CN113075332B - Method for determining low-content benzene series - Google Patents
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Abstract
The invention belongs to the technical field of food safety detection, and discloses a method for determining a low-content benzene series. The method is used for measuring the content of benzene series in paper for food, and comprises the steps of cutting a sample to be measured, placing the sample into a conical flask, and adding a normal hexane extraction solvent for extraction; and concentrating the extracted substances, detecting by a gas chromatograph-mass spectrometer, and quantifying by adopting a selective ion detection mode and an external standard method. The method has the advantages of simple operation, good linear range, accurate qualitative and quantitative determination and high sensitivity, and simultaneously, the method for determining 7 benzene series in paper for food contact meets the detection requirements.
Description
Technical Field
The invention relates to the technical field of food safety detection, in particular to a method for determining a low-content benzene series.
Background
With the vigorous development of the food industry, the food packaging and contact paper is widely applied in the food industry, for example, silicone oil paper is commonly called barbecue paper and is generally popular in the catering industry, has the advantages of high temperature resistance, moisture resistance and oil resistance, is commonly used in various barbecue shops, inevitably dirties the barbecue grill after the food contacts the barbecue grill in the process of roasting the meat, avoids the situation when the meat is roasted on the barbecue paper, and is cleaner and more convenient when being cleaned. Various processing aids, solvents, printing ink and the like are required to be introduced in the production process of the paper for food, but the quality of the aids used by manufacturers is uneven, gasoline is added as a cosolvent, benzene series pollution is inevitably introduced, and potential food safety risk is caused.
Benzene series includes toluene, ethylbenzene, xylene, cumene, styrene and the like, is an important chemical raw material, is widely applied to industries such as petrifaction, pesticide, medicine, coating and the like, and is also a class of organic pollutants widely existing in nature. Researches show that the benzene series has strong carcinogenicity, can cause leukemia and various cancers, and is harmful to human health.
The prior method for detecting the benzene series mainly focuses on a gas chromatography and a gas-mass combination method, wherein the pretreatment of a sample is focused on a headspace extraction sampling method, the headspace method needs long stabilization time, the sample injection amount of a target object is small, the stability and the repeatability are poor, the requirements on the precision and the system structure of a headspace sample injector are high, a large amount of steam volume is brought in during sampling, the target peak and peak spread is too wide easily during multi-component analysis, the separation of components is not facilitated, and for food paper, the paper volume is large and the paper volume is not suitable for the headspace extraction method. Meanwhile, the paper for food has low benzene content, and for samples with the benzene content lower than 0.0001%, the detection method in the prior art has high detection limit and is difficult to determine qualitatively and quantitatively.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a method for measuring a low-content benzene series, which is used for measuring the benzene series in paper for food and can accurately measure the benzene series with the content of less than 0.0001 percent.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for measuring the benzene series content in paper for food (such as breakfast packing paper, snack take-out oil-proof paper, western-style kraft paper packing bag, food sealing paper bag, etc.) comprises the following steps:
shearing a sample to be detected, placing the sample in a conical flask, and adding a normal hexane extraction solvent for extraction; and
concentrating the extracted substances, detecting by a gas chromatograph-mass spectrometer, and quantifying by adopting a selective ion detection mode and an external standard method;
and the external standard method comprises the steps of diluting the mixed standard solution into standard series solutions with different concentrations by using normal hexane step by step, drawing a standard curve, and substituting the standard curve with the peak area of each benzene series in the sample to calculate the content of the benzene series in the sample to be detected.
Further, the benzene series comprises toluene, ethylbenzene, paraxylene, metaxylene, cumene, orthoxylene and styrene; the content of the benzene series in the sample to be detected is lower than 0.0001%.
Further, the ratio of the addition amount of the extraction solvent to the volume of the conical flask is 1.5, the extraction temperature is 15-30 ℃, and the extraction time is 50-70 min.
Further, the concentration mode is rotary evaporation, and the temperature of a water bath kettle is 25 ℃.
