CN113219091B - Detection method for rapidly determining content of five persistent biological accumulated toxic substances in consumer product - Google Patents
Detection method for rapidly determining content of five persistent biological accumulated toxic substances in consumer product Download PDFInfo
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Abstract
The invention discloses a detection method for rapidly determining the content of five persistent biological accumulated toxic substances in a consumer product, which is characterized by comprising the following steps of: step a, preparing a sample; step b, extracting; step c, gas chromatography-mass spectrometry combined detection; and d, establishing a standard curve and obtaining a quantitative result. The detection method adopts ultrasonic extraction and gas chromatography-mass spectrometry combined analysis, is simple to operate, short in detection time, low in equipment cost and high in detection efficiency. Meanwhile, the repeatability of the method is 0.60-4.10%, the repeatability is 1.07-2.26%, the detection limits of the method for isopropylated triphenyl phosphate, 2,4, 6-tri (tert-butyl) phenol and hexachlorobutadiene are 0.5mg/kg, the detection limits of pentachlorothiophenol and decabromodiphenyl ether are 1mg/kg, the sensitivity is high, and the method completely meets the control requirements of TSCA and the detection of customers.
Description
Technical Field
The invention relates to the field of consumer product detection, in particular to a detection method for rapidly determining the content of five persistent biological accumulated toxic substances in a consumer product.
Background
The persistent bioaccumulation toxic substance (PBT for short) is a chemical substance with persistence, bioaccumulation and toxicity, the PBT substance is not easy to degrade in the environment, is easy to accumulate in the organism and has acute or chronic toxicity, and can cause serious harm to human bodies and ecological environment.
The united states Environmental Protection Agency (EPA) issued a final regulation for five PBT species (2, 4, 6-tri (tert-butyl) phenol (2, 4, 6-TTBP), decabromodiphenyl ether (10 PBDE), isopropylated triphenyl phosphate (PIP), pentachlorothiophenol (PCTP), and Hexachlorobutadiene (HBCD)) in 1 month 2021, which had been in force at 5 days 2 month 2021 and was implemented consecutively from 3 month 8 days 2021. Products containing decabromodiphenyl ether, isopropylated triphenyl phosphate and hexachlorobutadiene, products containing over 1% pentachlorothiophenol and containers (< 35 gallons) containing over 0.3% pentachlorothiophenol, motor oils and lubricating oils are prohibited from being processed and sold in the united states, as required by regulations.
Therefore, considering the product requirements of exported America, it is important to develop a detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in the consumer product.
Disclosure of Invention
The invention aims to provide a detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in a consumer product, which can solve one or more of the problems.
According to one aspect of the invention, a detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in a consumable product is provided, and comprises the following steps:
step a, sample preparation:
taking a clean and pollution-free sample, clamping the target sample, cutting the target sample into blocks or crushing the target sample by using a crusher, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is in a block shape or a granular shape;
step b, extraction:
weighing a certain mass of sample to be detected, placing the sample to be detected in a reaction tube, weighing toluene, adding the toluene into the reaction tube, placing the reaction tube in an ultrasonic generator, performing ultrasonic extraction under certain conditions, taking supernatant to obtain first sample liquid, and filtering the first sample liquid to obtain sample liquid to be detected;
step c, gas chromatography-mass spectrometry combined detection:
c, taking the sample liquid to be detected obtained in the step b, and carrying out gas chromatography-mass spectrometry detection under the following detection conditions:
gas chromatography conditions: the temperature raising program is that the temperature is kept at 50 ℃ for 4min, the temperature is raised to 100 ℃ at 15 ℃/min, then the temperature is raised to 250 ℃ at 30 ℃/min, the temperature is kept for 1min, and then the temperature is raised to 320 ℃ at 20 ℃/min, and the temperature is kept for 5 min; the sample injection amount is 1 mul; the sample introduction mode is non-shunting sample introduction; the carrier gas is high-purity helium; the flow rate is 1.0 ml/min;
mass spectrum conditions: the ion source is an electron bombardment ionization source; the ion source temperature is 250 ℃, and the injection port temperature is 280 ℃; scan range: 50-850, SIM ion: 799, 247, 118, 225, 282;
detecting to obtain a gas chromatogram and a mass spectrogram of a sample liquid to be detected, and comparing the spectrograms of standard substances to obtain qualitative results of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene;
step d, establishing a standard curve and obtaining a quantitative result:
respectively preparing standard curve working solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene with the concentration range of 5-50mg/L gradient concentration, obtaining a standard substance gas chromatogram of five substances of the 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene under the detection condition set in the step c, drawing by taking the concentration of the standard curve working solution as a horizontal coordinate and the peak area of each substance in the gas chromatogram as a vertical coordinate, namely respectively obtaining: standard curves for 2,4, 6-tri (t-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol, and hexachlorobutadiene; and d, substituting the peak areas of the substances in the gas chromatogram of the sample liquid to be detected obtained in the step c into the corresponding standard curves, and calculating the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the sample liquid to be detected, so as to obtain the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the target sample.
