CN114113380B - Rapid detection method for quinoline in textile - Google Patents
Rapid detection method for quinoline in textile Download PDFInfo
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- CN114113380B CN114113380B CN202111341082.2A CN202111341082A CN114113380B CN 114113380 B CN114113380 B CN 114113380B CN 202111341082 A CN202111341082 A CN 202111341082A CN 114113380 B CN114113380 B CN 114113380B
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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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- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
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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
- G01N2030/062—Preparation extracting sample from raw material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a rapid detection method of quinoline in textile, which adopts a thermal desorption-gas chromatography-mass spectrometry combined instrument to detect the quinoline, and comprises the following steps: (1) Shearing a sample to be detected into fragments with the particle size of less than 0.5mm, uniformly mixing, weighing a proper amount of the sample to be detected, placing the sample to be detected at the bottom of a thermal desorption sample cup, and covering a proper amount of silanized glass wool on the sample; (2) Preparing a quinoline standard substance of a PVC matrix, placing the quinoline standard substance of the PVC matrix at the bottom of a thermal desorption sample cup, and covering a proper amount of silanized glass wool on the quinoline standard substance; (3) Respectively placing the thermal desorption sample cups in the step (1) and the step (2) into a thermal desorption device for detection by a thermal desorption-gas chromatography mass spectrometer; (4) And (3) performing qualitative and quantitative detection on the quinoline according to the retention time, characteristic ions and peak response value comparison of the quinoline in the sample to be detected and the standard. The method ensures that the detection process of quinoline in the textile is more green and efficient.
Description
Technical Field
The invention relates to the field of textile detection, in particular to a rapid detection method of quinoline in textiles.
Background
Quinoline is an important alkaloid, has important physiological activity and is widely applied to the fields of textile printing and dyeing, fine chemical industry and the like. Quinoline is widely used as a solvent and a raw material in the textile printing industry, so that a large amount of quinoline enters the environment every year and becomes a common pollutant in soil and water. In addition to groundwater, quinoline and its derivatives have been shown to be present in aquifer sediments, urban air, tobacco smoke, seawater, carcinogenic, teratogenic, mutagenic to organisms, and extremely damaging to the environment. 2021 International ecological textile Standard 100 byQuinoline is included in the list of limiting substances. On 12 th 10 2018, the restriction bill of textiles and footwear products that are classified as carcinogenic, mutagenic, genito toxicity (CMR) 1 class a and 1B in the european union's REACH regulations (EC) No1907/2006 annex XVII, involving apparel and related accessories, direct skin contact, is specified, quinoline being listed wherein the limit requirement for it is 50mg/kg, which restriction requirement is to be implemented on 11 th 2020. In GB/T31531-2015 'determination of quinoline in dye and textile dyeing and finishing auxiliary products', ethyl acetate is adopted to extract quinoline from aqueous solution, then gas chromatography analysis is carried out, and organic solvent is adopted for extraction in pretreatment, so that a large amount of solvent and pretreatment time are consumed, and the environment is harmed to a certain extent.
At present, the detection of quinoline in textiles adopts a pretreatment mode of organic solvent extraction, a large amount of organic reagents are needed, and the operation process is tedious and time-consuming. There is a need to create a more environmentally friendly and efficient detection method for detecting quinoline content in textiles.
Disclosure of Invention
Aiming at the problems that the pretreatment process of the existing detection method is tedious and time-consuming in operation and consumes a large amount of organic solvent, the invention provides a rapid detection method for quinoline in textiles, so that the detection process is more environment-friendly and efficient.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a rapid detection method of quinoline in textile adopts thermal desorption-gas chromatography-mass spectrometry to detect quinoline, comprising the following steps:
(1) Shearing a sample to be detected into fragments with the particle size of less than 0.5mm, uniformly mixing, weighing a proper amount of sample to be detected, placing the fragment at the bottom of a thermal desorption sample cup, placing a proper amount of silanized glass wool into the thermal desorption sample cup, and covering the sample;
(2) Preparing a quinoline standard substance of a PVC matrix, placing the quinoline standard substance of the PVC matrix at the bottom of a thermal desorption sample cup, and covering a proper amount of silanized glass wool on the quinoline standard substance;
(3) Respectively placing the thermal desorption sample cup filled with the sample to be detected in the step (1) and the thermal desorption sample cup filled with the quinoline standard substance of the PVC matrix in the step (2) into a thermal desorption device for detection by a thermal desorption-gas chromatography mass spectrometer;
(4) And comparing the retention time, characteristic ions and peak response values of the quinoline in the sample to be detected with those of the quinoline in the standard sample, and carrying out qualitative and quantitative detection on the quinoline.
