CN113740456A - Detection method for testing 1, 4-dioxane in consumer product - Google Patents
Detection method for testing 1, 4-dioxane in consumer product Download PDFInfo
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- CN113740456A CN113740456A CN202111031917.4A CN202111031917A CN113740456A CN 113740456 A CN113740456 A CN 113740456A CN 202111031917 A CN202111031917 A CN 202111031917A CN 113740456 A CN113740456 A CN 113740456A
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- 238000012360 testing method Methods 0.000 title claims abstract description 21
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 117
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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
- G01N30/04—Preparation or injection of sample to be analysed
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- G01N30/14—Preparation by elimination of some components
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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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- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
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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
- G01N30/04—Preparation or injection of sample to be analysed
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Abstract
The invention discloses a detection method for testing 1, 4-dioxane in a consumer product, which comprises the following steps: step a, preparing a sample; step b, extracting; step c, gas chromatography-mass spectrometry combined detection; step d, qualitative analysis; and e, carrying out quantitative analysis. The method can fill the blank part which is lack of detection of 1, 4-dioxane in consumer goods in the market, adopts ultrasonic extraction and gas chromatography-mass spectrometry combined detection, is simple to operate, low in equipment cost and high in test efficiency, has the repeatability of 1.70-4.10%, the repeatability of 1.07%, the detection limit of the method is as low as 5mg/kg, and completely meets the SVHC control requirements and the customer test requirements.
Description
Technical Field
The invention relates to the field of consumer product detection, in particular to a detection method for detecting 1, 4-dioxane in a consumer product.
Background
1, 4-dioxane, namely 1, 4-dioxane, also known as dioxane, has strong dissolving capacity, is similar to dimethylformamide and stronger than tetrahydrofuran, is a solvent for chemical synthesis or a byproduct in chemical synthesis, and is widely used in various consumer products, such as medicines, cosmetics, detergents, paints, dyes, polyurethane synthetic leather and other products. The substance has certain harm to human body, has anesthesia and stimulation effects after contacting with human body, has accumulation effect in human body, and can cause dizziness, headache, lethargy, nausea or emesis, etc., and can cause liver and skin damage even uremia in severe cases.
The official website of the Australian health administration for the evaluation of 1, 4-dioxane and the recommended standards thereof has established that the desired limit for 1, 4-dioxane in consumer products (excluding food and pharmaceutical products) is 30ppm, whereas levels not exceeding 100ppm are toxicologically acceptable.
At 3 months 2021, the european chemical administration (ECHA) published a public review of 8 potential highly interesting Substances (SVHCs), ending at 4 months 2021 and listed as 25 th lot by 8 substances in the SVHC list, wherein 8 substances included 1, 4-dioxane and the amount should not exceed 0.1 wt%.
The REACH regulation is one of barrier regulations for consumer products to enter the european market, and therefore, in consideration of consumer product requirements for export to europe and regulatory requirements of other countries, it is important to develop a detection method for rapidly determining the content of 1, 4-dioxane in consumer products. There is no literature or data to provide a method for detecting 1, 4-dioxane in consumer products.
Disclosure of Invention
It is an object of the present invention to provide a method of testing 1, 4-dioxane in a consumer product that solves one or more of the above problems.
According to one aspect of the present invention, there is provided an assay for testing 1, 4-dioxane in a consumable product comprising the steps of:
step a, preparing a sample;
b, carrying out ultrasonic extraction pretreatment on a sample to be detected to form a sample solution;
step c, preparing a standard solution to prepare a standard curve;
d, taking the sample liquid to be detected, and carrying out gas chromatography-mass spectrometry combined detection through a gas chromatography-mass spectrometer to obtain a gas chromatogram and a mass spectrogram of the sample liquid to be detected;
and e, measuring the content of the 1, 4-dioxane in the test sample.
In certain embodiments, step a is specifically: when the consumer goods sample is solid, taking a consumer goods sample, cutting the consumer goods sample into blocks or crushing the consumer goods sample by using a crusher and then uniformly mixing the crushed consumer goods sample to obtain a sample to be detected; the length of the block shape cut by the sample to be detected is 1.5-2.5 mm, and the width is 1.5-2.5 mm; or
When the consumer product sample is liquid, the consumer product sample can be directly used after being uniformly stirred.
