatograph-mass spectrometer are as follows: the chromatographic column is HP-5MS capillary chromatographic column with specification of 30m × 0.25mm × 0.25 μm; the carrier gas is high-purity helium He, and the flow rate is 1.0mL/min in a constant-current mode; the temperature of a sample inlet is 290 ℃; the sample introduction amount is 1 mu L, and the sample introduction is not carried out by shunting; the programmed temperature rise condition is that the initial temperature is 70 ℃, the temperature is kept for 3min, the temperature is raised to 290 ℃ at the speed of 10 ℃/min, and the temperature is kept for 5 min.
Preferably, the mass spectrum conditions in the gas chromatography-mass spectrometer in the step (2) are as follows: an EI ionization mode, wherein the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature is 150 ℃; the scanning mode is a full scanning mode, and the mass number range is 29-550 amu; the solvent was delayed for 3 min.
Preferably, the qualitative analysis step in step (3): background subtraction is carried out on chromatographic peaks, NIST spectral library retrieval is adopted according to the retention time of the peaks, qualitative results with the matching degree of the spectral library higher than 70% are retained and recorded, and for suspected non-licensed substances found by qualitative retrieval, qualitative confirmation needs to be carried out by adopting a standard substance. Selective ion chromatographic peaks of the sample solution to be detected and the standard substance appear at the same retention time (+ -0.1 min), the mass-to-charge ratio of the quantitative ions and the auxiliary qualitative ions is consistent with that of the standard substance, and the abundance ratio of the quantitative ions and the auxiliary qualitative ions is consistent with that of the standard substance: ± 10% deviation is allowed for relative abundance > 50%; when the relative abundance is 20-50%, the deviation of +/-15% is allowed; when the relative abundance is 10-20%, the deviation of +/-20% is allowed; when the relative abundance is less than or equal to 10%, a deviation of +/-50% is allowed, and the target analyte can be qualitatively distinguished.
A quantitative analysis step: respectively taking a series of standard working solutions to carry out GC-MS analysis, drawing a standard working curve by taking the ratio of the quantitative ion peak area of each standard working solution to the internal standard substance as a vertical coordinate and the content of each standard working solution as a horizontal coordinate, and drawing a linear correlation coefficient R of the working curve2>0.99. And substituting the ratio of the chromatographic peak area of the qualitative substance to the reference peak area into the corresponding standard curve by taking the chromatographic peak area of the internal standard substance as a reference to obtain the corresponding content of the qualitative substance.
Compared with the prior art, the invention has the following beneficial effects:
1. the extraction method firstly traps migratable substances (additives) in the paper food packaging material, and then extracts the trapped migratable substances by using a solvent, can effectively extract the additives in the paper food packaging material on the premise of avoiding extracting other interfering impurities in the paper food packaging material, and compared with the prior art that the additives in the paper food packaging material are directly extracted by using the solvent extraction method, the extraction method is faster and more accurate, not only can effectively extract the additives in the paper food packaging material, but also can avoid the damage caused by the mass spectrum of other interfering impurities in the paper food packaging material and the chromatographic column in the gas chromatography in the subsequent screening process.
2. The invention provides a non-targeting rapid screening method of an additive in a paper food packaging material, which comprises the steps of firstly extracting the additive in the paper food packaging material, then taking deuterated anthracene as an internal standard substance, and determining the relative content of a target object in a sample by adopting a gas chromatography-mass spectrometry (GC/MS).
Drawings
FIG. 1 shows a chromatogram for screening a sample of a paper food packaging material according to an embodiment of the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention will be further described with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Reagents and drugs used in this example:
modified polyphenylene oxide (MPPO, commonly known under the trade name Tenax-TA adsorbent); acetonitrile, chromatographic purity; water, GB/T6682, first order; deuterated anthracene (C)14D10CAS: 1719-06-8), the purity is more than or equal to 98 percent; accurately weighing 10mg of deuterated anthracene from the internal standard solution to 0.1mg, dissolving the deuterated anthracene with acetonitrile, fixing the volume in a 100mL volumetric flask to prepare the deuterated anthracene internal standard solution with the concentration of 100 mu g/mL, sealing and storing the deuterated anthracene internal standard solution at 0-4 ℃ in a dark place, and keeping the effective period for 3 months.