The invention is further arranged that the mass of the sample to be tested is 0.5-1.00 mg, and the mass is accurate to 0.01mg.
The invention is further arranged that the instrument conditions of the thermal desorption device are as follows: the micro-furnace type heating is adopted, the thermal desorption temperature is 240-300 ℃, the thermal desorption time is 6-60 s, and the interface temperature is 280-320 ℃.
The invention further provides that the gas chromatograph-mass spectrometer has the following gas chromatograph conditions: the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m or other capillary columns of the same type; the carrier gas is high-purity helium; the flow rate of the column is 0.8-1.2 mL/min; the temperature of the sample inlet is 250-300 ℃; split-flow sample injection is adopted, and the split ratio (100-140): 1, a step of; programming temperature: the initial temperature is 40-80 ℃, kept for 0-5 min, heated to 260-330 ℃ at 10-50 ℃/min, and kept for 2-5 min.
The invention further provides that the mass spectrometer conditions of the gas chromatograph-mass spectrometer are as follows: mass spectrometry employed EI ion source: 70eV, ion source temperature 230-300 ℃, gas interface temperature 270-320 ℃, mass spectrum scanning is a selective ion detection (SIM) mode, and mass spectrum parameters are shown in the following table.
The invention further provides a preparation method of the quinoline standard substance of the PVC matrix, which comprises the following steps: and sucking a standard working solution of the quinoline, injecting the standard working solution into a thermal desorption sample cup, and volatilizing the solvent to obtain the quinoline standard product of the PVC matrix.
The invention further provides a preparation method of the standard working solution, which comprises the following steps: quantitatively weighing a quinoline standard substance, preparing a standard stock solution with the concentration of 1000-2000 mug/mL by taking a PVC polymer organic solution as a solvent, and diluting the standard stock solution into a standard working solution with the concentration of 0.5-100 mug/mL.
The invention further provides that the PVC macromolecule organic solution is prepared by dissolving PVC powder with tetrahydrofuran to prepare the PVC macromolecule organic solution with the concentration of 50000-100000 mug/mL.
The invention is further arranged that the content of the quinoline is calculated according to the following formula:
X＝A i ×C is /(A is ×m) (1)
wherein: x is the content of quinoline in the sample, and the unit is micrograms per gram (mug/g);
C is the unit is nanograms (ng) of the absolute mass of quinoline in a standard;
A i peak response value of quinoline in the sample;
A is peak response value of quinoline in standard;
m is the sample weight in milligrams (mg).
Compared with the prior art, the rapid detection method for quinoline in the textile provided by the invention can rapidly detect whether the textile contains quinoline or not, does not need any complex pretreatment, avoids the harm of an organic reagent, and can rapidly detect the quinoline in the textile, wherein the detection limit is 3.52mg/kg. The method overcomes the defects of a chemical solvent extraction pretreatment method, promotes the detection of quinoline to be more environment-friendly, and ensures that the textile can be high-efficiency, accurate and environment-friendly when being safely detected.
Drawings
FIG. 1 is a graph showing peak response values of quinoline in a standard working solution of quinoline prepared from a polyvinyl chloride (PVC) polymer organic solution, ethyl acetate, n-hexane and a methanol solvent in example 1.
FIG. 2 is a graph of PVC concentration versus peak quinoline response for example 2.
FIG. 3 is a selective ion chromatogram of the quinoline standard of example 3 (100 ng absolute mass).
FIG. 4 is a sample-selective ion chromatogram of example 3.
FIG. 5 is a selective ion chromatogram of the quinoline standard of example 4 (100 ng absolute mass).
FIG. 6 is a sample-selective ion chromatogram of example 4.
FIG. 7 is a selective ion chromatogram of the quinoline standard (100 ng absolute mass) of example 5.
FIG. 8 is a sample-selective ion chromatogram of example 5.
FIG. 9 is a selective ion chromatogram of the quinoline standard of example 6 (100 ng absolute mass).
FIG. 10 is a sample-selective ion chromatogram of example 6.
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that the examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the appended claims.