Wherein: the size of the sample to be detected is controlled to be 1.5-2.5 mm in block length and 1.5-2.5 mm in width, so that the target substance in the sample to be detected can be conveniently extracted, and the extraction dissolution efficiency is improved.
In certain embodiments, a consumer product comprises at least: medicinal products, cosmetics, detergent, paint, dye, polyurethane synthetic leather, and plastic.
Wherein: the pharmaceutical may be solid or liquid. When the liquid is used, the liquid is stirred uniformly and then is directly used; when the sample is solid, the sample needs to be cut into blocks or crushed by a crusher and then uniformly mixed to obtain a sample to be detected.
The cosmetic is liquid in general, and can be directly used after being uniformly stirred.
The detergent is generally liquid, and can be directly used after being uniformly stirred.
The paint is generally liquid, and can be directly used after being uniformly stirred.
The dye is generally liquid, and can be directly used after being uniformly stirred.
The polyurethane synthetic leather is solid, and needs to be cut into blocks or crushed by a crusher and then uniformly mixed to obtain a sample to be detected.
The plastic is solid and needs to be cut into blocks or crushed by a crusher and then uniformly mixed to obtain a sample to be detected.
Wherein: 1, 4-dioxane is mainly used as a solvent for chemical synthesis or a byproduct in chemical synthesis. The risk of detection in the above-mentioned consumer products is relatively high, so that it is necessary to monitor whether the amount or the residual quantity exceeds the regulatory range.
In certain embodiments, step b is specifically: weighing a certain mass of a sample to be detected, placing the sample to be detected in a reaction tube, measuring a certain amount of dichloromethane and n-hexane to be added into the reaction tube, placing the reaction tube in an ultrasonic generator to perform ultrasonic extraction, taking supernatant in the reaction tube after the ultrasonic extraction is completed, and filtering the supernatant through a polytetrafluoroethylene filter head to obtain a sample liquid to be detected.
Wherein: through carrying out ultrasonic extraction on the sample, the 1, 4-dioxane can be extracted more completely, efficiently and thoroughly, and the detection accuracy is improved.
In some embodiments, the sample to be detected is weighed to be 0.8-1.2 g, the total adding amount of dichloromethane and n-hexane is 8-12 mL, and the adding ratio of dichloromethane to n-hexane is 1: 1.
In some embodiments, the temperature of the ultrasonic extraction is 45-55 ℃, and the time of the ultrasonic extraction is 50-70 min.
Wherein: the extraction solvent selects dichloromethane and n-hexane, the substance 1, 4-dioxane of experimental research is a weak polar solvent, the n-hexane is a nonpolar solvent, and the 1, 4-dioxane is dissolved in the dichloromethane and the n-hexane according to the similarity and intermiscibility principle, so that the 1, 4-dioxane can be better extracted from the sample liquid to be detected. Meanwhile, the dichloromethane and the normal hexane are low-toxicity environment-friendly solvents, so that energy conservation and environmental protection are guaranteed; and dichloromethane and n-hexane are common laboratory reagents, so that the operation is convenient.
In certain embodiments, the standard solution in step c is prepared as follows:
step A, preparing a 1, 4-dioxane stock solution with the concentration of 2000 mg/L:
weighing 0.05g of 1, 4-dioxane, adding dichloromethane and n-hexane to dissolve the 1, 4-dioxane in a first volumetric flask, wherein the adding amount of the dichloromethane and the n-hexane is 1:1, and obtaining 25mL of 1, 4-dioxane stock solution;
step B, preparing a 1, 4-dioxane intermediate solution with the concentration of 200 mg/L:
transferring 1mL of the 1, 4-dioxane stock solution into a second volumetric flask, and adding dichloromethane and n-hexane into the second volumetric flask until the volume is 10mL, wherein the adding amount of the dichloromethane and the n-hexane is 1:1, so as to obtain a 1, 4-dioxane intermediate solution;
step C, preparing a standard working solution of 1, 4-dioxane:
transferring 0.025mL, 0.05mL, 0.1mL, 0.25mL and 0.5mL of the 1, 4-dioxane intermediate solution into 5 different third volumetric flasks, and adding dichloromethane and n-hexane to 10mL in each third volumetric flask, wherein the dichloromethane and n-hexane are added in an amount of 1:1, to obtain five 1, 4-dioxane standard working solutions with different concentrations of 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L and 10.0mg/L, respectively.