Instruments and materials used in this example:
gas chromatography-mass spectrometer (GC-MS); an analytical balance, a sensory mass of 0.1 mg; weighing a dish with the specification of 70mm multiplied by 35 mm; centrifuge tubes, 15mL, 50 mL; piston type pipette, 1000 μ L; 100mL of conical flask with cock; concentrate bottle, 50 mL.
The embodiment is a non-targeted screening method for additives in paper food packaging materials, and the method comprises the following steps:
(1) extraction of substance to be detected in paper food packaging material
Accurately weighing 1g of MPPO +/-0.0001 g of MPPO, and uniformly paving the MPPO at the bottom of a weighing dish; cutting food paper food packaging material packaging food area as sample, wherein the cutting area is 0.385dm2(diameter 70 mm). The sample was laid on MPPO and the gland sealed with the food-contacting side of the sample facing the modified polyphenylene ether. And (3) placing the weighing dish containing the sample in an oven at 70 ℃ for a migration test, taking out after 2 hours, and naturally cooling to room temperature. Transferring all MPPO in the weighing dish to a 50mL centrifuge tube, and adding 100 muPerforming ultrasonic extraction on an L deuterated anthracene acetonitrile internal standard solution and 20mL ethanol for 20min, performing centrifugal separation for 5min under the condition of 4000rpm, transferring all supernatant into a concentration bottle, performing nitrogen-blown concentration to 1mL under the condition of 40 ℃ water bath, filtering through a 0.45-micrometer organic phase filter membrane, and performing GC-MS analysis.
(2) Gas chromatography-mass spectrometer detection
Separating the liquid to be detected by a liquid chromatography system, wherein the chromatographic conditions are as follows: a chromatographic column: capillary chromatography column, stationary phase is (5% phenyl) -methyl polysiloxane, specification is [30m (length) × 0.25mm (inner diameter) × 0.25 μm (film thickness) ]; carrier gas: high purity helium (He), constant flow mode, flow rate of 1.0 mL/min; sample inlet temperature: 290 ℃; the sample introduction amount is 1 mu L, and the sample introduction is not carried out by shunting; temperature programming: the initial temperature was 70 deg.C, held for 3min, ramped up to 290 deg.C at a rate of 10 deg.C/min, and held for 5 min. Mass spectrometry reference conditions were as follows: an EI ionization mode, wherein the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature is 150 ℃; the scanning mode is as follows: full scan mode, mass number range 29-550 amu; solvent retardation: 3 min.
The chromatogram for screening the paper food packaging material sample is shown in fig. 1.
(3) Qualitative and quantitative determination of substances
After background subtraction is carried out on chromatographic peaks, NIST spectral library retrieval is adopted, and qualitative results with spectral library matching degree higher than 70% are reserved and recorded; for suspected non-licensed substances found by qualitative search, a standard substance is required for qualitative confirmation. Selective ion chromatographic peaks of the sample solution to be detected and the standard substance appear at the same retention time (+ -0.1 min), the mass-to-charge ratio of the quantitative ions and the auxiliary qualitative ions is consistent with that of the standard substance, and the abundance ratio of the quantitative ions and the auxiliary qualitative ions is consistent with that of the standard substance: ± 10% deviation is allowed for relative abundance > 50%; when the relative abundance is 20-50%, the deviation of +/-15% is allowed; when the relative abundance is 10-20%, the deviation of +/-20% is allowed; when the relative abundance is less than or equal to 10%, a deviation of +/-50% is allowed, and the target analyte can be qualitatively distinguished.
The chromatogram of the liquid to be detected has 19 identifiable peaks of the target substances, and the table 1 shows the recorded GC-MS parameters of the 19 target substances.