EXAMPLE 1 solvent selection of quinoline Standard working solution
Four different solvents of ethyl acetate, normal hexane, methanol and polyvinyl chloride (PVC) polymer organic solution are respectively selected to prepare quinoline standard working solutions with the same concentration, the four groups of prepared quinoline standard working solutions are respectively absorbed and added into thermal desorption sample cups and placed for 10 minutes, and the quinoline standard working solutions in the four groups of sample cups are respectively detected by adopting a thermal desorption-gas chromatography-mass spectrometer, and the detection results are shown in figure 1.
As can be seen from the quinoline response values corresponding to different solvents in the graph 1, the quinoline peak response value of the quinoline standard working solution prepared by adopting ethyl acetate, normal hexane and methanol solvents is obviously lower than that of the quinoline standard working solution prepared by adopting PVC high-molecular organic solution. The quinoline standard working solution prepared by the PVC macromolecule organic solution can reduce the volatilization of quinoline in the waiting analysis process, so that a more accurate detection result can be obtained.
Example 2 preparation of PVC Polymer organic solution
(1) Accurately weighing 10.0g (accurately to 0.0001 g) of PVC powder, preparing 100000 mug/mL of PVC polymer organic solution by using an analytically pure tetrahydrofuran solution, and gradually diluting the solution into PVC polymer organic solution with the concentration of 500 mug/mL, 1000 mug/mL, 5000 mug/mL, 10000 mug/mL, 25000 mug/mL and 50000 mug/mL;
(2) PVC high molecular organic solutions with different concentrations are used as solvents to respectively prepare quinoline standard working solutions with the same concentration;
(3) Respectively transferring 10 mu L of quinoline standard working solution into a thermal desorption sample cup, volatilizing the solvent to prepare a quinoline standard product of a PVC matrix;
(4) And (3) taking a proper amount of quinoline standard substance with silanized glass wool covered with PVC matrix, and then placing the sample cup into a thermal desorption device for thermal desorption-gas chromatography-mass spectrometry analysis. The peak quinoline response values for standard working solutions of different concentrations of PVC are shown in figure 2.
The result shows that the concentration of the PVC macromolecule organic solution is in the range of 500-100000 mug/mL, the response value of the volatile quinoline increases along with the increase of the PVC concentration, and when the PVC content is more than 50000 mug/mL, the peak response value is basically unchanged, namely when the PVC concentration reaches more than 50000 mug/mL, the volatilization of the quinoline can be effectively reduced.
With the further increase of the PVC concentration, when the PVC concentration reaches 100000 mug/mL, the viscosity of the PVC macromolecule organic solution is higher, which is unfavorable for preparing the quinoline standard working solution and sampling, so that 50000 mug/mL of PVC macromolecule organic solution is selected to prepare the quinoline standard working solution required later.
Example 3 determination of quinoline content in textiles
(1) Taking a brown woven textile, wherein the fiber component is 100% cotton, shearing the brown woven textile into fragments or powder with the particle size of less than 0.5mm by using scissors, uniformly mixing, weighing 0.60mg of sheared sample to be tested, and placing the sample at the bottom of a thermal desorption sample cup;
(2) Dissolving PVC powder by tetrahydrofuran solvent to prepare PVC macromolecule organic solution with the concentration of 50000 mu g/mL; quantitatively weighing a quinoline standard substance, preparing a standard stock solution with the concentration of 1000 mug/mL by taking a PVC polymer organic solution as a solvent, and gradually diluting the stock solution into a standard working solution with the concentration of 10 mug/mL, 20 mug/mL, 50 mug/mL, 80 mug/mL and 100 mug/mL; respectively transferring 10 mu L of standard working solutions with different concentrations into a thermal desorption sample cup, volatilizing the solvent to obtain a quinoline standard product of a PVC matrix, wherein the absolute contents of quinoline in the thermal desorption sample cup are respectively as follows: 100ng, 200ng, 500ng, 800ng, 1000ng.
(3) And (3) taking a proper amount of silanized glass wool, respectively putting the silanized glass wool into the thermal desorption sample cups of the step (1) and the step (2), and then putting the sample cups of the step (1) and the step (2) into a thermal desorption device for thermal desorption-gas chromatography-mass spectrometry analysis, wherein:
the thermal desorption adopts micro-furnace type heating, the thermal desorption temperature is 260 ℃, the thermal desorption time is 6s, and the interface temperature is 300 ℃;
the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m; the carrier gas is helium; column flow 1.1mL/min; the temperature of the sample inlet is 290 ℃; split sample injection, split ratio 110:1, a step of; programming temperature: the initial temperature was 70℃for 1min and the temperature was increased to 270℃at 50℃per min for 3min.