Further, the determination conditions of the gas chromatograph-mass spectrometer are as follows: a large-volume sample injection mode:
PTV injection port temperature program: 30-60 deg.c (0.07 min), 200-230 deg.c/min to 220-250 deg.c (20 min); a flow dividing procedure of the flow dividing valve: 0-0.07min split ratio 10:1,0.06-1.00min shunt valve is closed, 1.00 min-analysis is finished, the shunt ratio is 10:1.
further, the column oven temperature-rising program of the gas chromatograph-mass spectrometer is as follows: keeping the temperature at 35-60 ℃ for 5-10 min, and raising the temperature to 70-120 ℃ at 5 ℃/min; then raising the temperature to 230-260 ℃ at the speed of 20 ℃/min, and keeping the temperature for 5-10 min.
Further, the chromatographic column of the gas chromatograph-mass spectrometer is as follows: inertCap FFAP,30m × 0.32mm × 0.25 μm; rtx-5, 30m × 0.32mm × 0.25 μm; rtx-1701, 30 m.times.0.32 mm.times.0.25. Mu.m.
Further, the drawing of the standard curve comprises the following steps:
preparing a mixed standard series intermediate solution: accurately sucking 1.00mL to 100mL volumetric flasks of 7 benzene series mixed standard solutions (100 mu g/mL), fixing the volume to the scale with n-hexane, and uniformly mixing to obtain an intermediate solution with the concentration of 1 mu g/mL;
preparing a mixed standard series of use solutions: accurately sucking 0, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0mL of mixed intermediate solution respectively, metering the volume to 10mL by using normal hexane, and uniformly mixing to obtain mixed standard use solutions with the concentrations of 0, 10, 20, 40, 60, 80 and 100 ng/mL;
drawing a standard curve: and (3) measuring the standard working solution series according to selected instrument analysis conditions, and respectively drawing standard working curves by taking the concentration of 7 benzene series in the standard working solution as a horizontal coordinate and the corresponding chromatographic peak area as a vertical coordinate to obtain a linear regression equation.
Further, the method also comprises the preparation of a blank sample, and the extraction and measurement steps are the same as those of the sample except that the sample is not added into the conical flask.
Further, the content calculation formula of the benzene series is as follows:
in the formula:
c-the concentration of a certain benzene series in the sample is microgram per kilogram;
A sample (II) -peak area of a benzene series in the sample;
A blank space -peak area of a certain benzene series in the blank;
a-the slope of a standard curve of a certain benzene series in a sample;
b-intercept of a certain benzene series standard curve in the sample;
m-mass of the sample in g.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the technologies of extracting solution evaporation concentration and large-volume sample injection, thereby accurately measuring the benzene series with the content lower than 0.0001 percent in the paper for food and realizing ultra-trace analysis. Meanwhile, the method disclosed by the invention is accurate in detection and high in stability.
Drawings
FIG. 1 is a graph of the separation effect of the Rtx-5 capillary column of example 1;
FIG. 2 is a graph of the separation effect of the Rtx-1701 capillary column of example 1;
FIG. 3 is a graph of the separation effect of the InertCap FFAP capillary column of example 1;
FIG. 4 is the sum of the peak areas of 7 benzene series at different temperatures in example 2;
FIG. 5 is the sum of the peak areas of 7 benzene series at different times in example 3;
FIG. 6 is the total ion flow chromatogram of the 7 benzene series in example 4.
Detailed Description
For a further understanding of the present invention, the method and effects of the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be noted that the present embodiment is only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and that those skilled in the art can make modifications and adjustments in a non-essential way based on the above disclosure.
Example 1
Take 6dm 2 Cutting 1 piece of barbecue paper (the content of benzene series in the barbecue paper is less than 0.0001%), placing into a 250mL conical flask, adding benzene series standard solution, adding n-hexane extraction solvent 100mL, extracting at 15 deg.C for 60min; under the condition that the water bath temperature is 25 ℃, the extracting solution is rotationally concentrated to about 5mL, the extracting solution is transferred to a 10mL volumetric flask, the volume is fixed by normal hexane, and then the instrument detection is carried out, wherein the measurement conditions of the instrument are as follows:
a large-volume sample injection mode:
PTV injection port temperature program: 30 deg.C (0.07 min), 200 deg.C/min to 220 deg.C (20 min). A flow dividing procedure of the flow dividing valve: 0-0.07min split ratio 10:1,0.06-1.00min of shunt valve closing, 1.00min of analysis ending, the shunt ratio is 10:1.
column oven temperature program: keeping at 35 deg.C for 5min, increasing to 70 deg.C at 5 deg.C/min, increasing to 230 deg.C at 20 deg.C/min, and keeping for 5min.