The invention has the beneficial effects that: the detection method adopts ultrasonic extraction and gas chromatography-mass spectrometry combined analysis, is simple to operate, short in detection time, low in equipment cost and high in detection efficiency. Meanwhile, the repeatability of the method is 0.60-4.10%, the repeatability is 1.07-2.26%, and the detection limit of the method is as low as 0.5-1 mg/kg. Wherein, the detection limit of the method for isopropylated triphenyl phosphate, 2,4, 6-tri (tert-butyl) phenol and hexachlorobutadiene is 0.5mg/kg, the detection limit of pentachlorothiophenol and decabromodiphenyl ether is 1mg/kg, the sensitivity is high, and the method completely meets the control requirements of the United states toxic substance control method (TSCA) and the detection requirements of customers.
In some embodiments, the length of the block sample to be tested in step a is 1.5-2.5 cm, and the width is 1.5-2.5 cm. The size of the massive sample to be detected is convenient for extracting the target substance in the sample to be detected, and the extraction dissolution efficiency is improved.
In some embodiments, the particle size of the granular sample to be tested in step a is 0.4-0.6 mm. The size of the granular sample to be detected is convenient for extracting target substances in the sample to be detected, and the extraction dissolution efficiency is improved.
In some embodiments, the temperature of the ultrasonic extraction in step b is 45-55 ℃, the power of the ultrasonic generator is 500W, the frequency is 45kHz, and the extraction time is 50-70 min.
In some embodiments, the model number of the column in step c is DB-5 HT.
In some embodiments, the standard curve working solution of gradient concentration in step d is a standard curve working solution of concentration 5mg/L, 10mg/L, 20mg/L, 30mg/L, 50 mg/L.
In some embodiments, the standard curve working solution preparation: 0.25ml, 0.5ml, 1.0ml, 1.5ml and 2.5ml of the mixed intermediate solution are respectively transferred into a 5-branch 10ml brown volumetric flask, the volume is determined to a scale mark by toluene, and standard curve working solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene with the concentrations of 5mg/L, 10mg/L, 20mg/L, 30mg/L and 50mg/L are prepared. For the creation of a standard curve.
In some embodiments, preparation of the mixed intermediate solution: respectively transferring 1ml to 10ml of stock solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene into a brown volumetric flask, and fixing the volume to a scale mark by using toluene to prepare a mixed intermediate solution of the 2,4, 6-tri (tert-butyl) phenol, the decabromodiphenyl ether, the isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene. Mixed intermediate solutions of 2,4, 6-tri (t-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol, and hexachlorobutadiene were used to prepare standard curve working solutions.
In some embodiments, preparation of the stock solution: weighing five standard substances of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, namely 0.05g, dissolving the five standard substances with toluene, transferring the five standard substances into a 25ml brown volumetric flask, fixing the volume to a scale mark, and preparing stock solutions of the 2,4, 6-tri (tert-butyl) phenol, the decabromodiphenyl ether, the isopropylated triphenyl phosphate, the pentachlorothiophenol and the hexachlorobutadiene respectively. Stock solutions of 2,4, 6-tri (t-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol, and hexachlorobutadiene were used to prepare mixed intermediate solutions, facilitating the preparation of standard curve working solutions.