Mass spectrometry employed EI ion source: 70eV, ion source temperature 250 ℃, gas interface temperature 270 ℃, single ion detection (SIM) mode is selected, and mass spectrum parameters are shown in Table 1.
TABLE 1 quinoline Mass Spectrometry parameters
In the embodiment, the selected ion chromatogram in the quinoline standard of the PVC matrix is shown in figure 3, and the selected monitoring ions have high sensitivity, good selectivity, less interference, wide linear range, accurate qualitative and low quantitative limit. The sample selection monitoring ion chromatogram in this example is shown in fig. 4.
The sample to be tested and the quinoline standard substance of the PVC matrix show a quinoline peak at the same retention time of 4.08 min; according to the relation between the peak areas and the absolute contents of different concentration gradient standards, linear fitting is carried out to obtain a linear equation: y=5290x+11818700 (y is peak area, x is content, in ng), the minimum detection limit is 3.52mg/kg calculated from the 3-fold signal to noise ratio. The quinoline content in the 0.60mg textile sample was calculated according to formula (1): 34ng, i.e. 57mg/kg quinoline in the test sample.
Example 4 determination of quinoline content in textiles
(1) Taking black textiles, wherein the fiber components are 100% wool, shearing the black textiles into fragments or powder with the particle size of less than 0.5mm by using scissors, uniformly mixing the fragments or the powder, weighing 0.50mg of mixed sample, and placing the mixed sample at the bottom of a thermal desorption sample cup;
(2) Dissolving with tetrahydrofuran solvent to obtain PVC polymer solution with concentration of 50000 μg/mL as solvent, and weighing quinolineStandard substance, configured as standard stock solution with concentration of 1000 mug/mL, and then diluted step by step into standard working solution with concentration of 10 mug/mL, 20 mug/mL, 50 mug/mL, 80 mug/mL and 100 mug/mL; respectively transferring 10 mu L of standard working solutions with different concentrations into a thermal desorption sample cup, volatilizing the solvent,obtainingThe absolute contents of quinoline in the thermal desorption sample cup of the quinoline standard substance of the PVC matrix are respectively as follows: 100ng, 200ng, 500ng, 800ng, 1000ng.
(3) Putting a proper amount of silanized glass wool into thermal desorption sample cups in the steps (1) and (2), and putting the sample cups into a thermal desorption device for thermal desorption-gas chromatography-mass spectrometry analysis, wherein:
the thermal desorption device adopts micro-furnace type heating, the thermal desorption temperature is 250 ℃, the thermal desorption time is 12s, and the interface temperature is 280 ℃;
the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m; the carrier gas is helium; column flow 1.2mL/min; the temperature of the sample inlet is 250 ℃; split sample injection, split ratio of 100:1, a step of; programming temperature: the initial temperature was 80℃for 1min and the temperature was raised to 280℃at 40℃per min for 2min.
Mass spectrometry employed EI ion source: 70eV, ion source temperature 260 ℃, gas interface temperature 280 ℃, single ion detection (SIM) mode was selected, and mass spectral parameters were consistent with Table 1 in example 1.
The selective ion chromatogram of the quinoline standard substance of the PVC matrix in the embodiment is shown in figure 5, wherein each spectrum peak can be separated, each spectrum peak is sharp in shape and good in symmetry; the sample selection monitoring ion chromatogram is shown in fig. 6.
Quinoline peaks appear at the same retention time of 4.11min on the sample to be tested and the quinoline standard substance of the PVC matrix, and linear fitting is carried out according to the relation between the peak areas and the absolute contents of different concentration gradient standard substances, so as to obtain a linear equation: y=5290x+11818700 (y is peak area, x is content, in ng). The quinoline content in the 0.50mg textile sample was calculated according to formula (1): 156ng, i.e. 312mg/kg.
Example 5 determination of quinoline content in textiles
(1) Taking an off-white woven textile, wherein the fiber component is 100% polyester, shearing the textile into fragments or powder with the particle size of less than 0.5mm by using scissors, uniformly mixing, weighing 1.00mg of mixed sample, and placing the mixed sample at the bottom of a thermal desorption sample cup;
(2) Dissolving with tetrahydrofuran solvent to obtain PVC polymer solution with concentration of 50000 μg/mL as solvent, weighing quinoline standard substance, preparing into standard stock solution with concentration of 1000 μg/mL, and gradually diluting into standard working solution with concentration of 10 μg/mL, 20 μg/mL, 50 μg/mL, 80 μg/mL, 100 μg/mL; respectively transferring 10 mu L of standard working solutions with different concentrations into a thermal desorption sample cup, volatilizing the solvent, and respectively obtaining the absolute contents of quinoline in the thermal desorption sample cup: 100ng, 200ng, 500ng, 800ng, 1000ng.
