CN114527215B - Method for detecting environmental endocrine disruptors for solid waste - Google Patents
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Classifications
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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
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- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid 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
- G01N2030/062—Preparation extracting sample from raw material
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a detection method of environmental endocrine disruptors for solid waste, which comprises the following steps: configuring a first sample and a second sample; setting a sample extraction parameter, a sample purification parameter and a sample measurement parameter; collecting first solid waste; carrying out sample extraction operation to be purified based on the first sample, the sample extraction parameters and the first solid waste to obtain a sample to be purified; performing sample purification operation based on the first sample, the sample purification parameters and the sample to be purified to obtain a sample to be measured; performing a chromatographic analysis operation based on the second sample, the sample measurement parameter and the sample to be measured; the invention can effectively separate and detect bisphenol compounds and alkylphenol compounds with different structures without derivatization, and the detection method has extremely high selectivity, reproducibility and popularity, low use cost and operation difficulty, makes up the defects of the prior art and has extremely high application value.
Description
Technical Field
The invention relates to the technical field of solid detection, in particular to a detection method of an environmental endocrine disrupting material for solid waste.
Background
At present, bisphenol and alkylphenol compounds are typical environmental endocrine disruptors, and have extremely strong environmental estrogenic activity, can continuously interfere with endocrine systems of living bodies in the environment, influence reproduction and development of the living bodies, can generate extremely great potential harm to human ecological environment due to the carry-over of the compounds in the environment, and have the characteristics of toxicity, bioaccumulation, persistent pollution and the like;
on the basis of the background described above, there are therefore partial detection methods for bisphenols and alkylphenols in the prior art, the main methods including gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS); because of the higher boiling points of bisphenols and alkylphenols, derivatization is often required when analysis is performed by gas chromatography-mass spectrometry (GC-MS), thus complicating the operation process and reducing the accuracy of detection; when the liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) is adopted for analysis, although the liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) can achieve a better detection effect, the use of the device is expensive, the detection cost is high, and the popularity and the practicability are low; furthermore, the method is commonly used for food containers, water quality and soil, and has no related detection means for solid wastes;
based on the above background, in order to prevent the bisphenol and alkylphenol compounds from remaining in the environment to cause potential hazard to human ecological environment, it is necessary to develop a method for detecting bisphenol and alkylphenol compounds which has high popularity, low operation difficulty and can be used for solid waste, thereby improving the detection diversity.
Disclosure of Invention
The main purpose of the invention is to develop a bisphenol and alkylphenol compound detection method which has high popularity and low operation difficulty and can be used for solid waste.
In order to achieve the above purpose, the invention adopts a technical scheme that: the method for detecting the environmental endocrine disruptors for the solid waste comprises the following steps:
an initial configuration step: configuring a first sample and a second sample; setting a sample extraction parameter, a sample purification parameter and a sample measurement parameter; collecting first solid waste;
sample extraction: carrying out sample extraction operation to be purified based on the first sample, the sample extraction parameters and the first solid waste to obtain a sample to be purified;
sample purification: performing sample purification operation based on the first sample, the sample purification parameters and the sample to be purified to obtain a sample to be measured;
chromatographic analysis: and performing chromatographic analysis operation based on the second sample, the sample measurement parameters and the sample to be measured.
As an improvement, the sample extraction parameters include: a first proportioning parameter, a first ultrasonic extraction parameter and a first centrifugal processing parameter; the first sample includes: a first compound, a first mixed solvent, and a first replacement solvent;
the sample extraction operation to be purified comprises:
setting the repetition number, and performing ultrasonic-assisted extraction processing based on the first proportioning parameter, the first ultrasonic extraction parameter, the first centrifugal processing parameter, the first compound, the first mixed solvent, the first solid waste and the repetition number to obtain a plurality of first supernatants corresponding to the repetition number;
combining a plurality of the first supernatants to obtain a combined supernatant; concentrating the combined supernatant to near dryness to obtain a first primary concentrate; and concentrating the first primary concentrated solution by adopting the first replacement solvent as the solvent of the first primary concentrated solution to obtain the sample to be purified.
As an improved solution, the first proportioning parameter includes: a first grammage, a second grammage, and a first dose; the first ultrasound extraction parameters include: a first extraction temperature and a first extraction duration; the first centrifugation parameters include: a first rotational speed and a first centrifugation duration;
the step of ultrasound-assisted extraction processing further comprises: executing a first extraction step according to the repetition number;
the first extraction step includes:
performing first mixing treatment according to the first solid waste with the first gram weight, the first compound with the second gram weight and the first mixed solvent with the first dose to obtain a first mixture to be extracted;
performing ultrasonic extraction on the first mixture to be extracted according to the first extraction temperature and the first extraction duration to obtain an extraction product; centrifuging the extracted product according to the first rotating speed and the first centrifuging time length to obtain a centrifuged product; taking the supernatant of the centrifugal product as the first supernatant.
