CN106018592A - Quantitative analysis method for polychlorobiphenyls in dry food packaging paper - Google Patents
Quantitative analysis method for polychlorobiphenyls in dry food packaging paper Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Abstract
The invention discloses a quantitative analysis method for polychlorobiphenyls in dry food packaging paper. The quantitative analysis method is used for measuring the contents of seven main polychlorobiphenyls substances in the dry food packaging paper based on a gas chromatography-tandem mass spectrometer, and includes the steps of preparing an internal-standard solution, a standard work solution and a sample solution, carrying out GC-MS/MS analysis and calculating the measuring result. The optimized detection method is easy and convenient to operate, sensitive in response and accurate in quantitative analysis, the interference caused by complex sample substrates is effectively reduced, an analytical instrument aims at allowing target objects to have good signal responses and the good linear dependence, the detection limits of the seven polychlorobiphenyls substances are 0.99 ng/g, 0.74 ng/g, 1.05 ng/g, 1.29 ng/g, 0.75 ng/g, 1.11 ng/g and 1.19 ng/g respectively, the repeatability is smaller than 10%, and the adding standard recovery rate ranges from 68.4% to 147.0%. The quantitative analysis method is high in sensitivity, good in repeatability and recovery rate and suitable for measuring quantitative analysis of trace target objects in the dry food packaging paper.
Description
Technical field
The invention belongs to packaging material physical and chemical index detection technique field, be specifically related to a kind of quantitative analysis and do
The method of Polychlorinated biphenyls in property food wrapper.
Background technology
Polychlorinated biphenyls (polychlorobiphenyls, PCBs) is chloride biphenyl compound, has
Teratogenesis, carcinogenic and mutagenicity.It is colourless transparent oil liquid, water insoluble, is soluble in organic molten
Agent, has high temperature resistant, acid and alkali-resistance, the feature such as is not easily decomposed.In recent years, some wrapping enterprise is for reducing
Cost, uses a certain proportion of waste paper as the raw material of wrapping paper, and the paper pulp after deinking can be by residual
Polychlorinated biphenyls is brought in wrapping paper.Its quality is closely related with the health of consumers in general, packaging material
Safety problem cause and pay close attention to widely.
Dry food wrapping paper is important component part indispensable in wrapping paper, and its safety is very
An important aspect.In view of Polychlorinated biphenyls very likely can enter in packaging for foodstuff as raw materials for production,
Therefore the detection method of a kind of Polychlorinated biphenyls fast and accurately is explored, to many in food dryness wrapping paper
Chlordiphenyl control effectively, it is ensured that the safety that dry food wrapping paper uses is the most urgent and necessary
's.
The most about the analysis report of Polychlorinated biphenyls in packaging material.Guo Limin et al. uses Soxhlet to carry
Take-Food by Gas Chromatography packaging material in Polychlorinated biphenyls.Bai Yankun et al. uses GC-MS connection
With the Polychlorinated biphenyls measured in packaging material for food.Chen Qiaohua et al. also uses the analysis hands of GC-MS
Section measures the Polychlorinated biphenyls in packaging for foodstuff.Tan Jianhua et al. utilizes Solid-Phase Extraction/gas chromatography-mass spectrometry
Usage measures tell-tale Polychlorinated biphenyls in packaging material for food.Yao Weixi et al. utilizes supercritical fluid to carry
Take the Polychlorinated biphenyls in Wastewater from Bleaching in Paper Making.But current existing Polychlorinated biphenyls assay method pre-treatment is relative
Loaded down with trivial details, the longest, instrument is more expensive, is not easy to promote the use of.
Therefore, those skilled in the art need badly offer one quickly, efficiently, quantitative analysis method accurately
Detect the content of Polychlorinated biphenyls in food dryness wrapping paper.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of quantitative analysis dry food packaging
The method of Polychlorinated biphenyls in paper, the method uses gas chromatography tandem mass spectrometry instrument to measure dry food packaging
7 kinds of Polychlorinated biphenyls of trace in paper, measurement result is accurate, highly sensitive, and matrix interference is few.