In some embodiments, the repeatability of the detection method is 0.60% -4.10%, the repeatability is 1.07% -2.26%, the detection limit of the detection method for isopropylated triphenyl phosphate, 2,4, 6-tri (tert-butyl) phenol and hexachlorobutadiene is 0.5mg/kg, and the detection limit of the detection method for pentachlorothiophenol and decabromodiphenyl ether is 1 mg/kg. The repeatability of the method is 0.60-4.10%, the repeatability is 1.07-2.26%, the detection limit of the method is as low as 0.5-1mg/kg, the sensitivity is high, and the method completely meets the control requirements of the United states toxic substance control method and the detection requirements of customers.
Drawings
FIG. 1: a is a standard graph of decabromodiphenyl ether, b is a standard graph of 2,4, 6-tri (t-butyl) phenol, c is a standard graph of hexachlorobutadiene, d is a standard graph of isopropylated triphenyl phosphate, and e is a standard graph of pentachlorothiophenol.
FIG. 2: chromatograms of five substances, 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene.
FIG. 3: mass spectrum of 2,4, 6-tri (tert-butyl) phenol.
FIG. 4: mass spectrum of decabromodiphenyl ether.
FIG. 5 is a schematic view of: mass spectrum of isopropylated triphenyl phosphate.
FIG. 6: mass spectrum of pentachlorothiophenol.
FIG. 7 is a schematic view of: mass spectrum of hexachlorobutadiene.
Detailed Description
The present invention will be described in further detail with reference to examples.
Referring to fig. 1-7, the toluene used in the present invention was selected from chromatographically pure toluene supplied by guangzhou chemical reagent plant, 2,4, 6-tri (tert-butyl) phenol standard, decabromodiphenyl ether standard, isopropylated triphenyl phosphate standard, pentachlorothiophenol standard, and hexachlorobutadiene standard, all from dr.
The ultrasonic generator in the invention selects a KQ-500DE ultrasonic generator supplied by ultrasonic instruments of Kunshan city, the gas chromatography-mass spectrometer selects a GCMS-QP2010 Ultra gas chromatography-mass spectrometer supplied by Shimadzu corporation, the chromatographic column selects a DB-5HT, 15m 0.10um 0.25mm chromatographic column, and the pulverizer selects an LD-100 small laboratory pulverizer supplied by Macro mechanical equipment of Changshan city.
Example 1
A detection method for rapidly determining the content of five persistent biological accumulated toxic substances in a consumer product comprises the following steps:
step a, sample preparation:
taking a clean and pollution-free sample, clamping a target sample, wherein the target sample is plastic in a consumer product, cutting the target sample into blocks, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is a square block with the size of 2 x 2 cm;
step b, extraction:
weighing 1g of sample to be detected, placing the sample into a 40ml reaction tube with threads, weighing 10ml of methylbenzene, adding the methylbenzene into the reaction tube, covering a cover, placing the reaction tube into an ultrasonic generator, performing ultrasonic extraction for 60min under the conditions that the power of the ultrasonic generator is 500W, the frequency is 45kHz and the temperature is 50 ℃. Taking the supernatant to obtain a first sample solution, and filtering the first sample solution through a polytetrafluoroethylene filter head with the diameter of 0.45 mu m to obtain a sample solution to be detected;
step c, gas chromatography-mass spectrometry combined detection:
c, taking the sample liquid to be detected obtained in the step b, and carrying out gas chromatography-mass spectrometry detection under the following detection conditions:
gas chromatography conditions: the temperature raising program is that the temperature is kept at 50 ℃ for 4min, the temperature is raised to 100 ℃ at 15 ℃/min, then the temperature is raised to 250 ℃ at 30 ℃/min, the temperature is kept for 1min, and then the temperature is raised to 320 ℃ at 20 ℃/min, and the temperature is kept for 5 min; the sample injection amount is 1 mul; the sample introduction mode is non-shunting sample introduction; the carrier gas is high-purity helium; the flow rate is 1.0 ml/min; mass spectrum conditions: scan Range (m/z): 50-850, SIM ion (m/z): 799, 247, 118, 225, 282. Detecting to obtain a gas chromatogram and a mass spectrogram of a sample liquid to be detected, and comparing spectrograms of standard substances to obtain qualitative results of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene. And (4) determining the chromatographic peak area of the sample solution to be detected in the selective ion mode.
