CN110568104A - Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware - Google Patents
Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware Download PDFInfo
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- 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
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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
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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
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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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- G01N2030/062—Preparation extracting sample from raw material
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- G—PHYSICS
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- 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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Abstract
The invention provides a method for simultaneously measuring the migration volume of various chlorophenols in wooden tableware, which takes a wooden bowl as a research sample, selects 4% acetic acid, 50% ethanol and isooctane as simulated migration objects, and the sample is subjected to migration liquid soaking, acetic anhydride acylation, n-hexane extraction, measurement by a gas chromatography-mass spectrometer, and external standard method quantification.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a method for simultaneously measuring the migration amounts of various chlorophenols in wooden tableware, and specifically provides a method for simultaneously measuring the migration amounts of pentachlorophenol, 2,4, 6-trichlorophenol, 2, 4-dichlorophenol and 2-chlorophenol in wooden tableware by using a gas chromatography-mass spectrometry combined method.
Background
Wooden tableware, such as wooden bowls, wooden chopsticks and wooden spoons, are common tableware in life, are deeply favored by people due to the fact that the wooden tableware is made of natural biomass materials and has the characteristics of environmental protection and health, and the quality of the wooden tableware is closely related to safety and body health of consumers. However, because the wooden tableware is easy to decay and mildew during storage and use in a humid environment due to the nutrient substances reserved in the wooden tableware, some manufacturers add a certain amount of preservatives and mildewcides (chlorophenols) to treat wooden raw materials in order to prevent the above phenomena.
However, Chlorophenols (CPs) are hazardous to the environment, can cause pollution of water and soil, and enter the food chain through biological enrichment. Several CPs are listed as priority pollutants by the united states Environmental Protection Agency (EPA) and European Council (EC), and the european union REACH regulations prohibit the addition of pentachlorophenol and its esters to wood for construction, containers for planting, food contact.
At present, domestic researches on the determination method of the migration amount of the chlorinated phenols in the wooden tableware are relatively lacked, limited data are mostly related to single determination of the chlorinated phenols, or the specific samples are soil, underground water, paper, wooden toys and the like, and due to different product substrates, use environments and substance objects of the researches, the existing research results cannot be directly applied, so that a method capable of simultaneously determining the migration amounts of various chlorinated phenols in the wooden tableware is necessary to be established to meet the requirements of health supervision.
disclosure of Invention
The invention aims to provide a method for simultaneously determining the migration volume of various chlorinated phenols in wooden tableware, which takes 4 chlorinated phenols as research objects, carries out research on migration conditions, chromatographic conditions, mass spectrum conditions and the like of samples, provides migration conditions and a pretreatment method suitable for the 4 chlorinated phenols in wooden bowls through screening and optimization, and establishes a GC-MS method for simultaneously detecting the 4 chlorinated phenols in the wooden bowls, thereby laying a method foundation for risk monitoring and evaluation of the chlorinated phenols in the wooden tableware.