Under the gas phase conditions described above, 3 capillary column chromatography columns 1 of different polarities were compared: low polarity Rtx-5, 30m × 0.32mm × 0.25 μm; and (3) chromatographic column 2: medium polarity Rtx-1701, 30m × 0.32mm × 0.25 μm; a chromatographic column 3: the results of the separation effect of the strongly polar InertCap FFAP,30 m.times.0.32 mm.times.0.25 μm, on a mixed standard solution of 7 benzene series are shown in FIGS. 1 to 3.
As can be seen from FIGS. 1-3, the InertCap FFAP capillary column has the best separation effect on the benzene series, and the separation degree is more than 2.
Example 2
Take 6dm 2 Cutting 5 pieces of oil-proof paper (the content of benzene series in the oil-proof paper is less than 0.0001%), respectively placing into 5 conical flasks of 250mL, adding benzene series standard solution, adding 100mL of n-hexane extraction solvent, and extracting at 15, 30, 40, 50 and 60 deg.C for 60min; under the condition that the water bath temperature is 25 ℃, the extracting solution is rotationally concentrated to about 5mL, the extracting solution is transferred to a 10mL volumetric flask, the volume is constant by normal hexane, and then the instrument detection is carried out, wherein the instrument measurement conditions are as follows:
a large-volume sample injection mode:
PTV injection port temperature program: 30 deg.C (0.07 min), 200 deg.C/min to 220 deg.C (20 min). A flow dividing procedure of the flow dividing valve: 0-0.07min split ratio 10:1,0.06-1.00min shunt valve is closed, 1.00 min-analysis is finished, the shunt ratio is 10:1.
column oven temperature program: maintaining at 35 deg.C for 5min, increasing to 70 deg.C at 5 deg.C/min, increasing to 230 deg.C at 20 deg.C/min, and maintaining for 5min; constant linear velocity 55cm/sec, solvent delay time: 1.92min, the ion source temperature is 200 ℃, and the interface temperature is 250 ℃; an ionization mode: EI, ionization energy 70eV, SIM monitoring mode, detected ions are shown in Table 1, and the sum of the peak areas of 7 benzene series at different extraction temperatures is shown in FIG. 4.
TABLE 1 target Retention time and SIM parameters
Extraction environments below 15 ℃ require the use of additional refrigeration equipment, increasing laboratory experimental costs, and therefore lower experimental temperatures are not considered. The use environment of higher than 60 ℃ reaches the boiling point of the n-hexane solvent, so that great potential safety hazard exists, and meanwhile, the extract is evaporated violently at the temperature, and the loss of the target substance is serious.
As can be seen from FIG. 4, the extraction of benzene series can be achieved with a good effect at 15-30 deg.C, and the extraction temperature is 15-30 deg.C as the best scheme.
Example 3
Take 6dm 2 5 sealed food paper bags (the content of benzene series in the sealed food paper bags is lower than 0.0001 percent) are cut into pieces and respectively placed into 5-250 mL conical bottles, benzene series standard solution is added, the adding amount of n-hexane extraction solvent is 100mL, and extraction is carried out at 30 ℃ for 30, 60, 120, 180 and 240min. Under the condition that the water bath temperature is 25 ℃, the extracting solution is rotationally concentrated to about 5mL, the extracting solution is transferred to a 10mL volumetric flask, the volume is fixed by normal hexane, and then the instrument detection is carried out, wherein the measurement conditions of the instrument are as follows:
a large-volume sample injection mode:
PTV injection port temperature program: 30 deg.C (0.07 min), 200 deg.C/min to 220 deg.C (20 min). A flow dividing procedure of the flow dividing valve: 0-0.07min split ratio 10:1,0.06-1.00min of shunt valve closing, 1.00min of analysis ending, the shunt ratio is 10:1.
column oven temperature program: keeping at 35 deg.C for 5min, increasing to 70 deg.C at 5 deg.C/min, increasing to 230 deg.C at 20 deg.C/min, and keeping for 5min. Constant line speed 55cm/sec, solvent delay time: 1.92min, the ion source temperature is 200 ℃, and the interface temperature is 250 ℃. An ionization mode: EI, ionization energy 70eV, SIM monitoring mode, detected ions are shown in Table 2, and the sum of the peak areas of 7 benzene series at different times is shown in FIG. 5.