For achieving the above object, present invention employs techniques below scheme:
A kind of method of Polychlorinated biphenyls in quantitative analysis dry food wrapping paper, comprises the following steps:
S1, the preparation of inner mark solution: with heptadecane as internal standard substance, use normal hexane is solvent, system
Standby inner mark solution；
S2, the preparation of standard working solution: with 2,2 ', 5-trichloro biphenyl, 2,4,4 '-trichloro biphenyl, 2,2 ', 5,5 '-
Tetrachloro biphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyl, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene join
Benzene, 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl standard substance are object, and use normal hexane is solvent, through the dilutest
Release and be prepared as Standard Stock solutions, be then respectively adding inner mark solution and be prepared as standard working solution；
S3, the preparation of sample solution: weigh quantitative dry food wrapping paper sample, pulverize, use dichloro
Methane supersound extraction, crosses organic filter membrane, obtains sample solution；
S4, gas chromatography tandem mass spectrometry instrument are analyzed: with gas chromatography tandem mass spectrometry instrument i.e. GC-MS/MS
Standard working solution and sample solution carry out detection analyze；
S5, the drafting of standard working curve and the calculating of sample result.
Preferably, in step S1, the preparation of described inner mark solution comprises the following steps:
S10, internal standard storing solution: accurately weigh 0.2g heptadecane, be accurate to 0.1mg, in 100mL
Volumetric flask in, with n-hexane dissolution and be settled to scale.
S11, inner mark solution: accurately pipette 0.1mL internal standard storing solution, in the volumetric flask of 100mL,
Dilute with normal hexane and be settled to scale.
Preferably, in step S2, the preparation of described standard working solution comprises the following steps:
S20, primary standard storing solution: accurately weigh 2,2 ', 5-trichloro biphenyl, 2,4,4 '-trichloro biphenyl,
2,2 ', 5,5 '-tetrachloro biphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyl, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-
Chlordene biphenyl, 2,2 ', 3,4,4 ', 5, each 0.1g of 5 '-heptachlor biphenyl standard sample in the volumetric flask of 100mL,
It is accurate to 0.1mg, with n-hexane dissolution and be settled to scale；
S21, secondary standard storing solution: accurately pipette 0.5mL primary standard storing solution, in 50mL's
In volumetric flask, dilute with normal hexane and be settled to scale；
S22, grade III Standard storing solution: accurately pipette 0.5mL secondary standard storing solution, in 50mL's
In volumetric flask, dilute with normal hexane and be settled to scale；
S23, standard working solution: the most accurately pipette grade III Standard storing solution 10 μ L, 20 μ L, 50 μ L,
100 μ L, 200 μ L, 500 μ L and 1mL, to the volumetric flask of 10mL, more accurately add 1mL
Inner mark solution, dilutes with normal hexane and is settled to scale, obtains series standard working solution.
Preferably, in step S3, the preparation of described sample solution comprises the following steps: weigh paper sample
Product 10g, is accurate to 0.1mg, is shredded to 5mm × below 5mm, mixing, claims from aggregate sample
Take 1g sample, be placed in 100mL tool plug triangular flask, accurately pipette 40mL dichloromethane extractant,
Ultrasonic extraction 40min, takes appropriate extract after the 0.45 organic membrane filtration of μm, obtains sample solution.
Preferably, in step S4, the instrumental conditions that described GC-MS/MS analyzes is: use
HP-5MS capillary chromatographic column；Carrier gas is helium, and constant current speed is 1.0mL/min；Input mode:
Sample size is 1 μ L, pulse Splitless injecting samples, and sample introduction pressure is 25psi, and the persistent period is 1min；Enter
Sample mouth temperature is 280 DEG C；Transmission line temperature is 280 DEG C；Heating schedule be initial temperature be 50 DEG C, with
The speed of 15 DEG C/min is increased to 200 DEG C, keeps 10min, then is increased to the speed of 5 DEG C/min
220 DEG C, finally with the speed of 20 DEG C/min to 260 DEG C, keeping 4min, rear operational mode is at 280 DEG C
Under the conditions of keep 5min；Its mass spectral analysis condition is: ionization mode is EI source, positive ion mode；From
Source temperature: 230 DEG C；Quadrupole rod temperature: be 150 DEG C；Collision gas: nitrogen, flow velocity 1.5mL/min,
Carrier gas (helium) flow velocity is 2.25mL/min；Multiple-reaction monitoring (MRM) pattern, detail parameters arranges
In table 1 below.