(3) Putting a proper amount of silanized glass wool into the thermal desorption sample cup in the step (2) for covering the sample so as to prevent the sample from drifting out of the sample cup; then placing the sample cup in the (2) into a thermal desorption device for thermal desorption-gas chromatography-mass spectrometry analysis, wherein:
the thermal desorption device adopts micro-furnace type heating, the thermal desorption temperature is 240 ℃, the thermal desorption time is 48s, and the interface temperature is 310 ℃;
the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m; the carrier gas is helium; column flow 0.8mL/min; the temperature of the sample inlet is 300 ℃; split sample injection, split ratio 140:1, a step of; programming temperature: the initial temperature was 40℃for 1min and the temperature was raised to 260℃at 50℃per min for 3min.
Mass spectrometry employed EI ion source: 70eV, ion source temperature 270 ℃, gas interface temperature 300 ℃, single ion detection (SIM) mode selected, mass spectral parameters consistent with table 1 in example 1.
The selective ion chromatogram of the quinoline standard substance of the PVC matrix is shown in figure 7, and the monitoring ion selected by the method has high sensitivity, good selectivity, less interference, wide linear range, accurate qualitative and low quantitative limit. The selection monitor ion chromatogram of the sample is shown in fig. 8.
Quinoline peaks appear at the same retention time of 4.97min on the sample to be tested and the quinoline standard substance of the PVC matrix, and a linear equation is obtained: y=5290x+11818700 (y is peak area, x is content, in ng). The quinoline content in the 1.00mg textile sample was calculated according to formula (1): 620ng, 620mg/kg.
Example 6 determination of quinoline content in textiles
(1) Taking a green woven textile, wherein the fiber component is 100% nylon, shearing the nylon into fragments or powder with the particle size of less than 0.5mm by using scissors, uniformly mixing, weighing 0.80mg of mixed sample, and placing the mixed sample at the bottom of a thermal desorption sample cup;
(2) Dissolving with tetrahydrofuran solvent to obtain PVC polymer solution with concentration of 50000 μg/mL as solvent, weighing quinoline standard substance, preparing into standard stock solution with concentration of 1000 μg/mL, and gradually diluting into standard working solution with concentration of 10 μg/mL, 20 μg/mL, 50 μg/mL, 80 μg/mL, 100 μg/mL; respectively transferring 10 mu L of standard working solutions with different concentrations into a thermal desorption sample cup, volatilizing the solvent to obtain a quinoline standard product of a PVC matrix, wherein the absolute contents of quinoline in the thermal desorption sample cup are respectively as follows: 100ng, 200ng, 500ng, 800ng, 1000ng.
(3) Putting a proper amount of silanized glass wool into thermal desorption sample cups in the steps (1) and (2), and putting the sample cups into a thermal desorption device for thermal desorption-gas chromatography-mass spectrometry analysis, wherein:
the thermal desorption device adopts micro-furnace type heating, the thermal desorption temperature is 270 ℃, the thermal desorption time is 30s, and the interface temperature is 290 ℃;
the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m; the carrier gas is helium; column flow 0.9mL/min; the temperature of the sample inlet is 280 ℃; split sample injection, split ratio 130:1, a step of; programming temperature: the initial temperature was 80℃for 1min, and the temperature was raised to 260℃at 30℃per min for 1min.
Mass spectrometry employed EI ion source: 70eV, ion source temperature 250 ℃, gas interface temperature 280 ℃, single ion detection (SIM) mode is selected, and mass spectrum parameters are shown in Table 1.
FIG. 9 shows a selective ion chromatogram of a quinoline standard of the PVC matrix of the embodiment, wherein each spectrum peak can be separated, each spectrum peak is sharp in shape and good in symmetry, and a selective monitoring ion chromatogram of a sample is shown in FIG. 10.
Quinoline peaks appear at the same retention time of 4.86min on the sample to be tested and the quinoline standard substance of the PVC matrix to obtain a linear equation: y=5290x+11818700 (y is peak area, x is content, in ng). The quinoline content in the 0.80mg textile sample was calculated according to formula (1): 315ng, 394mg/kg.