Characterised by the above steps19 substances are respectively purchased with the mass concentration gradient as follows: the method comprises the steps of preparing standard working solutions of 500ng/mL, 200ng/mL, 100ng/mL, 50ng/mL and 20ng/mL, injecting the standard working solutions into a gas chromatography-mass spectrometer for determination, drawing a standard working curve by taking the ratio of the quantitative ion peak area of each standard working solution to the internal standard substance as a vertical coordinate and the content of each standard working solution as a horizontal coordinate for each qualitative substance, and obtaining a linear correlation coefficient R of the working curve2>0.99. And substituting the ratio of the chromatographic peak area of the qualitative substance to the reference peak area into the corresponding standard curve by taking the chromatographic peak area of the internal standard substance as a reference to obtain the corresponding content of the qualitative substance.
TABLE 119 GC-MS parameters for the targets
(4) Calculation of the relative content of target in the sample
The relative content (X) of the target in the paper food packaging material sample is calculated by the formula (1):
X＝(As-A0)*Ci*V*f/(Ai*S)……………………………………(1)
in the formula:
x-relative content of target (mg/m)2)
Peak area of As-target
A0 peak area of blank control sample
Peak area of Ai-internal standard
Ci-concentration of internal standard (ug/mL)
V-volume of internal standard (mL)
f-number of times of concentration in step (1)
S-cutting area (m) of paper food packaging material in step (1)2)
Wherein the blank control sample is an ethanol solvent sample which is not added with the paper food packaging material sample and the modified polyphenyl ether in the extraction process of the additive in the paper food packaging material in the step (1), namely the ethanol solvent sample which is not extracted with the additive in the paper food packaging material sample.
The relative contents of 19 identifiable target substances in the liquid to be measured are calculated respectively and summarized in table 2.
Table 219 relative content of targets in paper food packaging material
Claims (4)
1. A qualitative and quantitative screening method for additives in paper food packaging materials is characterized by comprising the following steps:
(1) preparing a substance to be tested: preparing an additive extract of the paper food packaging material according to the following steps (11) to (14), wherein the additive extract is used as a to-be-detected object, and the additive in the to-be-detected object is used as a target object, and the target objects are respectively: 1, 6-hexanediol, 2-methoxyphenol, glycerol monoacetate, 1, 3-di-tert-butylphenol, bis (3-hydroxy-2-butyl) ether, bis (1-methyl-2-hydroxyethyl) ether, glycerol triacetate, diethylene glycol butyl ether acetate, 1, 6-hexanediol diacrylate, biphenyl, 2-ethyl-5-methyl-1, 4-dioxane, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, tripropylene glycol diacrylate, 2, 4-di-tert-butylphenol, 1, 6-hexanediol diacrylate, palmitic acid, 2' -methylenebis- (4-methyl-6-tert-butylphenol), 1- (1,1' -biphenyl-4-) yl-2- (2-pyridylthio) ethanone;
the method for extracting the additive in the paper food packaging material comprises the following steps:
(11) weighing modified polyphenyl ether, and spreading the modified polyphenyl ether at the bottom of a weighing dish;
(12) cutting a part of food packaging area of the paper food packaging material as a sample, flatly paving the sample on modified polyphenyl ether, and sealing the sample by a gland, wherein the side of the sample, which is in contact with food, faces to the modified polyphenyl ether;
(13) placing the weighing dish containing the sample and the modified polyphenyl ether in the step (12) in an oven for transferring, taking out and cooling to room temperature;
(14) transferring all the modified polyphenyl ether in the weighing vessel to a centrifuge tube, adding an ethanol solvent, performing ultrasonic extraction, centrifuging, transferring all supernatant liquid after centrifuging to a concentration bottle, performing nitrogen blowing concentration under the condition of water bath, and filtering by an organic filter membrane to obtain an additive extract of the paper food packaging material;