The MRM parameter situation of table 1 object
Preferably, in step S5, described standard working curve is drawn and result is calculated as follows: with standard
In working solution, object is abscissa with the ratio of interior target concentration, with object in chromatogram and interior target
The ratio of peak area is vertical coordinate, carries out linear regression analysis, obtains standard working curve；By the same terms
Under object and interior target chromatographic peak area ratio in the sample solution that records, substitute into standard working curve, root
The content of object in outturn is tried to achieve according to following equation.
In formula:
W is the content of 7 kinds of Polychlorinated biphenyls in dry food wrapping paper, and unit is microgram every gram；
A is the peak area of 7 kinds of Polychlorinated biphenyls；
As is corresponding interior target peak area；
B is the intercept of standard working curve；
Ms is target quality in adding, and unit is microgram；
A is the slope of standard working curve；
M is the quality of dry food wrapping paper, and unit is gram.
Further, for 2,2 ', 5-trichloro biphenyl, the regression equation corresponding with standard working curve is
Y=0.4102x+0.0456, coefficient R2Being 0.9998, detection is limited to 0.99ng/g, and concentration range is
0.0103～1.026 μ g/mL；For 2,4,4 '-trichloro biphenyl, the recurrence corresponding with standard working curve
Equation is y=0.9922x+0.4026, coefficient R2Being 0.9988, detection is limited to 0.74ng/g, concentration
Scope is 0.0115～1.15 μ g/mL；For 2,2 ', 5,5 '-tetrachloro biphenyl is relative with standard working curve
The regression equation answered is y=0.2342x+0.1364, coefficient R2Being 0.9990, detection is limited to
1.05ng/g, concentration range is 0.0101～1.012 μ g/mL；For 2,2 ', 4,5,5 '-pentachlorodiphenyl, with mark
The corresponding regression equation of quasi-working curve is y=0.5533x+0.3037, coefficient R2It is 0.9990,
Detection is limited to 1.29ng/g, and concentration range is 0.0118～1.183 μ g/mL；For 2,2 ', 3,4,4 ', 5 '-six
Chlordiphenyl, the regression equation corresponding with standard working curve is y=0.5131x+0.1718, correlation coefficient
R2Being 0.9989, detection is limited to 0.75ng/g, and concentration range is 0.0120～1.203；For 2,2 ', 4,4 ', 5,5 '-
Chlordene biphenyl, the regression equation corresponding with standard working curve is y=0.7019x+0.2251, phase relation
Number R2Being 0.9983, detection is limited to 1.11ng/g, and concentration range is 0.0102～1.015；For
2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl, the regression equation corresponding with standard working curve is
Y=0.3558x+0.0785, coefficient R2Being 0.9993, detection is limited to 1.19ng/g, and concentration range is
0.0130～1.295.
Compared with prior art, the beneficial effects of the present invention is:
1) during, the inventive method creative use gas chromatography tandem mass spectrometry instrument measures food dryness wrapping paper
The 2,2 ' of trace, 5-trichloro biphenyl, 2,4,4 '-trichloro biphenyl, 2,2 ', 5,5 '-tetrachloro biphenyl, 2,2 ', 4,5,5 '-five
Chlordiphenyl, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl, 2,2 ', 3,4,4 ', 5,5 '-heptachlor
The content of 7 kinds of Polychlorinated biphenyls of biphenyl, has quick, accurate, sensitivity high, and can evade
The interference that substrate is brought, is particularly suitable for measuring the content of Polychlorinated biphenyls in food dryness wrapping paper.
2), the inventive method utilize inner mark method ration, can accurate constant volume, and can reduce by front
The error that processing method repeatability and instrument precision problem are brought.
Accompanying drawing explanation
Fig. 1 is the flow chart of quantitative analysis method of the present invention.
Fig. 2 is 7 kinds of Polychlorinated biphenyls and the ion pair of internal standard heptadecane in standard working solution of the present invention
Chromatogram.
