CN106018592B - A kind of method of Polychlorinated biphenyls in quantitative analysis dry food wrapping paper - Google Patents
A kind of method of Polychlorinated biphenyls in quantitative analysis dry food wrapping 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 present invention discloses a kind of detection method of Polychlorinated biphenyls in quantitative analysis dry food wrapping paper, this method is based on the content that gas-chromatography-tandem mass spectrometer measures 7 kinds of main Polychlorinated biphenyls substances in dry food wrapping paper, include the preparation of inner mark solution, standard working solution and sample solution, GC MS/MS analysis and the calculating of measurement result and etc..Detection method operation after the present invention is optimized is relatively simple, respond that sensitive, quantitative analysis is accurate, effectively reduce the interference come by sample substrate complicated band, used analytical instrument condition makes object be responded with preferable signal, and there is preferable linear dependence, the detection limit of 7 kinds of Polychlorinated biphenyls substances is respectively 0.99ng/g, 0.74ng/g, 1.05ng/g, 1.29ng/g, 0.75ng/g, 1.11ng/g and 1.19ng/g, repeatability<10%, recovery of standard addition is between 68.4%~147.0%.Illustrate the high sensitivity of this method, repeatability and the rate of recovery are preferable, are suitable for measuring the quantitative analysis of trace object in food dryness wrapping paper.
Description
Technical field
The invention belongs to packaging material physical and chemical index detection technique fields, and in particular to a kind of quantitative analysis dry food packet
The method for filling Polychlorinated biphenyls in paper.
Background technology
Polychlorinated biphenyls (polychlorobiphenyls, PCBs) is the biphenyl compound containing chlorine, has teratogenesis, carcinogenic
And mutagenicity.It is colourless transparent oil liquid, not soluble in water, is soluble in organic solvent, has high temperature resistant, acid and alkali-resistance, no
The features such as easily decomposing.In recent years, some wrapping enterprises are to reduce cost, using a certain proportion of waste paper as the former material of wrapping paper
Material, the paper pulp after deinking can bring remaining Polychlorinated biphenyls in wrapping paper into.Its quality and the health of consumers in general are closely
The safety problem of correlation, packaging material causes extensive concern.
Dry food wrapping paper is important component indispensable in wrapping paper, and safety is very important one
A aspect.It can very likely enter in food packaging as raw materials for production in view of Polychlorinated biphenyls, therefore explore one kind quickly, accurately
Polychlorinated biphenyls detection method, control effectively to the Polychlorinated biphenyls in food dryness wrapping paper, ensure dry food packet
The safety that dress paper uses is very urgent and necessary.
Analysis report about Polychlorinated biphenyls in packaging material is relatively more.Guo Li is quick et al. to use Soxhlet extraction-gas phase
Polychlorinated biphenyls in chromatography determination packaging material for food.Bai Yankun et al. is measured using GC-MS combinations in packaging material for food
Polychlorinated biphenyls.Chen Qiao China et al. also uses the Polychlorinated biphenyls in the analysis means measurement food packaging of GC-MS.Tan Jianhua etc.
People utilizes Polychlorinated biphenyls indicative in Solid Phase Extraction/gas chromatography/mass spectrometry packaging material for food.Yao Weixi etc.
People utilizes the Polychlorinated biphenyls in supercritical fluid extraction Wastewater from Bleaching in Paper Making.But before current existing Polychlorinated biphenyls assay method
Manage it is relatively cumbersome, take it is longer, instrument is more expensive, is not easy to promote the use of.
Therefore, it is urgent to provide a kind of quick, efficient, accurate quantitative analysis methods to detect food by those skilled in the art
The content of Polychlorinated biphenyls in dryness wrapping paper.
Invention content
Deficiency in for the above-mentioned prior art, the present invention provides more chlorine in a kind of quantitative analysis dry food wrapping paper
The method of biphenyl, this method measure the connection of chlorine more than 7 kinds of trace in dry food wrapping paper using gas chromatography tandem mass spectrometry instrument
Benzene, measurement result is accurate, high sensitivity, and matrix interference is few.