In certain embodiments, in step d, the detection conditions for the gc-ms are:
an acquisition mode: SCAN m/z: 20-300 parts of;
and (3) sample introduction mode: shunting and sampling;
the split ratio is as follows: 10: 1;
sample introduction volume: 1.0 μ L;
sample inlet temperature: 280 ℃;
ion source temperature: 230 ℃;
interface temperature: 250 ℃;
the type of the chromatographic column: DB-624 HT;
size of chromatographic column: 30m 0.10um 0.25 mm;
carrier gas: 99.999% helium;
column flow rate: GC: 1.5 mL/min;
initial temperature: 40 ℃;
temperature rising procedure: keeping at 40 deg.C for 5min, heating to 180 deg.C at 20 deg.C/min, keeping for 1min, heating to 250 deg.C at 40 deg.C/min, and keeping for 8 min.
In certain embodiments, the method for determining the 1, 4-dioxane content of the test sample in step e comprises:
and (3) qualitative analysis: firstly, observing gas chromatograms of the sample liquid to be detected and the 1, 4-dioxane standard substance, wherein the retention time of the 1, 4-dioxane is consistent with that of the 1, 4-dioxane, otherwise, judging that the 1, 4-dioxane does not exist in the sample liquid to be detected; and secondly, observing the mass spectrograms of the sample liquid to be detected and the 1, 4-dioxane standard substance, judging that the 1, 4-dioxane exists in the sample liquid to be detected, and carrying out quantitative analysis, otherwise, judging that the 1, 4-dioxane does not exist in the sample liquid to be detected, and not carrying out quantitative analysis.
In certain embodiments, the method for determining the 1, 4-dioxane content of a test sample in step e further comprises:
quantitative analysis: and obtaining a response value of the sample liquid to be detected according to the gas chromatogram of the sample liquid to be detected, and substituting the response value of the sample liquid to be detected into a standard curve or a standard curve equation to obtain the concentration of the 1, 4-dioxane in the sample liquid to be detected.
In some embodiments, the method for obtaining the standard curve and the standard curve equation comprises the following steps:
and 2, establishing a coordinate system by taking the concentration of the 1, 4-dioxane standard working solution as an abscissa and the response value as an ordinate, correspondingly obtaining a plurality of points in the coordinate system according to the solution concentration values and the corresponding response values of the 1, 4-dioxane standard working solution with different concentrations, fitting the points to obtain a standard curve, and converting the standard curve to obtain a standard curve equation.
The detection method for testing 1, 4-dioxane in a consumer product has the beneficial effects that:
1. the method can fill the blank part which is lack of detection of the 1, 4-dioxane in the consumer goods in the market, and the method adopts ultrasonic extraction and gas chromatography-mass spectrometry combined detection, so that the method is simple to operate, has lower equipment cost and has higher test efficiency.
2. The method adopts ultrasonic extraction, utilizes the multistage effects of strong cavitation response effect, mechanical vibration, disturbance effect, high acceleration, emulsification, diffusion, crushing, stirring and the like generated by ultrasonic radiation pressure, can effectively increase the molecular motion frequency and speed of a substance, increase the penetrating power of a solvent, and accelerate target components to enter the solvent, thereby effectively improving the extraction efficiency.
3. The method adopts gas chromatography-mass spectrometry combined detection, can effectively separate the sample liquid to be detected so as to effectively obtain a gas chromatogram and a mass spectrogram of the sample liquid to be detected, has extremely high sensitivity, respectively carries out qualitative and quantitative analysis, has simple and effective analysis steps, can effectively analyze whether the sample liquid to be detected has 1, 4-dioxane and the content of the 1, 4-dioxane, and accordingly can correspondingly and quickly determine the content of the 1, 4-dioxane in the consumer product sample, and has high efficiency and strong reliability.
4. The repeatability of the method is 1.70-4.10%, the repeatability is 1.07%, the detection limit of the method is as low as 5mg/kg, and the method completely meets the control requirements of SVHC and the test requirements of customers.
Drawings
FIG. 1 is a mass spectrum of 1, 4-dioxane according to one embodiment of the present invention.