Fig. 3 is 7 kinds of Polychlorinated biphenyls and the ion of internal standard heptadecane in dry food wrapping paper of the present invention
To chromatogram.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the present invention is carried out clear,
It is fully described by.Following example are only used for clearly illustrating technical scheme, and can not
Limit the scope of the invention with this.
Embodiment 1
The present embodiment is (the most described to the detection method of Trace Polychlorinated Biphenyls several in dry food wrapping paper
The flow chart of detection method is as shown in Figure 1):
S1, the preparation of inner mark solution
S10, internal standard storing solution: accurately weigh 0.203g heptadecane, in the volumetric flask of 100mL,
With n-hexane dissolution and be settled to scale；
S11, inner mark solution: accurately pipette 0.1mL internal standard storing solution, in the volumetric flask of 100mL,
Dilute with normal hexane and be settled to scale.Wherein the concentration of heptadecane is 2.03 μ g/mL.
S2, the preparation of standard working solution
S20, primary standard storing solution: accurately weigh 2,2 ', 5-trichloro biphenyl 0.1026g, 2,4,4 '-trichlorine
Biphenyl 0.1150g, 2,2 ', 5,5 '-tetrachloro biphenyl 0.1012g, 2,2 ', 4,5,5 '-pentachlorodiphenyl 0.1183g,
2,2 ', 3,4,4 ', 5 '-chlordene biphenyl 0.1203g, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl 0.1015g and
2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl 0.1295g, in the volumetric flask of 100mL, with n-hexane dissolution fixed
Hold to scale；
S21, secondary standard storing solution: accurately pipette 0.5mL primary standard storing solution, in 50mL's
In volumetric flask, dilute with normal hexane and be settled to scale；
S22, grade III Standard storing solution: accurately pipette 0.5mL secondary standard storing solution, in 50mL's
In volumetric flask, dilute with normal hexane and be settled to scale；
S23, standard working solution: the most accurately pipette grade III Standard storing solution 10 μ L, 20 μ L, 50 μ L,
100 μ L, 200 μ L, 500 μ L and 1mL, to the volumetric flask of 10mL, more accurately add 1mL
Inner mark solution, dilutes with normal hexane and is settled to scale, obtains series standard working solution.Wherein 2,2 ', 5-
The concentration range of trichloro biphenyl is 0.0103～1.026 μ g/mL, the concentration range of 2,4,4 '-trichloro biphenyl is
0.0115～1.15 μ g/mL, the concentration range of 2,2 ', 5,5 '-tetrachloro biphenyl be 0.0101～1.012 μ g/mL,
The concentration range of 2,2 ', 4,5,5 '-pentachlorodiphenyl is 0.0118～1.183 μ g/mL, 2,2 ', 3,4,4 ', 5 '-chlordene connection
The concentration range of benzene is 0.0120～1.203 μ g/mL, the concentration range of 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl is
0.0102～1.015 μ g/mL, the concentration range of 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl be 0.0130～
1.295 μ g/mL, wherein interior target concentration is 0.203 μ g/mL.
S3, the preparation of sample solution
Weigh certain wrapping paper sample 10g (being accurate to 0.1mg), shredded to 5mm × below 5mm,
Mixing, weighs 1g sample from aggregate sample, is placed in 100mL tool plug triangular flask, accurately pipettes 40mL
Dichloromethane extractant, ultrasonic extraction 40min, take appropriate extract through 0.45 μm organic filter membrane mistake
After filter, obtain sample solution.
S4, gas chromatography tandem mass spectrometry analysis
The standard working solution and the sample solution to be measured that take 7 kinds of Polychlorinated biphenyls variable concentrations respectively carry out gas phase
Chromatograph-Tandem Mass Spectrometry Analysis (object and internal standard substance in described standard working solution, typical sample solution
Chromatogram as shown in Figure 2 to 3).