the invention adopts the following technical scheme:
A method for simultaneously measuring the migration volume of various chlorinated phenols in wooden tableware comprises the following steps:
Step S1 equal clipping0.3-1dm2The wooden tableware sample is used as a sample to be tested, 4% acetic acid, 50% ethanol and isooctane are respectively added as simulated migrates, and standard mixed liquor containing pentachlorophenol, 2,4, 6-trichlorophenol, 2, 4-dichlorophenol and 2-chlorophenol is added, wherein the standard mixed liquor is not subjected to derivatization treatment, and the addition amount of each chlorophenol in the standard mixed liquor is 1: 1: 1: 1, soaking at a simulation set temperature for a simulation set time, and carrying out a simulation experiment to obtain a corresponding migration soak solution;
Step S2: filtering migration soaking liquid corresponding to 4% acetic acid and 50% ethanol until the migration soaking liquid is rotated and evaporated in a round-bottom flask, transferring the migration soaking liquid into a volumetric flask, adjusting the migration soaking liquid of the 4% acetic acid to be neutral by using a sodium hydroxide solution, and adding sodium carbonate into the volumetric flask respectively for shaking and dissolving; filtering the migration soak solution corresponding to isooctane until the migration soak solution is rotated in a round-bottom flask and evaporated to dryness, dissolving the migration soak solution by using a sodium carbonate solution, and transferring the migration soak solution into a volumetric flask;
step S3: adding acetic anhydride and normal hexane into each volumetric flask, oscillating and standing, adding a proper amount of ultrapure water until the normal hexane phase is positioned at the neck of the volumetric flask, moving the normal hexane phase to an anhydrous sodium sulfate solid-phase extraction small column after layering, adding a filter membrane at the tail end of the column, receiving leacheate by using the volumetric flasks, leaching the small columns by using the normal hexane until the volumetric flasks are constant in volume, and obtaining corresponding solution to be measured in migration volume;
step S4: detecting the solution to be detected with the migration quantity by adopting a gas chromatography-mass spectrometry combined method, wherein the detection conditions are as follows:
Chromatographic conditions are as follows: DB-5MS column or HP-5MS column; sample inlet temperature: 270 ℃; temperature rising procedure: the initial temperature is 50 ℃, the temperature is kept for 1min, and the temperature is increased to 260 ℃ at the speed of 15 ℃/min; carrier gas: high-purity helium with the purity more than or equal to 99.999 percent and the flow rate of 1.0 mL/min; and (3) sample introduction mode: injecting sample without shunting, wherein the sample injection volume is 1 mu L;
mass spectrum conditions: the ionization mode is EI, and the ionization energy is 70 eV; the ion source temperature is 230-280 ℃; the temperature of the quadrupole rods is 150 ℃; delaying the solvent for 5 min; a full scanning mode is adopted during qualitative analysis, and the mass scanning range is 80-350 amu;
Step S5: the migration amount of chlorophenols was calculated by the following formula: c ═ C1*V1/V0(ii) a C: migration volume concentration; c1: sampling and testing concentration; v1: finally, the volume is fixed; v0: the volume of the soak solution was transferred.
in the examples of the present invention, the standard mixture was prepared as follows: dissolving 2-chlorophenol with constant volume by using a methanol solution to obtain a 2-chlorophenol standard solution, wherein the concentrations of the 2-chlorophenol standard solution, the 2, 4-dichlorophenol standard solution, the 2,4, 6-trichlorophenol standard solution and the pentachlorophenol standard solution are the same; and transferring the 2-chlorophenol standard solution, the 2, 4-dichlorophenol standard solution, the 2,4, 6-trichlorophenol standard solution and the pentachlorophenol standard solution with the same volume, and mixing in a volumetric flask filled with 0.1mol/L sodium carbonate solution to obtain a standard mixture.
the content of the chlorophenols is quantified by adopting an external standard quantification method, the derivatized standard mixed liquor containing 4 types of chlorophenols with different concentrations is detected by adopting a gas chromatography-mass spectrometry combined method, the response peak area of each substance in the standard mixed liquor and the concentration of each substance are selected as horizontal and vertical coordinates, a standard curve of each substance is drawn, and each substance is quantified by using the standard curve. Within the scope of the invention, the standard mixed solution with the injection concentration of 0.2-10.0 mug/mL is selected and prepared.
The specific derivatization steps are as follows: respectively adding acetic anhydride and normal hexane into the solution mixed with the four mixtures, then oscillating and standing, adding a proper amount of ultrapure water until the normal hexane phase is positioned at the neck of the volumetric flask, moving the normal hexane phase to an anhydrous sodium sulfate solid phase extraction small column after layering, adding a filter membrane at the tail end of the column, receiving eluent by the volumetric flask, and leaching the small column by the normal hexane until the volumetric flask is constant in volume.
In some embodiments, the concentration of 2-chlorophenol standard and 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, pentachlorophenol is selected to be 100 μ g/mL.
Specifically, in one embodiment, 0.1000g of 2-chlorophenol is accurately weighed into a 10mL volumetric flask, methanol is used for fixing the volume to the scale to serve as a standard stock solution, and the stock solution is stored at 4 ℃ in a dark place (can be stably stored for 3 months). 0.100mL of 2-chlorophenol standard stock solution is transferred into a 10mL volumetric flask, and methanol is used for metering volume to scale to prepare a 2-chlorophenol standard solution with the concentration of 100 mu g/mL.