To achieve the above object, present invention employs following technical schemes：
The method of Polychlorinated biphenyls, includes the following steps in a kind of quantitative analysis dry food wrapping paper：
The preparation of S1, inner mark solution：Using heptadecane as internal standard compound, the use of n-hexane is solvent, prepares inner mark solution；
The preparation of S2, standard working solution：With 2,2 ', 5- trichloro biphenyls, 2,4,4 '-trichloro biphenyls, 2,2 ', 5,5 '-four
Chlordiphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyls, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl,
2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl standard items are object, the use of n-hexane are solvent, through diluting the standard of being prepared into step by step
Stock solution is then respectively adding inner mark solution and is prepared into standard working solution；
The preparation of S3, sample solution：Quantitative dry food wrapping paper sample is weighed, crushes, is carried with dichloromethane ultrasound
It takes, excessively organic filter membrane obtains sample solution；
S4, the analysis of gas chromatography tandem mass spectrometry instrument：It is worked standard with gas chromatography tandem mass spectrometry instrument, that is, GC-MS/MS
Solution and sample solution are detected analysis；
S5, the drafting of standard working curve and the calculating of sample result.
Preferably, in step S1, the preparation of the inner mark solution includes the following steps：
S10, internal standard storing solution：0.2g heptadecanes accurately are weighed, are accurate to 0.1mg, in the volumetric flask of 100mL,
With n-hexane dissolution and it is settled to scale.
S11, inner mark solution：0.1mL internal standard storing solutions accurately are pipetted, in the volumetric flask of 100mL, simultaneously with n-hexane dilution
It is settled to scale.
Preferably, in step S2, the preparation of the standard working solution includes the following steps：
S20, primary standard storing solution：Accurately weigh 2,2 ', 5- trichloro biphenyls, 2,4,4 '-trichloro biphenyls, 2,2 ', 5,5 '-
Tetrachloro biphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyls, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordenes connection
Benzene, 2,2 ', 3,4,4 ', 5,5 '-each 0.1g of heptachlor biphenyl standard sample are accurate to 0.1mg, with just in the volumetric flask of 100mL
Hexane dissolves and is settled to scale；
S21, secondary standard storing solution：0.5mL primary standard storing solutions accurately are pipetted, in the volumetric flask of 50mL, with just
Hexane dilutes and is settled to scale；
S22, grade III Standard storing solution：0.5mL secondary standard storing solutions accurately are pipetted, in the volumetric flask of 50mL, with just
Hexane dilutes and is settled to scale；
S23, standard working solution：10 μ L of grade III Standard storing solution, 20 μ L, 50 μ L, 100 μ L, 200 μ are accurately pipetted respectively
L, 500 μ L and 1mL, until in the volumetric flask of 10mL, then accurate addition 1mL inner mark solutions respectively, it is diluted and is settled to n-hexane
Scale obtains series standard working solution.
Preferably, in step S3, the preparation of the sample solution includes the following steps：Outturn 10g is weighed, is accurate to
0.1mg is shredded to 5mm × 5mm hereinafter, mixing, weighs 1g samples from aggregate sample, is placed in 100mL conical flask with stopper,
40mL dichloromethane extractants accurately are pipetted, ultrasonic extraction 40min takes appropriate extract liquor through 0.45 μm of organic membrane filtration
Afterwards, sample solution is obtained.
Preferably, in step S4, the instrumental conditions of the GC-MS/MS analyses are：Using HP-5MS capillary chromatographies
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, sample introduction pressure
Power is 25psi, duration 1min；Injector temperature is 280 DEG C；Transmission line temperature is 280 DEG C；Temperature program is initial temperature
Degree is 50 DEG C, is increased to 200 DEG C with the rate of 15 DEG C/min, keeps 10min, then be increased to 220 DEG C with the rate of 5 DEG C/min,
Finally with the rate of 20 DEG C/min to 260 DEG C, 4min, rear operational mode is kept to keep 5min under the conditions of 280 DEG C；Its mass spectrum point
Analysis condition is：Ionization mode is the sources EI, positive ion mode；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；Collision
Gas：Nitrogen, flow velocity 1.5mL/min, carrier gas (helium) flow velocity are 2.25mL/min；Multiple-reaction monitoring (MRM) pattern, detail parameters
It is listed in the table below 1.
The MRM parameter situations of 1 object of table
Preferably, in step S5, the standard working curve is drawn and result calculating is as follows：With mesh in standard working solution
It is abscissa to mark the ratio between object and interior target concentration, with the ratio between object in chromatogram and interior target peak area for ordinate, is carried out
Linear regression analysis obtains standard working curve；By object in the sample solution measured under the same terms and interior target chromatography
Peak area ratio substitutes into standard working curve, the content of object in outturn is acquired according to following equation.