D, establishing a standard curve and obtaining a quantitative result:
d1, preparation of stock solution: weighing 0.05g of five standard substances of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene respectively, dissolving the five standard substances with toluene, transferring the five standard substances into a 25ml brown volumetric flask, and fixing the volume to a scale mark to prepare stock solutions of the 2,4, 6-tri (tert-butyl) phenol, the decabromodiphenyl ether, the isopropylated triphenyl phosphate, the pentachlorothiophenol and the hexachlorobutadiene respectively.
d2, preparation of mixed intermediate solution: respectively transferring 1ml to 10ml of brown volumetric flasks of stock solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, and metering volume to a scale mark by using toluene to prepare a mixed intermediate solution of the 2,4, 6-tri (tert-butyl) phenol, the decabromodiphenyl ether, the isopropylated triphenyl phosphate, the pentachlorothiophenol and the hexachlorobutadiene.
d3, standard curve working solution preparation: 0.25ml, 0.5ml, 1.0ml, 1.5ml and 2.5ml of the mixed intermediate solution are respectively transferred into a 5-branch 10ml brown volumetric flask, the volume is determined to a scale mark by toluene, and standard curve working solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene with the concentrations of 5mg/L, 10mg/L, 20mg/L, 30mg/L and 50mg/L are prepared.
Under the detection conditions set in the step c, standard curve working solutions of 5mg/L, 10mg/L, 20mg/L, 30mg/L and 50mg/L of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in concentration are respectively measured to obtain a standard substance gas chromatogram of the five substances of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, the concentration of the standard curve working solution is taken as a horizontal coordinate, and the peak area of each substance in the gas chromatogram is taken as a vertical coordinate to draw, namely respectively obtain: standard curves for 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene:
standard curve for 2,4, 6-tri (tert-butyl) phenol: y =385837.807812 x-283888.179687
Standard curve for decabromodiphenyl ether: y =5325.464063 x-12415.273438
Standard curve for pentachlorothiophenol: y =28882.884375 x-45838.140625
Standard curve for isopropylated triphenyl phosphate: y =19875.704688 x-46010.007812
Standard curve for hexachlorobutadiene: y =65365.578125 x-81119.296875
Substituting the peak areas of the substances in the gas chromatogram of the sample liquid to be detected obtained in the step c into the corresponding standard curves, and calculating the contents of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, in the sample liquid to be detected, so as to obtain the contents of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, in the target sample, which are respectively 79 mg/kg, 93mg/kg, 102 mg/kg, 152 mg/kg and 201 mg/kg.
Example 2
A detection method for rapidly determining the content of five persistent biological accumulated toxic substances in a consumer product comprises the following steps:
step a, sample preparation:
taking a clean and pollution-free sample, clamping a target sample which is a textile in a consumer product, cutting the target sample into blocks, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is a square block with the size of 1.5 multiplied by 1.5 cm;
step b, extraction:
weighing 1g of sample to be detected, placing the sample into a 40ml reaction tube with threads, weighing 10ml of methylbenzene, adding the methylbenzene into the reaction tube, covering a cover, placing the reaction tube into an ultrasonic generator, performing ultrasonic extraction under the conditions that the power of the ultrasonic generator is 500W, the frequency is 45kHz and the temperature is 45 ℃, and extracting for 50 min. Taking the supernatant to obtain a first sample solution, and filtering the first sample solution through a 0.45-micrometer polytetrafluoroethylene filter head to obtain a sample solution to be detected;
step c, gas chromatography-mass spectrometry combined detection:
b, taking the sample liquid to be detected obtained in the step b, and carrying out gas chromatography-mass spectrometry detection under the following detection conditions:
gas chromatography conditions: the temperature raising program is that the temperature is kept at 50 ℃ for 4min, the temperature is raised to 100 ℃ at 15 ℃/min, then the temperature is raised to 250 ℃ at 30 ℃/min, the temperature is kept for 1min, and then the temperature is raised to 320 ℃ at 20 ℃/min, and the temperature is kept for 5 min; the sample introduction amount is 1 mul; the sample injection mode is non-shunting sample injection; the carrier gas is high-purity helium; the flow rate is 1.0 ml/min; mass spectrum conditions: scan Range (m/z): 50-850, SIM ion (m/z): 799, 247, 118, 225, 282. Detecting to obtain a gas chromatogram and a mass spectrogram of a sample liquid to be detected, and comparing spectrograms of standard substances to obtain qualitative results of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene. And (4) determining the chromatographic peak area of the sample solution to be detected in the selective ion mode.