The detection method provided by the invention realizes the efficient and accurate detection of the quinoline content in the textile by a simpler and environment-friendly method.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes using the description and drawings are included in the scope of the invention.
Claims (8)
1. A rapid detection method of quinoline in textile is characterized in that thermal desorption-gas chromatography-mass spectrometry is adopted to detect quinoline, and the method comprises the following steps:
(1) Shearing a sample to be detected into fragments with the particle size of less than 0.5mm, uniformly mixing, weighing a proper amount of sample to be detected, placing the fragment at the bottom of a thermal desorption sample cup, placing a proper amount of silanized glass wool into the thermal desorption sample cup, and covering the sample;
(2) Preparing a quinoline standard substance of a PVC matrix, placing the quinoline standard substance of the PVC matrix at the bottom of a thermal desorption sample cup, and covering a proper amount of silanized glass wool on the quinoline standard substance;
(3) Respectively placing the thermal desorption sample cup filled with the sample to be detected in the step (1) and the thermal desorption sample cup filled with the quinoline standard substance of the PVC matrix in the step (2) into a thermal desorption device for detection by a thermal desorption-gas chromatography mass spectrometer;
(4) Performing qualitative and quantitative detection on quinoline according to the retention time, characteristic ions and peak response value comparison of the quinoline in the sample to be detected and the standard;
heating by a micro furnace, wherein the thermal desorption temperature is 240-300 ℃, the thermal desorption time is 6-60 s, and the interface temperature is 280-320 ℃; the gas chromatography conditions were: the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m or other capillary columns of the same type; the temperature of the sample inlet is 250-300 ℃; split-flow sample injection is adopted, and the split ratio (100-140): 1, a step of; programming temperature: the initial temperature is 40-80 ℃, kept for 0-5 min, heated to 260-330 ℃ at 30-50 ℃/min, and kept for 2-5 min.
2. The method for rapid detection of quinoline in textiles according to claim 1, wherein the mass of the sample to be detected is 0.5-1.00 mg, accurate to 0.01mg.
3. The method for rapid detection of quinoline in textiles according to claim 1, wherein the gas chromatograph-mass spectrometer conditions of the gas chromatograph-mass spectrometer are: the chromatographic column is DB-5MS,30.0m multiplied by 0.25mm multiplied by 0.25 mu m or other capillary columns of the same type; the carrier gas is high-purity helium; the flow rate of the column is 0.8-1.2 mL/min; the temperature of the sample inlet is 250-300 ℃; split-flow sample injection is adopted, and the split ratio (100-140): 1, a step of; programming temperature: the initial temperature is 40-80 ℃, kept for 0-5 min, heated to 260-330 ℃ at 30-50 ℃/min, and kept for 2-5 min.
4. The method for rapid detection of quinoline in textiles according to claim 1, wherein the mass spectrometry instrument conditions of the gas chromatograph-mass spectrometer are: mass spectrometry employed EI ion source: 70eV, ion source temperature 230-300 ℃, gas interface temperature 270-320 ℃, mass spectrum scanning is a selective ion detection (SIM) mode, and mass spectrum parameters are shown in the following table.
5. The method for rapid detection of quinoline in textiles according to claim 1, wherein the preparation method of the quinoline standard of the PVC matrix is as follows: and sucking a standard working solution of the quinoline, injecting the standard working solution into a thermal desorption sample cup, and volatilizing the solvent to obtain the quinoline standard product of the PVC matrix.
6. The method for rapid detection of quinoline in a textile according to claim 5, wherein the preparation method of the standard working solution comprises the steps of: quantitatively weighing a quinoline standard substance, preparing a standard stock solution with the concentration of 1000-2000 mug/mL by taking a PVC polymer organic solution as a solvent, and diluting the standard stock solution into a standard working solution with the concentration of 0.5-100 mug/mL.
7. The method for rapid detection of quinoline in textile according to claim 6, wherein the PVC polymer organic solution is prepared by dissolving PVC powder with tetrahydrofuran to prepare the PVC polymer organic solution with the concentration of 50000-100000 mug/mL.
8. The method for rapid detection of quinoline in textiles according to claim 1, wherein the quinoline content is calculated according to the following formula:
X＝A i ×C is /(A is ×m) (1)
wherein: x is the content of quinoline in the sample, and the unit is micrograms per gram (mug/g);
C is the unit is nanograms (ng) of the absolute mass of quinoline in a standard;
A i peak response value of quinoline in the sample;
A is peak response value of quinoline in standard;
m is the sample weight in milligrams (mg).
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