In formula：
W is the content of 7 kinds of Polychlorinated biphenyls in dry food wrapping paper, and unit is every gram of microgram；
A is the peak area of 7 kinds of Polychlorinated biphenyls；
As is target peak area in corresponding；
B is the intercept of standard working curve；
Ms is target quality in addition, 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 biphenyls, regression equation corresponding with standard working curve is y=
0.4102x+0.0456, coefficient R2It is 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 biphenyls, regression equation corresponding with standard working curve is y=0.9922x+0.4026, related
Coefficients R2It is 0.9988, detection is limited to 0.74ng/g, and concentration range is 0.0115~1.15 μ g/mL；For 2,2 ', 5,5 '-four
Chlordiphenyl, regression equation corresponding with standard working curve are y=0.2342x+0.1364, coefficient R2It is 0.9990,
Detection is limited to 1.05ng/g, and concentration range is 0.0101~1.012 μ g/mL；For 2,2 ', 4,5,5 '-pentachlorodiphenyls, with standard
The corresponding regression equation of working curve is y=0.5533x+0.3037, coefficient R2It is 0.9990, detection is limited to
1.29ng/g, concentration range are 0.0118~1.183 μ g/mL；For 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, work with standard
The corresponding regression equation of curve is y=0.5131x+0.1718, coefficient R2It is 0.9989, detection is limited to 0.75ng/g,
Concentration range is 0.0120~1.203；For 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl, corresponding with standard working curve time
It is y=0.7019x+0.2251, coefficient R to return equation2It is 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, regression equation corresponding with standard working curve is y
=0.3558x+0.0785, coefficient R2It is 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 are：
1), the method for the present invention creative use gas chromatography tandem mass spectrometry instrument measures 2 of trace in food dryness wrapping paper,
2 ', 5- trichloro biphenyl, 2,4,4 '-trichloro biphenyls, 2,2 ', 5,5 '-tetrachloro biphenyls, 2,2 ', 4,5,5 '-pentachlorodiphenyls, 2,2 ', 3,
4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl, 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl, 7 kinds of Polychlorinated biphenyls
Content, have the characteristics that quickly, accurate, high sensitivity, and the interference that matrix belt is come can be evaded, be eaten particularly suitable for measuring
The content of Polychlorinated biphenyls in product dryness wrapping paper.
2), the method for the present invention utilizes inner mark method ration, can not have to accurate constant volume, and can reduce by pre-treating method weight
The error that existing property and instrument precision problem are brought.
Description of the drawings
Fig. 1 is the flow chart of quantitative analysis method of the present invention.
Fig. 2 is the Ion-pair chromalography figure of 7 kinds of Polychlorinated biphenyls and internal standard heptadecane in standard working solution of the present invention.
Fig. 3 is the Ion-pair chromalography figure of 7 kinds of Polychlorinated biphenyls and internal standard heptadecane in dry food wrapping paper of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, is clearly and completely retouched to the technical solution in the present invention
It states.The following examples are only intended to illustrate the technical solution of the present invention more clearly, and the guarantor of the present invention cannot be limited with this
Protect range.
Embodiment 1
The present embodiment is to the following (detection method of the detection method of several Trace Polychlorinated Biphenyls in dry food wrapping paper
Flow chart it is as shown in Figure 1)：
The preparation of S1, inner mark solution
S10, internal standard storing solution：0.203g heptadecanes accurately are weighed, it is molten with n-hexane in the volumetric flask of 100mL
It solves and is settled to scale；
S11, inner mark solution：0.1mL internal standard storing solutions accurately are pipetted, in the volumetric flask of 100mL, simultaneously with n-hexane dilution
It is settled to scale.The wherein a concentration of 2.03 μ g/mL of heptadecane.