FIG. 2 is a gas chromatogram of 1, 4-dioxane according to one embodiment of the present invention.
FIG. 3 is a standard graph of 1, 4-dioxane in a test consumable of one embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Referring to fig. 1, 2 and 3, the detection method for testing 1, 4-dioxane in a consumable product of the present embodiment includes the following steps:
step a, sample preparation:
the method comprises the following steps of taking a consumer goods sample which can be medicinal products (solid) leather and plastic, cutting the consumer goods sample into blocks, wherein the length of each block cut by the sample to be detected can be 1.5mm to 2.5mm, and the width of each block cut by the sample to be detected can be 1.5mm to 2.5mm, in the embodiment, the length of each block cut by the sample to be detected is 2mm, and the width of each block is 2mm, or crushing the consumer goods sample by using a crusher and then uniformly mixing the crushed sample, and obtaining the sample to be detected in both modes.
Step b, extraction:
weighing a certain amount of the sample to be detected obtained in the step a, placing the sample to be detected in a 40mL reaction tube, weighing a certain amount of dichloromethane and n-hexane, and adding the dichloromethane and n-hexane into the reaction tube through a pipette, wherein the weighing amount of the sample to be detected can be between 0.8g and 1.2g, the total adding amount of dichloromethane and n-hexane can be between 8mL and 12mL, the adding ratio of dichloromethane and n-hexane is 1:1, in the embodiment, the weighing amount of the sample to be detected is preferably 1g, and the adding amounts of dichloromethane and n-hexane are respectively 5 mL.
And (3) placing the reaction tube in an ultrasonic generator for ultrasonic extraction, taking out supernatant liquid from the reaction tube after the ultrasonic extraction is finished, and filtering the supernatant liquid through a polytetrafluoroethylene filter head to obtain sample liquid to be detected.
The temperature of the ultrasonic extraction can be between 45 ℃ and 55 ℃, the time of the ultrasonic extraction can be between 50min and 70min, in the embodiment, the temperature of the ultrasonic extraction is preferably 50 ℃, and the time of the ultrasonic extraction is preferably 60 min.
Step c, gas chromatography-mass spectrometry combined detection:
and c, carrying out gas chromatography-mass spectrometry combined detection on the sample liquid to be detected obtained in the step b through a gas chromatography-mass spectrometer, and obtaining a gas chromatogram and a mass spectrogram of the sample liquid to be detected.
The detection conditions of the gas chromatography-mass spectrometry combined detection are preferably as follows:
step d, qualitative analysis:
and e, observing the gas chromatogram and the mass spectrogram of the sample liquid to be detected obtained in the step c, judging that 1, 4-dioxane exists in the sample liquid to be detected when the retention time of the 1, 4-dioxane in the gas chromatogram of the sample liquid to be detected is between 6.55min and 6.65min and the mass spectrogram of the sample liquid to be detected is the same as the mass spectrogram of the 1, 4-dioxane, and then considering that the 1, 4-dioxane exists in the consumer product sample, and performing the step e.
And when the retention time of the 1, 4-dioxane in the gas chromatogram of the sample liquid to be detected is not between 6.55min and 6.65min, or the mass spectrogram of the sample liquid to be detected is different from the mass spectrogram of the 1, 4-dioxane, judging that the 1, 4-dioxane does not exist in the sample liquid to be detected, and determining that the 1, 4-dioxane does not exist in the consumer product sample, so that the step e is not performed.
The mass spectrum of the 1, 4-dioxane can be the standard mass spectrum of the 1, 4-dioxane.
Step e, quantitative analysis:
and c, obtaining a response value of the sample liquid to be detected according to the gas chromatogram of the sample liquid to be detected obtained in the step c, substituting the response value of the sample liquid to be detected into a standard curve or a standard curve equation to obtain the concentration of the 1, 4-dioxane in the sample liquid to be detected, wherein the standard curve equation is as follows:
response value is 59940 × concentration + 7391.
And the concentration of the 1, 4-dioxane in the sample liquid to be detected is obtained, namely the concentration of the 1, 4-dioxane contained in the consumer product sample.
Example 2
The detection method for testing 1, 4-dioxane in a consumable product of the embodiment comprises the following steps:
step a, sample preparation:
taking a consumable sample, wherein the consumable sample can be medicinal products (liquid), cosmetics, detergents, paints and dyes, and stirring uniformly for direct use.