In some embodiments, the standard mixture is injected at a concentration of 0.2, 0.5, 1.0, 2.0, 5.0, 10.0 μ g/mL. The corresponding configuration process may be: 0.010mL, 0.025mL, 0.05mL, 0.100mL, 0.250mL, 0.500mL of 2-chlorophenol at a concentration of 100. mu.g/mL, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, and pentachlorophenol were each transferred into 6 100mL volumetric flasks containing 30mL of 0.1mol/L sodium carbonate.
in step S1, 100mL of 4% acetic acid, 50% ethanol, and isooctane was added as a model migration substance, and the concentration of the migration solution after the addition of the standard mixed solution was 0.05. mu.g/mL.
In some examples, with reference to the addition of 100mL of the simulated migration substance, 100mL of 4% acetic acid and 50% ethanol migration soaking solution are filtered to be evaporated in a round-bottomed flask to about 30mL, then transferred to a 100mL volumetric flask (wherein the 4% acetic acid migration solution is first adjusted to be neutral by sodium hydroxide solution), and 0.3180g of sodium carbonate is added into each volumetric flask respectively to be dissolved by shaking; after 100mL of isooctane transfer soak solution is filtered to be rotated and evaporated to dryness in a round-bottom flask, the solution is dissolved and transferred into a 100mL volumetric flask by using 30mL of 0.1mol/L sodium carbonate solution, and the volume can be adjusted proportionally.
Respectively adding 1mL of acetic anhydride into 100mL volumetric flasks, accurately adding 5.000mL of n-hexane, oscillating for 2min, standing for 5min, adding a proper amount of ultrapure water into the volumetric flasks until the n-hexane phase is positioned at the neck of the volumetric flasks, layering, transferring the n-hexane phase onto an anhydrous sodium sulfate solid phase extraction small column (wet leaching with n-hexane in advance), adding a filter membrane at the tail end of the column, receiving a leaching solution by using the 5mL volumetric flasks, leaching the small column with n-hexane until the volumetric flasks have a constant volume, and measuring.
Compared with the prior art, the invention has the following beneficial effects:
1. The method is characterized in that 4% acetic acid, 50% ethanol and isooctane are used as migration simulators, the conditions that the wooden tableware is contacted with water-based food, alcoholic beverages and oil-containing food are simulated according to the use characteristics of the wooden tableware, the migration simulators soak samples of the wooden tableware, and the migration amount of various chlorinated phenols in the wooden tableware under different migration conditions is measured by a gas chromatography-mass spectrometry combined method.
2. And the migration volumes of pentachlorophenol, 2,4, 6-trichlorophenol, 2, 4-dichlorophenol and 2-chlorophenol are measured simultaneously, so that the measurement cost is reduced, the measurement efficiency is improved, and the method is easy, accurate and sensitive to operate.
drawings
FIG. 1 is a graph of four chlorophenols: total ion chromatograms of pentachlorophenol, 2,4, 6-trichlorophenol, 2, 4-dichlorophenol, 2-chlorophenol standards.
figure 2 is a graphical representation of the results of recovery for different soak temperatures and soak times.
Detailed Description
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
it will be understood by those skilled in the art that in the present disclosure, the terms "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for ease of description and simplicity of description, and do not indicate or imply that the referenced devices or components must be constructed and operated in a particular orientation and thus are not to be considered limiting.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
Preparation of the sample:
Anhydrous sodium carbonate, sodium hydroxide, acetic anhydride, anhydrous ethanol, glacial acetic acid and isooctane are analytically pure, and methanol and n-hexane are chromatographically pure and purchased from Shanghai Linfeng chemical reagent company Limited; anhydrous sodium sulfate solid phase extraction cartridge (2g/6mL) from Agilent; the laboratory water was Milli-Q purified ultrapure water.
Chlorophenols (CPs) were purchased from Hager Biotech, Beijing, where pentachlorophenol (CAS No.: 87-86-5), 2,4, 6-trichlorophenol (CAS No.: 88-06-2), 2, 4-dichlorophenol (CAS No.: 120-83-2), all 100. mu.g/mL; 2-chlorophenol (CAS No.: 95-57-8) with a purity of 99.8%.