Its instrumental conditions is: use HP-5MS (30m × 0.25mm × 0.25 μm) capillary chromatography
Post；Carrier gas is helium, and constant current speed is 1.0mL/min；Input mode: sample size is 1 μ L, pulse
Splitless injecting samples, sample introduction pressure is 25psi, and the persistent period is 1min；Injector temperature is 280 DEG C；
Transmission line temperature is 280 DEG C；Heating schedule be initial temperature be 50 DEG C, with the speed liter of 15 DEG C/min
Up to 200 DEG C, keep 10min, then be increased to 220 DEG C with the speed of 5 DEG C/min, finally with 20 DEG C/min
Speed to 260 DEG C, keep 4min, rear operational mode keeps 5min under the conditions of 280 DEG C.Its mass spectrum
Analysis condition is: ionization mode is EI source, positive ion mode；Ion source temperature: 230 DEG C；Quadrupole rod
Temperature: be 150 DEG C；Collision gas: nitrogen, flow velocity 1.5mL/min, carrier gas (helium) flow velocity is
2.25mL/min；Multiple-reaction monitoring (MRM) pattern, detail parameters is listed in the table below 1.
The MRM parameter situation of table 1 object
S5, Specification Curve of Increasing and result calculate
First, in standard working solution, object and the ratio of interior target concentration are as abscissa, with chromatogram
Middle object is vertical coordinate with the ratio of interior target peak area, carries out linear regression analysis, obtains standard work
Curve.Take the standard working solution of least concentration, do 9 Parallel testing analyses, calculate its standard deviation,
With the concentration that the standard deviations of 3 times are corresponding, conversion draws the detection limit of method.With standard working curve phase
The data such as the regression equation of correspondence, correlation coefficient, detection limit see table.
Working curve and the detection limit of method analyzed by table 2
Object and interior target chromatographic peak area ratio in the sample solution that will record under the same terms, substitute into mark
Quasi-working curve, tries to achieve the content of object in cigarette sample according to following equation.
In formula:
W is the content of 7 kinds of Polychlorinated biphenyls in food dryness wrapping paper, and unit is microgram every gram (μ g/ gram)；
A is the peak area of 7 kinds of Polychlorinated biphenyls；
As is corresponding interior target peak area；
B is the intercept of standard working curve；
Ms is target quality in adding, and unit is microgram (μ g)；
A is the slope of standard working curve；
M is the quality of food dryness wrapping paper, and unit is gram (g).
7 kinds of Polychlorinated biphenyls material testing results in certain food dryness wrapping paper in table 3 the present embodiment
| Material title | Content (μ g/ gram) |
| 2,2 ', 5-trichloro biphenyl | n.d |
| 2,4,4 '-trichloro biphenyl | n.d |
| 2,2 ', 5,5 '-tetrachloro biphenyl | n.d |
| 2,2 ', 4,5,5 '-pentachlorodiphenyl | n.d |
| 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl | n.d |
| 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl | n.d |
| 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl | n.d |
Remarks: n.d represents that result is less than detection limit, is considered as not detecting.
Embodiment 2
The present embodiment is as follows to the precision of the present invention and the detection method of recovery of standard addition:
Food dryness wrapping paper sample used in embodiment 1, for analyzing object, has been carried out in a few days respectively
Precision Experiment, withinday precision experiment is (same for same sample parallel assay 5 times under identical conditions
Batch processed), calculate the relative standard deviation (RSD) of 5 parallel determinations, measurement result respectively
See table.In table, result shows, the RSD < 10% of the in a few days repeatability of this experimental technique, for trace
For the quantitative analysis of material, show that method has good precision.
The RSD of 4 experimental techniques of table in a few days repeatability
| Material title | RSD (%) |
| 2,2 ', 5-trichloro biphenyl | 5.24 |
| 2,4,4 '-trichloro biphenyl | 2.30 |
| 2,2 ', 5,5 '-tetrachloro biphenyl | 4.36 |
| 2,2 ', 4,5,5 '-pentachlorodiphenyl | 2.89 |
| 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl | 4.05 |
| 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl | 4.61 |
| 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl | 5.07 |
With food dryness wrapping paper sample used by replica test for analyzing object, locate according to before above-mentioned sample
Reason method processes, and adds the standard specimen of the suitable content of its burst size, carries out substrate mark-on test, knot
Fruit see table.As can be seen from the table, the recovery of standard addition of sample, between 68.4%～147.0%, is said
Bright method has preferable accuracy.