Substituting the peak areas of the substances in the gas chromatogram of the sample liquid to be detected obtained in the step c into the standard curve of the corresponding substances obtained in the example 1, and calculating the contents of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropyltriphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the sample liquid to be detected, so as to obtain the contents of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropyltriphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, in the target sample, wherein the contents are respectively 80mg/kg, 94mg/kg, 107 mg/kg, 156 mg/kg and 201 mg/kg.
Example 3
A detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in a consumer product comprises the following steps:
step a, sample preparation:
taking a clean and pollution-free sample, clamping a target sample, wherein the target sample is artificial leather in consumer goods, cutting the target sample into blocks, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is a square block with the size of 2.5 multiplied by 2.5 cm;
step b, extraction:
weighing 1g of sample to be detected, placing the sample into a 40ml reaction tube with threads, weighing 10ml of methylbenzene, adding the methylbenzene into the reaction tube, covering a cover, placing the reaction tube into an ultrasonic generator, performing ultrasonic extraction under the conditions that the power of the ultrasonic generator is 500W, the frequency is 45kHz and the temperature is 55 ℃, and extracting for 70 min. Taking the supernatant to obtain a first sample solution, and filtering the first sample solution through a polytetrafluoroethylene filter head with the diameter of 0.45 mu m to obtain a sample solution to be detected;
step c, gas chromatography-mass spectrometry detection:
c, taking the sample liquid to be detected obtained in the step b, and carrying out gas chromatography-mass spectrometry detection under the following detection conditions:
gas chromatography conditions: the temperature raising program is that the temperature is kept at 50 ℃ for 4min, the temperature is raised to 100 ℃ at 15 ℃/min, then the temperature is raised to 250 ℃ at 30 ℃/min, the temperature is kept for 1min, and then the temperature is raised to 320 ℃ at 20 ℃/min, and the temperature is kept for 5 min; the sample injection amount is 1 mul; the sample introduction mode is non-shunting sample introduction; the carrier gas is high-purity helium; the flow rate is 1.0 ml/min; mass spectrum conditions: scan Range (m/z): 50-850, SIM ion (m/z): 799, 247, 118, 225, 282. And detecting to obtain a gas chromatogram and a mass spectrogram of the sample liquid to be detected, and comparing the spectrograms of the standard substances to obtain qualitative results of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene. And (4) determining the chromatographic peak area of the sample solution to be detected in the selective ion mode.
Substituting the peak areas of the substances in the gas chromatogram of the sample liquid to be detected obtained in the step c into the standard curves of the corresponding substances obtained in the embodiment 1, and calculating the contents of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, in the sample liquid to be detected, so as to obtain the contents of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, in the target sample, wherein the contents are 79 mg/kg, 99 mg/kg, 106 mg/kg, 154mg/kg and 206mg/kg respectively.