Preparation of instruments and equipment:
GC, Agilent 7890A/5975C, Agilent Inc., USA;
Milli-Q ultra pure water instruments, Millipore, USA;
RV 10 rotary evaporator, IKA, Germany.
acquiring standard sample chromatograms of four chlorophenols and corresponding parameters:
After drying and filtering the standard mixed solution containing 2-chlorophenol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol and pentachlorophenol standard mixed solution by a filter membrane, measuring the standard mixed solution by using a gas chromatography-mass spectrometer to obtain four standard sample chromatograms containing chlorophenol, retention time, quantitative ion and qualitative ion parameters of Chlorophenols (CPs), and the following table 1:
TABLE 1 Chlorophohenol parameters
by taking the standard as a standard, four kinds of chlorophenols, namely 2-chlorophenol standard solution, 2, 4-dichlorophenol standard solution, 2,4, 6-trichlorophenol standard solution and pentachlorophenol, can be simultaneously measured in the measuring process.
Secondly, selecting a chromatographic column:
The method comprises the steps of taking a mixed standard solution containing chlorophenol with the concentration of 0.5 mu g/mL as a test sample, measuring the standard mixed solution after drying and filtering by a filter membrane by using a gas chromatography-mass spectrometer, respectively selecting two chromatographic columns of an HP-5MS column and a DB-5MS column, and controlling other conditions to be unchanged, wherein the result shows that compared with the HP-5MS column, the DB-5MS column has better separation effect, so that the DB-5MS column is preferably used as the chromatographic column. In the examples of the present invention, the selected DB-5MS column size is 30m 0.25mm 0.25 μm.
Selecting the ion source temperature:
The boiling point of the Chlorophenols (CPs) is increased along with the increase of the number of the chloridions, the boiling point of the pentachlorophenol is as high as 310 ℃, the loss of the chlorophenols is accelerated due to the overhigh temperature of the ion source, the boiling point of the chlorophenols is reduced by acetylating the chlorophenols, so that the proper temperature of the ion source needs to be comprehensively considered to ensure the effective detection of the chlorophenols, therefore, three temperatures of 230 ℃, 250 ℃ and 280 ℃ are selected for carrying out experiments, and the temperature of the ion source at 230 ℃ is preferably used as the detection condition of the chlorophenols by comprehensively comparing the response value of an instrument and the loss.
and fourthly, simulating the influence of the migration substance on the migration quantity:
Test examples:
Respectively cut to 0.6dm2Adding 100mL of 4% acetic acid, 50% ethanol and isooctane into a blank wooden bowl sample, adding 4 Chlorophenol (CPs) containing mixed standard solutions (the concentration of the added migration solution is 0.05 mu g/mL), and soaking the solution for 6h at the temperature of 40 ℃; filtering 100mL of 4% acetic acid migration soak solution and 50% ethanol migration soak solution respectively until the solution is rotatably evaporated to about 30mL in a round-bottom flask, transferring the solution to a 100mL volumetric flask (wherein the 4% acetic acid migration solution is firstly adjusted to be neutral by a sodium hydroxide solution), respectively adding 0.3180g of sodium carbonate into the volumetric flask respectively, and shaking to dissolve the solution; filtering 100mL of isooctane migration soak solution until the solution is rotated and evaporated to dryness in a round-bottom flask, dissolving the solution by using 30mL of 0.1mol/L sodium carbonate solution, and transferring the solution to a 100mL volumetric flask; respectively adding 1mL of acetic anhydride into the volumetric flask, accurately adding 5.000mL of n-hexane, oscillating for 2min, standing for 5min, adding appropriate amount of ultrapure water into the volumetric flask until the n-hexane phase is at the neck of the volumetric flask, layering, and removing n-hexaneand (3) carrying out phase separation on an anhydrous sodium sulfate solid phase extraction small column (leaching and wetting by n-hexane in advance), adding a filter membrane at the tail end of the column, receiving leaching liquor by using a 5mL volumetric flask, leaching the small column by using the n-hexane until the volume of the volumetric flask is constant, and obtaining a solution to be measured in migration volume.