Step b, extraction:
weighing a certain amount of the sample to be detected obtained in the step a, placing the sample to be detected in a 40mL reaction tube, weighing a certain amount of dichloromethane and n-hexane, and adding the dichloromethane and n-hexane into the reaction tube through a pipette, wherein the weighing amount of the sample to be detected can be between 0.8g and 1.2g, the total adding amount of dichloromethane and n-hexane can be between 8mL and 12mL, the adding ratio of dichloromethane and n-hexane is 1:1, in the embodiment, the weighing amount of the sample to be detected is preferably 1g, and the adding amounts of dichloromethane and n-hexane are respectively 5 mL.
And (3) placing the reaction tube in an ultrasonic generator for ultrasonic extraction, taking out supernatant liquid from the reaction tube after the ultrasonic extraction is finished, and filtering the supernatant liquid through a polytetrafluoroethylene filter head to obtain sample liquid to be detected.
The temperature of the ultrasonic extraction can be between 45 ℃ and 55 ℃, the time of the ultrasonic extraction can be between 50min and 70min, in the embodiment, the temperature of the ultrasonic extraction is preferably 50 ℃, and the time of the ultrasonic extraction is preferably 60 min.
Step c, gas chromatography-mass spectrometry combined detection:
and c, carrying out gas chromatography-mass spectrometry combined detection on the sample liquid to be detected obtained in the step b through a gas chromatography-mass spectrometer, and obtaining a gas chromatogram and a mass spectrogram of the sample liquid to be detected.
The detection conditions of the gas chromatography-mass spectrometry combined detection are preferably as follows:
step d, qualitative analysis:
and e, observing the gas chromatogram and the mass spectrogram of the sample liquid to be detected obtained in the step c, judging that 1, 4-dioxane exists in the sample liquid to be detected when the retention time of the 1, 4-dioxane in the gas chromatogram of the sample liquid to be detected is between 6.55min and 6.65min and the mass spectrogram of the sample liquid to be detected is the same as the mass spectrogram of the 1, 4-dioxane, and then considering that the 1, 4-dioxane exists in the consumer product sample, and performing the step e.
And when the retention time of the 1, 4-dioxane in the gas chromatogram of the sample liquid to be detected is not between 6.55min and 6.65min, or the mass spectrogram of the sample liquid to be detected is different from the mass spectrogram of the 1, 4-dioxane, judging that the 1, 4-dioxane does not exist in the sample liquid to be detected, and determining that the 1, 4-dioxane does not exist in the consumer product sample, so that the step e is not performed.
The mass spectrum of the 1, 4-dioxane can be the standard mass spectrum of the 1, 4-dioxane.
Step e, quantitative analysis:
and c, obtaining a response value of the sample liquid to be detected according to the gas chromatogram of the sample liquid to be detected obtained in the step c, substituting the response value of the sample liquid to be detected into a standard curve or a standard curve equation to obtain the concentration of the 1, 4-dioxane in the sample liquid to be detected, wherein the standard curve equation is as follows:
response value is 59940 × concentration + 7391.
And the concentration of the 1, 4-dioxane in the sample liquid to be detected is obtained, namely the concentration of the 1, 4-dioxane contained in the consumer product sample.
Example 3
A method of testing for the detection of 1, 4-dioxane in a consumable as set forth in example 1 wherein the standard curve and standard curve equation of step e is obtained by the steps of:
The operating conditions of the gas chromatography-mass spectrometer are preferably in this embodiment:
and 2, establishing a coordinate system by taking the concentration of the 1, 4-dioxane standard working solution as an abscissa and the response value as an ordinate, correspondingly obtaining a plurality of points in the coordinate system according to the solution concentration values and the corresponding response values of the 1, 4-dioxane standard working solution with different concentrations, fitting by a computer according to the plurality of points to obtain a standard curve, and converting according to the standard curve to obtain a standard curve equation.