The preparation of S2, standard working solution
S20, primary standard storing solution：Accurately weigh 2,2 ', 5- trichloro biphenyls 0.1026g, 2,4,4 '-trichloro biphenyls
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 with n-hexane dissolution and is settled to scale in the volumetric flask of 100mL；
S21, secondary standard storing solution：0.5mL primary standard storing solutions accurately are pipetted, in the volumetric flask of 50mL, with just
Hexane dilutes and is settled to scale；
S22, grade III Standard storing solution：0.5mL secondary standard storing solutions accurately are pipetted, in the volumetric flask of 50mL, with just
Hexane dilutes and is settled to scale；
S23, standard working solution：10 μ L of grade III Standard storing solution, 20 μ L, 50 μ L, 100 μ L, 200 μ are accurately pipetted respectively
L, 500 μ L and 1mL, until in the volumetric flask of 10mL, then accurate addition 1mL inner mark solutions respectively, it is diluted and is settled to n-hexane
Scale obtains series standard working solution.The concentration range of wherein 2,2 ', 5- trichloro biphenyls be 0.0103~1.026 μ g/mL, 2,
The concentration range of 4,4 '-trichloro biphenyls is 0.0115~1.15 μ g/mL, the concentration range of 2,2 ', 5,5 '-tetrachloro biphenyls is
0.0101~1.012 μ g/mL, 2,2 ', 4,5,5 '-pentachlorodiphenyls concentration range be 0.0118~1.183 μ g/mL, 2,2 ', 3,
The concentration range of 4,4 ', 5 '-chlordene biphenyl is the concentration of 0.0120~1.203 μ g/mL, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl
Ranging from 0.0102~1.015 μ g/mL, 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl concentration range be 0.0130~1.295 μ
G/mL, wherein a concentration of 0.203 μ g/mL of interior target.
The preparation of S3, sample solution
Certain wrapping paper sample 10g (being accurate to 0.1mg) is weighed, is shredded to 5mm × 5mm hereinafter, mixing, from aggregate sample
In weigh 1g samples, be placed in 100mL conical flask with stopper, accurately pipette 40mL dichloromethane extractants, ultrasonic extraction
40min takes appropriate extract liquor after 0.45 μm of organic membrane filtration, obtains sample solution.
S4, gas chromatography tandem mass spectrometry analysis
The standard working solution and sample solution progress gas-chromatography-string to be measured of 7 kinds of Polychlorinated biphenyls various concentrations are taken respectively
Join the mass spectral analysis (chromatogram of object and internal standard compound such as Fig. 2~Fig. 3 institutes in the standard working solution, typical sample solution
Show).
Its instrumental conditions is：Using HP-5MS (30m × 0.25mm × 0.25 μm) capillary chromatographic column；Carrier gas is helium
Gas, constant current speed are 1.0mL/min；Input mode：Sample size is 1 μ L, and pulse Splitless injecting samples, sample introduction pressure is 25psi, is held
The continuous time is 1min；Injector temperature is 280 DEG C；Transmission line temperature is 280 DEG C；Temperature program is that initial temperature is 50 DEG C, with
The rate of 15 DEG C/min is increased to 200 DEG C, keeps 10min, then be increased to 220 DEG C with the rate of 5 DEG C/min, finally with 20 DEG C/
The rate of min keeps 4min, rear operational mode to keep 5min under the conditions of 280 DEG C to 260 DEG C.Its mass spectral analysis condition is：Electricity
It is the sources EI, positive ion mode from mode；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；Collision gas：Nitrogen, stream
Fast 1.5mL/min, carrier gas (helium) flow velocity are 2.25mL/min；Multiple-reaction monitoring (MRM) pattern, detail parameters are listed in the table below 1.
The MRM parameter situations of 1 object of table
S5, Specification Curve of Increasing and result calculate
First, with the ratio between object in standard working solution and interior target concentration for abscissa, with object in chromatogram
It is ordinate with the ratio between interior target peak area, carries out linear regression analysis, obtain standard working curve.Take the standard of minimum concentration
Working solution does 9 Parallel testing analyses, calculates its standard deviation, with the corresponding concentration of 3 times of standard deviation, conversion obtains
The detection limit of method.The data such as regression equation corresponding with standard working curve, related coefficient, detection limit see the table below.
The working curve and detection limit of 2 analysis method of table
By object in the sample solution measured under the same terms and interior target chromatographic peak area ratio, it is bent to substitute into standard work
Line acquires 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 every gram of microgram (μ g/ gram)；
A is the peak area of 7 kinds of Polychlorinated biphenyls；
As is target peak area in corresponding；
B is the intercept of standard working curve；
Ms is target quality in addition, 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 substance testing results in certain food dryness wrapping paper in 3 the present embodiment of table
| Substance title | Content (μ g/ gram) |
| 2,2 ', 5- trichloro biphenyl | n.d |
| 2,4,4 '-trichloro biphenyls | n.d |
| 2,2 ', 5,5 '-tetrachloro biphenyls | n.d |
| 2,2 ', 4,5,5 '-pentachlorodiphenyls | 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 indicates that result is limited less than detection, is considered as and is not detected.