Example 4
A detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in a consumer product comprises the following steps:
step a, sample preparation:
taking a clean and pollution-free sample, clamping a target sample, wherein the target sample is a coating in a consumer product, crushing the target sample into particles by using a crusher, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is the particles with the particle size of 0.5 mm;
step b, extraction:
weighing 1g of sample to be detected, placing the sample into a 40ml reaction tube with threads, weighing 10ml of methylbenzene, adding the methylbenzene into the reaction tube, covering a cover, placing the reaction tube into an ultrasonic generator, performing ultrasonic extraction at the power of the ultrasonic generator of 500W and the frequency of 45kHz at 50 ℃, and extracting for 60 min. Taking the supernatant to obtain a first sample solution, and filtering the first sample solution through a 0.45-micrometer polytetrafluoroethylene filter head to obtain a sample solution to be detected;
step c, gas chromatography-mass spectrometry combined detection:
c, taking the sample liquid to be detected obtained in the step b, and carrying out gas chromatography-mass spectrometry detection under the following detection conditions:
gas chromatography conditions: the temperature raising program is that the temperature is kept at 50 ℃ for 4min, the temperature is raised to 100 ℃ at 15 ℃/min, then the temperature is raised to 250 ℃ at 30 ℃/min, the temperature is kept for 1min, and then the temperature is raised to 320 ℃ at 20 ℃/min, and the temperature is kept for 5 min; the sample introduction amount is 1 mul; the sample introduction mode is non-shunting sample introduction; the carrier gas is high-purity helium; the flow rate is 1.0 ml/min; mass spectrum conditions: scan Range (m/z): 50-850, SIM ion (m/z): 799, 247, 118, 225, 282. Detecting to obtain a gas chromatogram and a mass spectrogram of a sample liquid to be detected, and comparing spectrograms of standard substances to obtain qualitative results of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene. And (3) determining the chromatographic peak area of the sample solution to be detected in the selected ion mode.
Substituting the peak areas of the substances in the gas chromatogram of the sample liquid to be detected obtained in the step c into the standard curve of the corresponding substances obtained in the example 1, and calculating the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropyltriphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the sample liquid to be detected, so as to obtain the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropyltriphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the target sample, which are respectively 85mg/kg, 96mg/kg, 110 mg/kg, 159 mg/kg and 209 mg/kg.
Example 5
In order to prove the repeatability and reproducibility of the detection method of the present invention, 3 detection personnel were arranged, and 2,4, 6-tri (tert-butyl) phenol, isopropylated triphenyl phosphate, hexachlorobutadiene of 0.5mg/kg and decabromodiphenyl ether, pentachlorothiophenol of 1.0 mg/kg were added to the same target sample according to the detection method of example 1, 3 parallel samples were set for each sample, and the spiked recovery rate at this addition concentration level was calculated. The results are shown in Table 1.
TABLE 1
The repeatability of the detection method is 0.60-4.10% and the reproducibility is 1.07-2.26% as shown in table 1, and the method detection limit of the method for the target substance is lower to 0.5-1mg/kg as shown in table 1.
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 (9)
1. A detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in a consumer product is characterized by comprising the following steps:
step a, sample preparation:
taking a clean and pollution-free sample, clamping a target sample, cutting the target sample into blocks or crushing the target sample by using a crusher, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is in a block shape or a granular shape;
step b, extraction:
weighing a certain mass of the sample to be detected, placing the sample to be detected in a reaction tube, weighing toluene, adding the toluene into the reaction tube, placing the reaction tube in an ultrasonic generator, performing ultrasonic extraction under certain conditions, taking supernatant to obtain first sample liquid, and filtering the first sample liquid to obtain sample liquid to be detected;
step c, gas chromatography-mass spectrometry combined detection:
c, taking the sample liquid to be detected obtained in the step b, and carrying out gas chromatography-mass spectrometry detection, wherein the model of a chromatographic column is DB-5HT, and the detection conditions are set as follows:
gas chromatography conditions: the temperature raising program is that the temperature is kept at 50 ℃ for 4min, the temperature is raised to 100 ℃ at 15 ℃/min, then the temperature is raised to 250 ℃ at 30 ℃/min, the temperature is kept for 1min, and then the temperature is raised to 320 ℃ at 20 ℃/min, and the temperature is kept for 5 min; the sample injection amount is 1 mul; the sample injection mode is non-shunting sample injection; the carrier gas is high-purity helium; the flow rate is 1.0 ml/min;
mass spectrum conditions: the ion source is an electron bombardment ionization source; the ion source temperature is 250 ℃, and the injection port temperature is 280 ℃; scan range: 50-850, SIM ion: 799, 247, 118, 225, 282;
detecting to obtain a gas chromatogram and a mass spectrogram of a sample solution to be detected, and comparing spectrograms of standard substances to obtain qualitative results of five substances, namely 2,4, 6-tri (tert-butyl) phenol (2, 4,6-TTBP for short), decabromodiphenyl ether (10 PBDE for short), isopropyltriphenyl phosphate (PIP for short), pentachlorothiophenol (PCTP for short) and hexachlorobutadiene (HBCD for short);
step d, establishing a standard curve and obtaining a quantitative result:
respectively preparing standard curve working solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene with the concentration range of 5-50mg/L gradient concentration, obtaining standard substance gas chromatogram maps of five substances of the 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene under the detection conditions set in the step c, and drawing by taking the concentration of the standard curve working solutions as a horizontal coordinate and the peak areas of the substances in the gas chromatogram maps as a vertical coordinate, namely respectively obtaining: standard curves for 2,4, 6-tri (t-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol, and hexachlorobutadiene; and d, substituting the peak areas of the substances in the gas chromatogram of the sample liquid to be detected obtained in the step c into the corresponding standard curves, and calculating the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the sample liquid to be detected, so as to obtain the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the target sample.
2. The method as claimed in claim 1, wherein the block sample to be tested in step a has a length of 1.5-2.5 cm and a width of 1.5-2.5 cm.
3. The method as claimed in claim 1, wherein the particle size of the granular sample to be tested in step a is 0.4-0.6 mm.
4. The method for rapidly detecting the content of five persistent bioaccumulation toxic substances in a consumer product according to claim 1, wherein the temperature of ultrasonic extraction in the step b is 45-55 ℃, the power of an ultrasonic generator is 500W, the frequency is 45kHz, and the extraction time is 50-70 min.
5. The method as claimed in claim 1, wherein the standard curve working solution with gradient concentration in step d is standard curve working solution with concentration of 5mg/L, 10mg/L, 20mg/L, 30mg/L, 50 mg/L.
6. The assay of claim 5, wherein the standard curve working solution is prepared by: transferring 0.25ml, 0.5ml, 1.0ml, 1.5ml and 2.5ml of the mixed intermediate solution into a 5-branch 10ml brown volumetric flask, and metering the volume to the scale mark by using toluene to prepare standard curve working solutions of 5mg/L, 10mg/L, 20mg/L, 30mg/L and 50mg/L of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene respectively.
7. The assay for the rapid determination of the content of five persistent bioaccumulation toxic substances in a consumable of claim 6, wherein the preparation of the mixed intermediate solution comprises: respectively transferring 1ml to 10ml of brown volumetric flasks of stock solutions of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene, and metering volume to a scale mark by using toluene to prepare a mixed intermediate solution of the 2,4, 6-tri (tert-butyl) phenol, the decabromodiphenyl ether, the isopropylated triphenyl phosphate, the pentachlorothiophenol and the hexachlorobutadiene.
8. The method for rapid determination of five persistent bioaccumulation toxic substance content in a consumable of claim 7, wherein the stock solution is prepared by: weighing 0.05g of five standard substances of 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene respectively, dissolving the five standard substances with toluene, transferring the five standard substances into a 25ml brown volumetric flask, and fixing the volume to a scale mark to prepare stock solutions of the 2,4, 6-tri (tert-butyl) phenol, the decabromodiphenyl ether, the isopropylated triphenyl phosphate, the pentachlorothiophenol and the hexachlorobutadiene respectively.
9. The detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in a consumer product according to claim 1, wherein the repeatability of the detection method is 0.60-4.10%, the repeatability is 1.07-2.26%, the detection limit of the detection method for isopropylated triphenyl phosphate, 2,4, 6-tri (tert-butyl) phenol and hexachlorobutadiene is 0.5mg/kg, and the detection limit of the detection method for pentachlorothiophenol and decabromodiphenyl ether is 1 mg/kg.
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