Example 4
The method for obtaining standard working solutions of 1, 4-dioxane of different concentrations in the method for obtaining the standard curve and the standard curve equation mentioned in example 3 comprises the following steps:
step A, preparing a 1, 4-dioxane stock solution with the concentration of 2000 mg/L:
weighing 0.05g of 1, 4-dioxane, adding dichloromethane and n-hexane to dissolve the 1, 4-dioxane in a 25mL first volumetric flask, adding dichloromethane and n-hexane to fix the volume to the scale mark of the first volumetric flask, wherein the adding amount of the dichloromethane and the n-hexane is 1:1, so that 25mL of 1, 4-dioxane stock solution can be obtained;
step B, preparing a 1, 4-dioxane intermediate solution with the concentration of 200 mg/L:
transferring 1mL of 1, 4-dioxane stock solution into a second volumetric flask by a pipette, adding dichloromethane and n-hexane into the 10mL second volumetric flask, adding dichloromethane and n-hexane to a constant volume to scale marks of the second volumetric flask, wherein the adding amount of the dichloromethane and the n-hexane is 1:1, and obtaining 10mL of 1, 4-dioxane intermediate solution;
step C, preparing a standard working solution of 1, 4-dioxane:
transferring 0.025mL, 0.05mL, 0.1mL, 0.25mL and 0.5mL of the 1, 4-dioxane intermediate solution into 5 different 10mL third volumetric flasks, respectively, by a pipette, and adding dichloromethane and n-hexane to the scale mark of each third volumetric flask in a constant volume of 1:1, thereby obtaining five different concentrations of 1, 4-dioxane standard working solutions with concentrations of 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L and 10.0mg/L, respectively.
Example 5
To demonstrate the reproducibility and reproducibility of the detection method of example 1, 3 examiners were arranged, and 3 replicates of each sample were set for the same target sample to which a standard substance having a 1, 4-dioxane concentration of 5mg/kg was added with reference to the detection method of example 1, and the normalized recovery rate at the added concentration level was calculated. The results are shown in the following table.
From the above table, it can be seen that the repeatability of the detection method of example 1 is 1.70% to 4.10%, and the reproducibility is 1.07%, and the detection limit of the detection method of example 1 to 1, 4-dioxane is as low as 5 mg/kg. The detection method of the embodiment 1 has good precision, good repeatability and reproducibility of the detection result, and completely meets the control requirements of SVHC and the test requirements of customers.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A method for detecting 1, 4-dioxane in a test consumable comprising the steps of:
step a, preparing a sample;
b, carrying out ultrasonic extraction pretreatment on a sample to be detected to form a sample solution;
step c, preparing a standard solution to prepare a standard curve;
d, taking the sample liquid to be detected, and carrying out gas chromatography-mass spectrometry combined detection through a gas chromatography-mass spectrometer to obtain a gas chromatogram and a mass spectrogram of the sample liquid to be detected;
and e, measuring the content of the 1, 4-dioxane in the test sample.
2. The method according to claim 1, wherein the step a is specifically as follows: when the consumer goods sample is solid, taking a consumer goods sample, cutting the consumer goods sample into blocks or crushing the consumer goods sample by using a crusher and then uniformly mixing the crushed consumer goods sample to obtain a sample to be detected; the length of the block shape cut by the sample to be detected is 1.5-2.5 mm, and the width is 1.5-2.5 mm; or
When the consumer product sample is liquid, the consumer product sample can be directly used after being uniformly stirred.
3. The method according to claim 1, wherein step b is specifically as follows: weighing a certain mass of a sample to be detected, placing the sample to be detected in a reaction tube, measuring a certain amount of dichloromethane and n-hexane to be added into the reaction tube, placing the reaction tube in an ultrasonic generator to perform ultrasonic extraction, taking supernatant in the reaction tube after the ultrasonic extraction is completed, and filtering the supernatant through a polytetrafluoroethylene filter head to obtain a sample liquid to be detected.
4. The method for detecting 1, 4-dioxane in a test consumer product according to claim 3, wherein the weighed amount of the sample to be detected is 0.8-1.2 g, the total adding amount of the dichloromethane and the n-hexane is 8-12 mL, and the adding ratio of the dichloromethane to the n-hexane is 1: 1.
5. The method of claim 3, wherein the temperature of the ultrasonic extraction is 45 to 55 ℃ and the time of the ultrasonic extraction is 50 to 70 min.