TABLE 2 target Retention time and SIM parameters
As can be seen from FIG. 5, the extraction effect is not very different after 60min, and 60min extraction time is selected as the optimization scheme. Extraction time less than 50min is difficult to realize the technical effect of the experiment, and the time as pretreatment after exceeding 60min is too long, which is not beneficial to the improvement of experiment efficiency.
Example 4
Take 6dm 2 Cutting 6 snack packaging paper (the content of benzene series in the snack packaging paper is lower than 0.0001%), putting the cut snack packaging paper into a 250mL conical flask, adding 10 mu L of benzene series mixed standard solution respectively, adding 100mL of n-hexane extraction solvent, extracting at 20 ℃ for 60min; rinsing the conical flask with a small amount of solvent, mixing the extractive solutions in a heart-shaped flask, rotary concentrating to about 5mL at 25 deg.C in water bath, transferring to a 10mL volumetric flask, and diluting with n-hexane.
Preparing a mixed standard series intermediate solution: accurately sucking 1.00mL to 100mL volumetric flasks of 7 benzene series mixed standard solutions (100 mu g/mL), metering to the scale with n-hexane, and uniformly mixing to obtain an intermediate solution with the concentration of 1 mu g/mL.
Preparing a mixed standard series of use solutions: accurately sucking 0, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0mL of the mixed intermediate solution respectively, diluting to 10mL with n-hexane, and mixing to obtain mixed standard use solutions with concentrations of 0, 10, 20, 40, 60, 80 and 100 ng/mL.
A large-volume sample injection mode:
PTV injection port temperature program: 30 deg.C (0.07 min), 200 deg.C/min to 220 deg.C (20 min). A flow dividing procedure of the flow dividing valve: 0-0.07min split ratio 10:1,0.06-1.00min shunt valve is closed, 1.00 min-analysis is finished, the shunt ratio is 10:1.
column oven temperature program: keeping at 35 deg.C for 5min, increasing to 70 deg.C at 5 deg.C/min, increasing to 230 deg.C at 20 deg.C/min, and keeping for 5min. The capillary chromatographic column is: inertCap FFAP,30m by 0.32mm by 0.25 μm.
Drawing a standard curve: according to the selected instrument analysis conditions, the standard working solution series is measured, a standard working curve is respectively drawn by taking the concentration of 7 benzene series substances in the standard working solution as a horizontal coordinate and the corresponding chromatographic peak area as a vertical coordinate to obtain a linear regression equation, the detection limit is calculated by 3 times of signal-to-noise ratio, the quantitative limit is calculated by 10 times of signal-to-noise ratio, and the 7 benzene series total ion flow chromatogram is shown in a figure 6 as shown in a table 3.
Preparation of blank sample, except that no sample is added to the Erlenmeyer flask, the extraction and measurement steps are the same as those of the sample.
The content calculation formula of the benzene series is as follows:
in the formula:
c-the concentration of a certain benzene series in the sample is microgram per kilogram;
A sample (A) -peak area of a certain benzene series in the sample;
A blank space -peak area of a certain benzene series in the blank;
a-the slope of a standard curve of a certain benzene series in a sample;
b-intercept of a certain benzene series standard curve in the sample;
m-mass of the sample in g.
TABLE 3
TABLE 4
As can be seen from tables 3 and 4, the present example can realize ultra trace analysis of 7 benzene series by establishing an extract concentration and large volume sampling method, while maintaining good precision.