adding 10-20mL of ethanol in the step (14), performing ultrasonic extraction, centrifuging, transferring all supernatant liquid after centrifuging to a concentration bottle, and performing nitrogen blowing concentration to 1-2mL under the condition of water bath at 40-60 ℃; the ultrasonic frequency is 2000-4000Hz, and the ultrasonic time is 10-20 min; the centrifugal speed is 2000-4000rpm, and the centrifugal time is 5 min; the organic filter membrane is a 0.45 mu m organic filter membrane;
(2) gas chromatography-mass spectrometry detection: detecting the object to be detected in a full-scanning mode with a monitoring mass number range of 29-550amu by taking an HP-5MS chromatographic column as a separation means;
(3) qualitative and quantitative analysis of target: after background subtraction is carried out on a chromatographic peak of an object to be detected, NIST spectral library retrieval is adopted, a qualitative result that the matching degree of the spectral library is higher than 70% is reserved and recorded, and when an unlicensed additive is found in the qualitative result, qualitative confirmation is carried out by adopting a standard product of the unlicensed additive; the quantitative method is an internal standard method;
(4) calculating the relative content of the target object in the paper food packaging material, wherein the relative content X of the target object in the paper food packaging material is calculated by the formula (1):
X=（As-A0）*Ci* V*f/(Ai*S)……………………………………（1）
in the formula:
x-relative content of target in mg/m2；
Peak area of As-target
A0 peak area of blank control sample
Peak area of Ai-internal standard
Ci-concentration of internal standard in ug/mL
V-volume of internal standard in mL
f-number of times of concentration in step (1)
S-intercepting area of the paper food packaging material in the step (1), wherein the unit is m2；
The chromatographic conditions in the gas chromatography-mass spectrometer in the step (2) are as follows: the chromatographic column is HP-5MS capillary chromatographic column with specification of 30m × 0.25mm × 0.25 μm; the carrier gas is high-purity helium He, and the flow rate is 1.0mL/min in a constant-current mode; the temperature of a sample inlet is 290 ℃; the sample introduction amount is 1 mu L, and the sample introduction is not carried out by shunting; the temperature programming condition is that the initial temperature is 70 ℃, the temperature is kept for 3min, the temperature is increased to 290 ℃ at the speed of 10 ℃/min, and the temperature is kept for 5 min;
the mass spectrum conditions in the gas chromatography-mass spectrometer in the step (2) are as follows: an EI ionization mode, wherein the ionization energy is 70eV, the ion source temperature is 230 ℃, and the quadrupole rod temperature is 150 ℃; the scanning mode is a full scanning mode, and the mass number range is 29-550 amu; the solvent was delayed for 3 min.
2. The screening method according to claim 1, wherein the step (12) of cutting out a portion of the food-wrapped region of the paper food wrapping material as a sample, the cut-out region being 0.385 to 0.435dm2。
3. The screening method according to claim 1, wherein the oven temperature in step (13) is 70-90 ℃ and the migration time is 2-4 h.
4. The screening method of claim 1, wherein the internal standard method employs an internal standard substance that is deuterated anthracene.
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|---|---|---|---|---|
| JP2004108967A (en) * | 2002-09-19 | 2004-04-08 | Dainippon Printing Co Ltd | System and method for measuring volatilizing amount of volatile organic compound |
| CN103837617B (en) * | 2014-03-16 | 2015-07-08 | 国家烟草质量监督检验中心 | Method for analyzing migration volume from photoinitiator to modified polyphenylene oxide (MPPO) in printed wrapping paper based on liquid chromatograph-tandem mass spectrometer (LC-MS/MS) technology |
| CN103822990B (en) * | 2014-03-16 | 2015-09-09 | 国家烟草质量监督检验中心 | Based on light trigger in GC-MS/MS technical Analysis printed wrapper to the method for MPPO migration amount |
| CN104267121B (en) * | 2014-09-26 | 2015-11-25 | 云南中烟工业有限责任公司 | Tenax measures the method for the migration amount of volatilization and Semi-volatile organism in paper and paperboard as analogies HS-GC/MS |
| CN104237438B (en) * | 2014-09-26 | 2016-06-15 | 云南中烟工业有限责任公司 | Tenax makes analogies-GCMS and measures the method for the migration amount of aromatic amine in paper and cardboard |
| CN206223599U (en) * | 2016-12-01 | 2017-06-06 | 上海烟草集团有限责任公司 | For the device of Special migration test in the packaging material of dry food |
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2019
- 2019-07-26 CN CN201910682713.3A patent/CN110514752B/en active Active
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