Detecting the solution to be detected with the migration quantity by adopting a gas chromatography-mass spectrometry combined method, wherein the detection conditions are as follows:
Chromatographic conditions are as follows: DB-5MS column (30m 0.25mm 0.25 u m); sample inlet temperature: 270 ℃; temperature rising procedure: the initial temperature is 50 ℃, the temperature is kept for 1min, and the temperature is increased to 260 ℃ at the speed of 15 ℃/min; carrier gas: high-purity helium with the purity more than or equal to 99.999 percent and the flow rate of 1.0 mL/min; and (3) sample introduction mode: injecting sample without shunting, wherein the sample injection volume is 1 mu L;
Mass spectrum conditions: the ionization mode is EI, and the ionization energy is 70 eV; the ion source temperature is 230 ℃; the temperature of the quadrupole rods is 150 ℃; delaying the solvent for 5 min; a full scanning mode is adopted during qualitative analysis, and the mass scanning range is 80-350 amu; calculating the recovery rate, and adding the standard recovery rate P ═ C1-CK)/CO*100％；
P: adding a standard and recovering rate; c1: adding a standard to test the concentration; cK: testing the concentration of a blank sample; c0: theoretical sample concentration;
the recovery statistics for 4 CPs for each simulated migration are shown in Table 2 below:
TABLE 2 recovery of 4 CPs from different simulated migrates
It can be seen that the 50% ethanol migration solution plus recovery rate for Chlorinated Phenols (CPs) is relatively high, while the polarity of isooctane is low, the migration dissolution for Chlorinated Phenols (CPs) is less, and the solid recovery rate is relatively low.
Fifthly, the influence of the soaking time and the soaking temperature on the migration quantity
Test examples:
Respectively forward cuttingCollecting 0.6dm2Adding 50% ethanol into a blank wooden bowl sample, adding 2-chlorophenol with the concentration of a migration solution of 0.05 mu g/mL, soaking for different times under different temperature conditions, filtering the 50% ethanol migration soaking solution until the solution is rotatably evaporated to about 30mL in a round-bottomed flask, transferring the solution to a 100mL volumetric flask, respectively adding 0.3180g of sodium carbonate into the volumetric flask, and oscillating and dissolving; respectively adding 1mL of acetic anhydride into volumetric flasks, accurately adding 5.000mL of n-hexane, oscillating for 2min, standing for 5min, adding a proper amount of ultrapure water into the volumetric flasks until the n-hexane phase is positioned at the neck of the volumetric flasks, moving the n-hexane phase onto an anhydrous sodium sulfate solid phase extraction small column (leaching and wetting by n-hexane in advance) after layering, adding a filter membrane at the tail ends of the columns, receiving leacheate by using the 5mL volumetric flasks, leaching the small columns by using the n-hexane until the volumetric flasks are constant in volume, obtaining a solution to be detected in a migration amount, keeping the conditions of gas chromatography mass spectrometry detection unchanged, and preparing a graph of recovery rates corresponding to different soaking temperatures and soaking times.
The data statistics for specific conditions and recovery rates are given in table three below:
table 3: effect of different soaking temperatures and soaking times on recovery
From fig. 2, it can be known that the recovery rate is relatively improved along with the increase of the extraction temperature, the fluctuation of the recovery rate is small after the recovery rate is higher than 40 ℃, the difference of the obtained recovery rates is small after the soaking time is longer than 6 hours at the same time when the temperature is selected to be 40 ℃, and the soaking temperature is selected to be 40 ℃ and the soaking time is selected to be 6 hours by comprehensively considering relevant experimental data.
Sixthly, feeding back the linear range, the lower limit of quantification, the recovery rate and the precision of the detection method:
test examples:
the prepared standard mixed solution of 0.2-10.0. mu.g/mL is subjected to GC-MS test respectively, and the corresponding value of Chlorophenols (CPs) is plotted as ordinate and concentration gradient as abscissa, and the results are shown in Table 4, wherein 4 chlorophenols have good linear relationship.