Embodiment 2
The present embodiment is as follows to the precision of the present invention and the detection method of recovery of standard addition：
It is analysis object with food dryness wrapping paper sample used in embodiment 1, has carried out withinday precision reality respectively
It tests, withinday precision experiment is same sample parallel determination 5 times (same batch processeds) under identical conditions, is calculated separately 5 times
The relative standard deviation (RSD) of parallel determinations, measurement result see the table below.In table the results show that this experimental method in a few days
The RSD of repeatability<10%, for the quantitative analysis of trace materials, show that method has good precision.
The in a few days repeated RSD of 4 experimental methods of table
| Substance title | RSD (%) |
| 2,2 ', 5- trichloro biphenyl | 5.24 |
| 2,4,4 '-trichloro biphenyls | 2.30 |
| 2,2 ', 5,5 '-tetrachloro biphenyls | 4.36 |
| 2,2 ', 4,5,5 '-pentachlorodiphenyls | 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 in repetitive test be analysis object, according to above-mentioned sample-pretreating method into
Row processing, is added the standard specimen of the comparable content of its burst size, carries out matrix mark-on experiment, as a result see the table below.It can from table
Go out, for the recovery of standard addition of sample between 68.4%~147.0%, illustration method has preferable accuracy.
The recovery of standard addition of 5 method of table
| Substance title | Recovery of standard addition (%) |
| 2,2 ', 5- trichloro biphenyl | 126.4 |
| 2,4,4 '-trichloro biphenyls | 119.2 |
| 2,2 ', 5,5 '-tetrachloro biphenyls | 93.0 |
| 2,2 ', 4,5,5 '-pentachlorodiphenyls | 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 |
What the standard solution used in the present embodiment was only illustrated by taking one of concentration as an example, other concentration values institute
The standard solution of preparation analyzes obtained standard curve and regression equation and above-described embodiment through gas chromatography tandem mass spectrometry instrument
It is identical, it is not enumerating herein.Illustrated embodiment is intended merely to be better understood from the method for the present invention, and does not have any restrictions
Effect, the i.e. method of the above method or equivalent the above situation are all contained in the protection domain of technical scheme of the present invention.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of method of Polychlorinated biphenyls in quantitative analysis dry food wrapping paper, it is characterised in that include the following steps：
The preparation of S1, inner mark solution：Using heptadecane as internal standard compound, the use of n-hexane is solvent, prepares inner mark solution；
The preparation of S2, standard working solution：With 2,2 ', 5- trichloro biphenyls, 2,4,4 '-trichloro biphenyls, 2,2 ', 5,5 '-tetrachloros connection
Benzene, 2,2 ', 4,5,5 '-pentachlorodiphenyls, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl, 2,2 ',
3,4,4 ', 5,5 '-heptachlor biphenyl standard items are object, the use of n-hexane are solvent, standard inventory is prepared into through diluting step by step
Solution is then respectively adding inner mark solution and is prepared into standard working solution；
The preparation of S3, sample solution：Quantitative dry food wrapping paper sample is weighed, is crushed, with dichloromethane ultrasonic extraction, mistake
Organic filter membrane, obtains sample solution；
S4, the analysis of gas chromatography tandem mass spectrometry instrument：With gas chromatography tandem mass spectrometry instrument, that is, GC-MS/MS to standard working solution
It is detected analysis with sample solution；
Wherein, the instrumental conditions of the GC-MS/MS analyses are：Using HP-5MS capillary chromatographic columns；Carrier gas is helium,
Constant current speed is 1.0mL/min；Input mode：Sample size is 1 μ L, and pulse Splitless injecting samples, sample introduction pressure is 25psi, is continued
Time is 1min；Injector temperature is 280 DEG C；Transmission line temperature is 280 DEG C；Temperature program is that initial temperature is 50 DEG C, with 15
DEG C/rate of min is increased to 200 DEG C, 10min is kept, then 220 DEG C are increased to the rate of 5 DEG C/min, finally with 20 DEG C/min
Rate to 260 DEG C, keep 4min, rear operational mode keeps 5min under the conditions of 280 DEG C；Its mass spectral analysis condition is：Ionization
Mode is the sources EI, positive ion mode；Ion source temperature：230℃；Quadrupole rod temperature：It is 150 DEG C；Collision gas：Nitrogen, flow velocity
1.5mL/min, flow rate of carrier gas 2.25mL/min；The MRM parameter situations of multiple-reaction monitoring, that is, MRM patterns, object are：Positive ten
Seven carbon alkane, 2,2 ', 5- trichloro biphenyls, 2,4,4 '-trichloro biphenyls, 2,2 ', 5,5 '-tetrachloro biphenyls, 2,2 ', 4,5,5 '-pentachloro-s connection
Benzene, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl, 2,2 ', 3,4,4 ', 5,5 '-heptachlor biphenyl
Parent ion be respectively 240,256,256,292,326,360,360,394, product ion is respectively 57,221,186,257,
256,325,325,359, collision energy is respectively 15,15,25,15,25,10,15,15eV；
S5, the drafting of standard working curve and the calculating of sample result.