6. The method of claim 1, wherein the standard solution of step c is prepared by the following steps:
step A, preparing a 1, 4-dioxane stock solution with the concentration of 2000 mg/L:
weighing 0.05g of 1, 4-dioxane, adding dichloromethane and n-hexane to dissolve the 1, 4-dioxane in a first volumetric flask, wherein the adding amount of the dichloromethane and the n-hexane is 1:1, and obtaining 25mL of 1, 4-dioxane stock solution;
step B, preparing a 1, 4-dioxane intermediate solution with the concentration of 200 mg/L:
transferring 1mL of the 1, 4-dioxane stock solution into a second volumetric flask, and adding dichloromethane and n-hexane into the second volumetric flask until the volume is 10mL, wherein the adding amount of the dichloromethane and the n-hexane is 1:1, so as to obtain a 1, 4-dioxane intermediate solution;
step C, preparing a standard working solution of 1, 4-dioxane:
transferring 0.025mL, 0.05mL, 0.1mL, 0.25mL and 0.5mL of the 1, 4-dioxane intermediate solution into 5 different third volumetric flasks, and adding dichloromethane and n-hexane to 10mL in each third volumetric flask, wherein the dichloromethane and n-hexane are added in an amount of 1:1, to obtain five 1, 4-dioxane standard working solutions with different concentrations of 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L and 10.0mg/L, respectively.
7. The method of claim 1, wherein in step d, the conditions for detecting 1, 4-dioxane in the consumable are as follows:
an acquisition mode: SCAN m/z: 20-300 parts of;
and (3) sample introduction mode: shunting and sampling;
the split ratio is as follows: 10: 1;
sample introduction volume: 1.0 μ L;
sample inlet temperature: 280 ℃;
ion source temperature: 230 ℃;
interface temperature: 250 ℃;
the type of the chromatographic column: DB-624 HT;
size of chromatographic column: 30m 0.10um 0.25 mm;
carrier gas: 99.999% helium;
column flow rate: GC: 1.5 mL/min;
initial temperature: 40 ℃;
temperature rising procedure: keeping at 40 deg.C for 5min, heating to 180 deg.C at 20 deg.C/min, keeping for 1min, heating to 250 deg.C at 40 deg.C/min, and keeping for 8 min.
8. The method of claim 1, wherein the step e of determining the 1, 4-dioxane content of the test sample comprises the steps of:
and (3) qualitative analysis: firstly, observing gas chromatograms of the sample liquid to be detected and the 1, 4-dioxane standard substance, wherein the retention time of the 1, 4-dioxane is consistent with that of the 1, 4-dioxane, otherwise, judging that the 1, 4-dioxane does not exist in the sample liquid to be detected; and secondly, observing the mass spectrograms of the sample liquid to be detected and the 1, 4-dioxane standard substance, judging that the 1, 4-dioxane exists in the sample liquid to be detected, and carrying out quantitative analysis, otherwise, judging that the 1, 4-dioxane does not exist in the sample liquid to be detected, and not carrying out quantitative analysis.
9. The method of claim 1, wherein the step e of determining the 1, 4-dioxane content of the test sample further comprises:
quantitative analysis: and obtaining a response value of the sample liquid to be detected according to the gas chromatogram of the sample liquid to be detected, and substituting the response value of the sample liquid to be detected into a standard curve or a standard curve equation to obtain the concentration of the 1, 4-dioxane in the sample liquid to be detected.
10. The method of claim 9, wherein the standard curve and the standard curve equation are obtained by the method comprising the steps of:
step 1, taking 1, 4-dioxane standard working solutions with different concentrations, respectively using a gas chromatography-mass spectrometer for the 1, 4-dioxane standard working solutions with different concentrations to obtain gas chromatograms of the 1, 4-dioxane standard working solutions with different concentrations, and obtaining response values of the 1, 4-dioxane standard working solutions with different concentrations according to the gas chromatograms of the 1, 4-dioxane standard working solutions with different concentrations;
and 2, establishing a coordinate system by taking the concentration of the 1, 4-dioxane standard working solution as an abscissa and the response value as an ordinate, correspondingly obtaining a plurality of points in the coordinate system according to the solution concentration values and the corresponding response values of the 1, 4-dioxane standard working solution with different concentrations, fitting the points to obtain a standard curve, and converting the standard curve to obtain a standard curve equation.
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