TABLE 4 Standard Curve equations, quantitation limits and detection limits of the four CPs
Test examples:
A blank wooden bowl sample is used for testing the standard adding recovery rate and the precision of three simulated transfer liquid of 4% acetic acid, 50% ethanol and isooctane respectively, each transfer liquid sample is subjected to a standard adding recovery test of 3 concentration levels, each concentration level is subjected to parallel measurement for 6 times, an average value is obtained, the recovery rate and the relative standard deviation are shown in tables 5-7, and the method has better accuracy and precision.
Table 54% recovery of four CPs spiked and RSD in acetic acid migration simulant.
Table 650% ethanol migration simulation four CPs spiked recovery and RSD.
TABLE 7 recovery of four CPs spiked and RSD in isooctane migration simulant
In conclusion, the gas chromatography-mass spectrometry analysis method for simultaneously determining 4 chlorophenols in the wooden bowl is established, the detection limit of the method is low and can reach 0.06 mu g/mL, the sensitivity is high, the reproducibility is good, and the simultaneous detection requirement of various chlorophenols in the wood-bamboo product can be met. Migration behaviors of chlorophenols in wooden bowls are researched, and migration behaviors are influenced by different simulated migration liquids and temperature and time differences selected by wood and bamboo products, wherein the extraction recovery rate of the 50% ethanol migration liquid is relatively high, and the migration recovery rate of the chlorophenols increases along with the increase of the time and the temperature within a certain range of soaking time and temperature.
it is worth mentioning that the wooden tableware mentioned herein includes, but is not limited to, wooden bowls, wooden spoons, wooden chopsticks; due to the special use environment of the wooden tableware, 4% acetic acid, 50% ethanol and isooctane are selected as simulated migrates.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (10)
1. A method for simultaneously measuring the migration volume of various chlorinated phenols in wooden tableware is characterized by comprising the following steps:
s1 equal cutting 0.3-1dm2the wooden tableware sample is used as a sample to be tested, 4% acetic acid, 50% ethanol and isooctane are respectively added as simulated migrants, standard mixed liquor containing pentachlorophenol, 2,4, 6-trichlorophenol, 2, 4-dichlorophenol and 2-chlorophenol is added, the sample is soaked at a simulated set temperature for a simulated set time, and a simulation experiment is carried out to obtain a corresponding migration soaking solution;
Step S2: filtering migration soaking liquid corresponding to 4% acetic acid and 50% ethanol until the migration soaking liquid is rotated and evaporated in a round-bottom flask, transferring the migration soaking liquid into a volumetric flask, adjusting the migration soaking liquid of the 4% acetic acid to be neutral by using a sodium hydroxide solution, and adding sodium carbonate into the volumetric flask respectively for shaking and dissolving; filtering the migration soak solution corresponding to isooctane until the migration soak solution is rotated in a round-bottom flask and evaporated to dryness, dissolving the migration soak solution by using a sodium carbonate solution, and transferring the migration soak solution into a volumetric flask;
Step S3: adding acetic anhydride and normal hexane into each volumetric flask, oscillating and standing, adding a proper amount of ultrapure water until the normal hexane phase is positioned at the neck of the volumetric flask, moving the normal hexane phase to an anhydrous sodium sulfate solid-phase extraction small column after layering, adding a filter membrane at the tail end of the column, receiving leacheate by using the volumetric flasks, leaching the small columns by using the normal hexane until the volumetric flasks are constant in volume, and obtaining corresponding solution to be measured in migration volume;
step S4: detecting the solution to be detected with a migration amount by adopting a gas chromatography-mass spectrometry combined method;
step S5: the migration amount of chlorophenols was calculated by the following formula:
C＝C1*V1/V0(ii) a C: migration volume concentration; c1: sampling and testing concentration; v1: finally, the volume is fixed; v0: the volume of the soak solution was transferred.