2. the method for Polychlorinated biphenyls, feature exist in a kind of quantitative analysis dry food wrapping paper according to claim 1
In step S1, the preparation of the inner mark solution includes the following steps：
S10, internal standard storing solution：0.2g heptadecanes accurately are weighed, are accurate to 0.1mg, in the volumetric flask of 100mL, with just
Hexane dissolves and is settled to scale；
S11, inner mark solution：0.1mL internal standard storing solutions accurately are pipetted, in the volumetric flask of 100mL, with n-hexane dilution and constant volume
To scale.
3. the method for Polychlorinated biphenyls, feature exist in a kind of quantitative analysis dry food wrapping paper according to claim 1
In step S2, the preparation of the standard working solution includes the following steps：
S20, primary standard storing solution：Accurately weigh 2,2 ', 5- trichloro biphenyls, 2,4,4 '-trichloro biphenyls, 2,2 ', 5,5 '-tetrachloros
Biphenyl, 2,2 ', 4,5,5 '-pentachlorodiphenyls, 2,2 ', 3,4,4 ', 5 '-chlordene biphenyl, 2,2 ', 4,4 ', 5,5 '-chlordene biphenyl, 2,
2 ', 3,4,4 ', 5,5 '-each 0.1g of heptachlor biphenyl standard sample are accurate to 0.1mg in the volumetric flask of 100mL, molten with n-hexane
It solves and is settled to scale；
S21, secondary standard storing solution：Accurately pipette 0.5mL primary standard storing solutions uses n-hexane in the volumetric flask of 50mL
It dilutes and is settled to scale；
S22, grade III Standard storing solution：Accurately pipette 0.5mL secondary standard storing solutions uses n-hexane in the volumetric flask of 50mL
It dilutes and is settled to scale；
S23, standard working solution：10 μ L of grade III Standard storing solution, 20 μ L, 50 μ L, 100 μ L, 200 μ L, 500 are accurately pipetted respectively
μ L and 1mL, until in the volumetric flask of 10mL, then accurate addition 1mL inner mark solutions respectively, scale is diluted and is settled to n-hexane,
Obtain series standard working solution.
4. the method for Polychlorinated biphenyls, feature exist in a kind of quantitative analysis dry food wrapping paper according to claim 1
In step S3, the preparation of the sample solution includes the following steps：Outturn 10g is weighed, 0.1mg is accurate to, is cut
5mm × 5mm is broken to hereinafter, mixing, weighs 1g samples from aggregate sample, is placed in 100mL conical flask with stopper, accurately pipettes 40mL
Dichloromethane extractant, ultrasonic extraction 40min take appropriate extract liquor after 0.45 μm of organic membrane filtration, it is molten to obtain sample
Liquid.
5. the method for Polychlorinated biphenyls, feature exist in a kind of quantitative analysis dry food wrapping paper according to claim 1
In step S5, the standard working curve is drawn and result calculating is as follows：With object in standard working solution and interior target
The ratio between concentration is abscissa, with the ratio between object in chromatogram and interior target peak area for ordinate, carries out linear regression analysis,
Obtain standard working curve；By object in the sample solution measured under the same terms and interior target chromatographic peak area ratio, substitute into
Standard working curve acquires 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 every gram of microgram；
A is the peak area of 7 kinds of Polychlorinated biphenyls；
As is target peak area in corresponding；
B is the intercept of standard working curve；
Ms is target quality in addition, 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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