The recovery of standard addition of table 5 method
| Material title | Recovery of standard addition (%) |
| 2,2 ', 5-trichloro biphenyl | 126.4 |
| 2,4,4 '-trichloro biphenyl | 119.2 |
| 2,2 ', 5,5 '-tetrachloro biphenyl | 93.0 |
| 2,2 ', 4,5,5 '-pentachlorodiphenyl | 127.0 |
| 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl | 82.2 |
| 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl | 79.5 |
| 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl | 68.4 |
Standard solution used in the present embodiment only illustrates as a example by one of them concentration, other
Standard curve that standard solution prepared by concentration value is obtained through gas chromatography tandem mass spectrometry instrument analysis and
Regression equation is same as the previously described embodiments, is not enumerating at this.Illustrated embodiment is intended merely to more preferably
Understanding the inventive method, not there is any restriction effect, i.e. said method or be equal to above-mentioned situation
Method be all contained in the protection domain of technical scheme.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement
And deformation, these improve and deformation also should be regarded as protection scope of the present invention.
Claims (6)
1. the method for Polychlorinated biphenyls in a quantitative analysis dry food wrapping paper, it is characterised in that include
Following steps:
S1, the preparation of inner mark solution: with heptadecane as internal standard substance, use normal hexane is solvent, system
Standby inner mark solution；
S2, the preparation of standard working solution: with 2,2 ', 5-trichloro biphenyl, 2,4,4 '-trichloro biphenyl, 2,2 ', 5,5 '-
Tetrachloro biphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyl, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene join
Benzene, 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl standard substance are object, and use normal hexane is solvent, through the dilutest
Release and be prepared as Standard Stock solutions, be then respectively adding inner mark solution and be prepared as standard working solution；
S3, the preparation of sample solution: weigh quantitative dry food wrapping paper sample, pulverize, use dichloro
Methane supersound extraction, crosses organic filter membrane, obtains sample solution；
S4, gas chromatography tandem mass spectrometry instrument are analyzed: with gas chromatography tandem mass spectrometry instrument i.e. GC-MS/MS
Standard working solution and sample solution carry out detection analyze；
S5, the drafting of standard working curve and the calculating of sample result.
Polychlorinated biphenyls in a kind of quantitative analysis dry food wrapping paper the most according to claim 1
Method, it is characterised in that in step S1, the preparation of described inner mark solution comprises the following steps:
S10, internal standard storing solution: accurately weigh 0.2g heptadecane, be accurate to 0.1mg, in 100mL
Volumetric flask in, with n-hexane dissolution and be settled to scale；
S11, inner mark solution: accurately pipette 0.1mL internal standard storing solution, in the volumetric flask of 100mL,
Dilute with normal hexane and be settled to scale.
Polychlorinated biphenyls in a kind of quantitative analysis dry food wrapping paper the most according to claim 1
Method, it is characterised in that in step S2, the preparation of described standard working solution comprises the following steps:
S20, primary standard storing solution: accurately weigh 2,2 ', 5-trichloro biphenyl, 2,4,4 '-trichloro biphenyl,
2,2 ', 5,5 '-tetrachloro biphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyl, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-
Chlordene biphenyl, 2,2 ', 3,4,4 ', 5, each 0.1g of 5 '-heptachlor biphenyl standard sample in the volumetric flask of 100mL,
It is accurate to 0.1mg, with n-hexane dissolution and be settled to scale；
S21, secondary standard storing solution: accurately pipette 0.5mL primary standard storing solution, in 50mL's
In volumetric flask, dilute with normal hexane and be settled to scale；
S22, grade III Standard storing solution: accurately pipette 0.5mL secondary standard storing solution, in 50mL's
In volumetric flask, dilute with normal hexane and be settled to scale；
S23, standard working solution: the most accurately pipette grade III Standard storing solution 10 μ L, 20 μ L, 50 μ L,
100 μ L, 200 μ L, 500 μ L and 1mL, to the volumetric flask of 10mL, more accurately add 1mL
Inner mark solution, dilutes with normal hexane and is settled to scale, obtains series standard working solution.