2. The method of claim 1, wherein the chromatographic conditions are as follows: DB-5MS column or HP-5MS column; sample inlet temperature: 270 ℃; temperature rising procedure: the initial temperature is 50 ℃, the temperature is kept for 1min, and the temperature is increased to 260 ℃ at the speed of 15 ℃/min; carrier gas: high-purity helium with the purity more than or equal to 99.999 percent and the flow rate of 1.0 mL/min; and (3) sample introduction mode: injecting sample without shunting, wherein the sample injection volume is 1 mu L;
Mass spectrum conditions: the ionization mode is EI, and the ionization energy is 70 eV; the ion source temperature is 230-280 ℃; the temperature of the quadrupole rods is 150 ℃; delaying the solvent for 5 min; the qualitative analysis adopts a full scanning mode, and the mass scanning range is 80-350 amu.
3. the method for simultaneously measuring the migration volume of chlorinated phenols in wooden tableware according to claim 2, wherein the chromatographic column is selected from DB-5MS column; the ion source temperature was chosen to be 230 ℃.
4. The method of claim 1, wherein the calibration curve is prepared by the method comprising: adding acetic anhydride and n-hexane into standard mixed liquid containing 4 types of chlorophenols, oscillating and standing, adding a proper amount of ultrapure water until the n-hexane phase is positioned at the neck of a volumetric flask, moving the n-hexane phase to an anhydrous sodium sulfate solid-phase extraction small column after layering, adding a filter membrane at the tail end of the column, receiving eluent by the volumetric flask, leaching the small column by the n-hexane until the volumetric flask has a constant volume, detecting by adopting a gas chromatography-mass spectrometry condition the same as the detection condition, selecting the response peak area of each substance in the standard mixed liquid and the concentration of each substance as horizontal and vertical coordinates, and drawing a standard curve of each substance.
5. the method of claim 1, wherein the standard mixture is prepared by: dissolving 2-chlorophenol with constant volume by using a methanol solution to obtain a 2-chlorophenol standard solution, wherein the concentrations of the 2-chlorophenol standard solution, the 2, 4-dichlorophenol standard solution, the 2,4, 6-trichlorophenol standard solution and the pentachlorophenol standard solution are the same; and transferring the 2-chlorophenol standard solution, the 2, 4-dichlorophenol standard solution, the 2,4, 6-trichlorophenol standard solution and the pentachlorophenol standard solution with the same volume, and mixing in a volumetric flask filled with 0.1mol/L sodium carbonate solution to obtain a standard mixture.
6. The method of claim 5, wherein the standard mixture with a sample concentration of 0.2-10.0 μ g/mL is selected and prepared.
7. The method of claim 1, wherein in step S1, 100mL of 4% acetic acid, 50% ethanol, isooctane are added as simulated migrates; the concentration of the migration solution after the addition of the standard mixture was 0.05. mu.g/mL.
8. The method for simultaneously measuring the migration volume of the chlorinated phenols in the wooden tableware according to claim 7, wherein 100mL of the simulated migration is used as a reference ratio, 100mL of the 4% acetic acid and 50% ethanol migration soaking solution is filtered into a round-bottomed flask, is rotated and evaporated to about 30mL, is transferred into a 100mL volumetric flask, and is added with 0.3180g of sodium carbonate respectively into the volumetric flask for shaking and dissolving; the 100mL isooctane transfer soak was filtered to a round-bottomed flask and evaporated to dryness by rotation, dissolved in 30mL of 0.1mol/L sodium carbonate solution and transferred to a 100mL volumetric flask.
9. The method for simultaneously measuring the migration volume of the chlorinated phenols in the wooden tableware according to claim 8, wherein 1mL of acetic anhydride is respectively added into a volumetric flask mixed with 100mL of the volumetric flask, 5.000mL of n-hexane is accurately added, the mixture is shaken for 2min, after standing for 5min, a proper amount of ultrapure water is added into the volumetric flask until the n-hexane phase is positioned at the neck of the volumetric flask, after layering, the n-hexane phase is removed to an anhydrous sodium sulfate solid phase extraction column, wherein the solid phase extraction column is rinsed and wetted with n-hexane in advance, after a filter membrane is added at the tail end of the column, a 5mL volumetric flask is used for receiving a rinsing solution, and the n-hexane is used for rinsing the volumetric flask to a constant volume for measurement.
10. the method of any one of claims 1 to 9, wherein the suitable wooden tableware includes but is not limited to wooden bowls, wooden spoons and wooden chopsticks.
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