The embodiment shows that the applicant establishes a method for simultaneously determining 7 benzene series in paper for food contact, which has the advantages of simple and convenient operation, good linear range, accurate qualitative and quantitative determination, high sensitivity and the like through optimization of a plurality of experimental conditions and result comparison research, and meets the detection requirements.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. A method for measuring low-content benzene series is characterized in that the method is used for measuring the content of the benzene series in paper for food, and the detection limit and the quantitative limit reach the magnitude of mu g/kg, and the method comprises the following steps:
shearing a sample to be detected, placing the sample in a conical flask, and adding a normal hexane extraction solvent for extraction; and
concentrating the extracted substances, detecting by a gas chromatograph-mass spectrometer, and quantifying by adopting a selective ion detection mode and an external standard method;
the external standard method comprises the steps of diluting a mixed standard solution into standard series solutions with different concentrations by using normal hexane step by step, drawing a standard curve, and substituting the standard curve according to the peak area of each benzene series in a sample to calculate the content of the benzene series in the sample to be detected;
the benzene series comprises toluene, ethylbenzene, paraxylene, metaxylene, cumene, orthoxylene and styrene; the content of the benzene series in a sample to be detected is lower than 0.0001%;
the determination conditions of the gas chromatograph-mass spectrometer are as follows: a large-volume sample injection mode:
PTV injection port temperature program: keeping the temperature at 30-60 ℃ for 0.07min, raising the temperature at 200-230 ℃/min to 220-250 ℃ and keeping the temperature for 20min; a flow dividing procedure of the flow dividing valve: 0-0.07min split ratio 10:1,0.06-1.00min shunt valve is closed, 1.00 min-analysis is finished, the shunt ratio is 10:1;
the ratio of the addition amount of the extraction solvent to the volume of the conical flask is 1.5, the extraction temperature is 15-30 ℃, and the extraction time is 50-70 min;
the concentration mode is rotary evaporation, and the temperature of a water bath kettle is 25 ℃;
the column oven temperature rise program of the gas chromatograph-mass spectrometer is as follows: keeping the temperature at 35-60 ℃ for 5-10 min, and raising the temperature to 70-120 ℃ at 5 ℃/min; raising the temperature to 230-260 ℃ at the speed of 20 ℃/min, and keeping the temperature for 5-10 min;
the chromatographic column of the gas chromatograph-mass spectrometer is as follows: inertCap FFAP,30m × 0.32mm × 0.25 μm; rtx-5, 30m × 0.32mm × 0.25 μm; rtx-1701, 30 m.times.0.32 mm.times.0.25. Mu.m.
2. The method of claim 1, wherein the step of plotting the standard curve comprises the steps of:
preparing a mixed standard series intermediate solution: accurately sucking 7 benzene series mixed standard solutions into a volumetric flask with the volume ranging from 100 mu g/mL to 100mL, metering the volume to a scale by using normal hexane, and uniformly mixing to obtain an intermediate solution with the concentration of 1 mu g/mL;
preparing a mixed standard series of use solutions: accurately sucking 0, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0mL of mixed intermediate solution respectively, metering the volume to 10mL by using normal hexane, and uniformly mixing to obtain mixed standard use solutions with the concentrations of 0, 10, 20, 40, 60, 80 and 100 ng/mL;
drawing a standard curve: and (3) measuring the standard working solution series according to selected instrument analysis conditions, and respectively drawing standard working curves by taking the concentration of 7 benzene series in the standard working solution as a horizontal coordinate and the corresponding chromatographic peak area as a vertical coordinate to obtain a linear regression equation.
3. The method of claim 1 or 2, further comprising preparing a blank sample, wherein the extraction assay is performed in the same manner as the sample except that no sample is added to the erlenmeyer flask.
4. The method according to claim 2, wherein the benzene-based compound content is calculated by the formula:
in the formula:
c-the concentration of a certain benzene series in the sample is microgram per kilogram;
A sample (II) -peak area of a certain benzene series in the sample;
A blank space -peak area of a certain benzene series in the blank;
a-the slope of a standard curve of a certain benzene series in a sample;
b-intercept of a certain benzene series standard curve in the sample;
m-mass of the sample in g.
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| CN106596826A (en) * | 2017-01-25 | 2017-04-26 | 江苏中烟工业有限责任公司 | Method for determining benzene and benzene series content in cellulose acetate fiber and cellulose acetate fiber mouth stick |
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| JP2009092404A (en) * | 2007-10-04 | 2009-04-30 | Kaneka Corp | Method for analyzing residual agricultural chemical in spice |
| CN109991349A (en) * | 2019-03-25 | 2019-07-09 | 上海市质量监督检验技术研究院 | The detection method of benzene-like compounds content in food contact material |
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