Polychlorinated biphenyls in a kind of quantitative analysis dry food wrapping paper the most according to claim 1
Method, it is characterised in that in step S3, the preparation of described sample solution comprises the following steps: weigh paper
Opening sample 10g, be accurate to 0.1mg, shredded to 5mm × below 5mm, mixing, from aggregate sample
In weigh 1g sample, be placed in 100mL tool plug triangular flask in, accurately pipette 40mL dichloromethane extraction
Solvent, ultrasonic extraction 40min, take appropriate extract after the 0.45 organic membrane filtration of μm, obtain sample
Product solution.
Polychlorinated biphenyls in a kind of quantitative analysis dry food wrapping paper the most according to claim 1
Method, it is characterised in that in step S4, the instrumental conditions that described GC-MS/MS analyzes is: adopt
Use HP-5MS capillary chromatographic column；Carrier gas is helium, and constant current speed is 1.0mL/min；Input mode:
Sample size is 1 μ L, pulse Splitless injecting samples, and sample introduction pressure is 25psi, and the persistent period is 1min；Enter
Sample mouth temperature is 280 DEG C；Transmission line temperature is 280 DEG C；Heating schedule be initial temperature be 50 DEG C, with
The speed of 15 DEG C/min is increased to 200 DEG C, keeps 10min, then is increased to the speed of 5 DEG C/min
220 DEG C, finally with the speed of 20 DEG C/min to 260 DEG C, keeping 4min, rear operational mode is at 280 DEG C
Under the conditions of keep 5min；Its mass spectral analysis condition is: ionization mode is EI source, positive ion mode；From
Source temperature: 230 DEG C；Quadrupole rod temperature: be 150 DEG C；Collision gas: nitrogen, flow velocity 1.5mL/min；
Flow rate of carrier gas is 2.25mL/min；Multiple-reaction monitoring i.e. MRM pattern, detail parameters is listed in the table below 1.
The MRM parameter situation of table 1 object
Polychlorinated biphenyls in a kind of quantitative analysis dry food wrapping paper the most according to claim 1
Method, it is characterised in that in step S5, described standard working curve is drawn and result is calculated as follows: with
In standard working solution, object is abscissa with the ratio of interior target concentration, with object in chromatogram with interior
The ratio of target peak area is vertical coordinate, carries out linear regression analysis, obtains standard working curve；By identical
Under the conditions of object and interior target chromatographic peak area ratio in the sample solution that records, substitute into standard work song
Line, tries to achieve the content of object in outturn according to following equation.
In formula:
W is the content of 7 kinds of Polychlorinated biphenyls in dry food wrapping paper, and unit is microgram every gram；
A is the peak area of 7 kinds of Polychlorinated biphenyls；
As is corresponding interior target peak area；
B is the intercept of standard working curve；
Ms is target quality in adding, and unit is microgram；
A is the slope of standard working curve；
M is the quality of dry food wrapping paper, and unit is gram.
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| CN107064371A (en) * | 2017-04-28 | 2017-08-18 | 西安理工大学 | The detection method of multiple harmful substances in a kind of fast food wrappers bag |
| CN109696492A (en) * | 2018-11-19 | 2019-04-30 | 云南中烟工业有限责任公司 | A method of measurement cigarette Polychlorinated Biphenyls in papery contact material |
| CN110470767A (en) * | 2019-08-27 | 2019-11-19 | 甘肃烟草工业有限责任公司 | Phthalic acid ester and measuring method while Polychlorinated biphenyls in food wrapper |
| CN115248258A (en) * | 2021-04-27 | 2022-10-28 | 湖南中烟工业有限责任公司 | Preparation and detection method of to-be-detected sample of polychlorinated biphenyl in packaging material |
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| CN110470767A (en) * | 2019-08-27 | 2019-11-19 | 甘肃烟草工业有限责任公司 | Phthalic acid ester and measuring method while Polychlorinated biphenyls in food wrapper |
| CN115248258A (en) * | 2021-04-27 | 2022-10-28 | 湖南中烟工业有限责任公司 | Preparation and detection method of to-be-detected sample of polychlorinated biphenyl in packaging material |
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