As an improvement, the first sample further includes: a second compound, a third compound, and a fourth compound;
the sample purification parameters include: a second dose, a third dose, a fourth dose, a fifth dose, a first duration of vacuum treatment, a first concentration parameter, and a second concentration parameter;
the sample purification operation includes:
activating a solid phase extraction column with the second dose of the second compound and the third dose of the third compound to obtain a first extraction column; transferring the sample to be purified into the first extraction column to obtain a second extraction column; washing the carrying container of the sample to be purified by adopting the third compound with the fourth dosage to obtain a first washing liquid; transferring the first washing liquid into the second extraction column to obtain a third extraction column;
and carrying out an extraction purification step based on the second compound, the third compound, the fourth compound, the third dose, the fourth dose, the fifth dose, the first vacuum treatment duration, the first concentration parameter, the second concentration parameter and the third extraction column to obtain the sample to be determined.
As an improvement, the extraction purification step includes:
leaching the third extraction column by adopting the third dose of the third compound, and carrying out vacuum drying treatment on the third extraction column according to the first vacuum treatment duration after leaching to obtain a fourth extraction column;
eluting the fourth extraction column by adopting the fifth dose of the second compound to obtain a first eluent;
concentrating the first eluent according to the first concentration parameter to obtain a first concentrated eluent; adding the fourth compound in the fourth dose to the first concentrated eluent to obtain a second concentrated eluent; concentrating the second concentrated eluent according to the second concentration parameter to obtain a third concentrated eluent;
and adopting the fourth compound as a solvent of the third concentrated eluent to fix the volume of the third concentrated eluent to obtain the sample to be measured.
As a modification, the second sample includes a first mixed standard solution;
the sample measurement parameters include: a first chromatographic condition parameter, a first concentration step parameter, and a first analysis order;
the chromatographic analysis operation includes:
configuring a plurality of first to-be-measured liquids matched with the first concentration step parameters based on the to-be-measured sample and the first mixed standard liquid;
based on the first chromatographic condition parameters, sequentially carrying out chromatographic analysis on a plurality of first liquids to be detected according to the first analysis sequence to obtain analysis results;
drawing a result graph by taking the first concentration step parameter as a first coordinate and the analysis result as a second coordinate; and analyzing the interfering substance measurement data based on the result graph.
As an improvement, the configuring step of the first sample further includes:
setting a first purity, and configuring the second, third, and fourth compounds according to the first purity;
setting a second purity, a first baking temperature and a first baking time period, configuring a first compound to be treated according to the second purity, and baking the first compound to be treated according to the first baking temperature and the first baking time period to obtain the first compound.
As an improvement, the configuring step of the second sample further includes:
preparing a standard solution proportioning compound, and carrying out dissolution and dilution treatment on the standard solution proportioning compound based on the fourth compound to obtain the first mixed standard solution.
As an improvement, the first chromatographic condition parameters include: the method comprises the steps of first chromatographic column parameters, first mobile phase parameters, first column temperature, first sample injection amount parameters, first flow rate and first ultraviolet detection wavelength parameters.
As an improvement, the sample extraction step and the sample purification step are performed based on the interaction between a numerical control ultrasonic cleaner, a high-speed bench centrifuge, a high-throughput vacuum parallel concentrator, and a solid-phase extraction device;
the chromatographic step is based on the interaction between a high performance liquid chromatograph and an ultraviolet detector.
The beneficial effects of the invention are as follows: the detection method of the environmental endocrine disruptors for solid waste can realize effective separation and detection of bisphenol and alkylphenol compounds with different structures under the condition of no need of derivation, and has extremely high selectivity, reproducibility and popularity, low use cost and operation difficulty, makes up the defects of the prior art, and has extremely high application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart showing a method for detecting an environmental endocrine disrupter for solid waste according to example 1 of the present invention;
FIG. 2 is a schematic flow chart showing a method for detecting an environmental endocrine disrupter for solid waste according to example 1 of the present invention;
fig. 3 is a schematic view showing the effect of the results of the graph of embodiment 1 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present invention.
In the description of the present invention, it should be noted that the described embodiments of the present invention are some, but not all embodiments of the present invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the terms "first," second, "" third, "" fourth, "and fifth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, unless explicitly specified and defined otherwise, the terms "sample", "sample extraction parameter", "sample purification parameter", "sample measurement parameter", "solid waste", "sample to be purified sample extraction operation", "sample to be purified", "sample purification operation", "sample to be measured", "chromatography analysis operation", "proportioning parameter", "ultrasonic extraction parameter", "centrifugation parameter", "mixed solvent", "displacement solvent", "ultrasonic assisted extraction process", "primary concentrate", "mixture to be extracted", "extraction product", "centrifugation product", "washing process", "vacuum-drying process", "elution process", "concentrated eluent", "chromatographic condition parameter", "concentration step parameter", "result graph", "interfering substance measurement data", "baking process", "dissolution dilution process" are to be understood in a broad sense. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In describing the present invention, it should be noted that: APEOs (Alkylphenol ethoxylates) is a nonionic surfactant alkylphenol ethoxylate; UP water (Ultrapure water) is Ultrapure water.
Example 1
The embodiment provides a detection method of environmental endocrine disruptors for solid waste, as shown in fig. 1-3, comprising the following steps:
s100, an initial configuration step, specifically comprising the following steps:
s110, configuring a first sample and a second sample; setting a sample extraction parameter, a sample purification parameter and a sample measurement parameter; collecting first solid waste;
specifically, in the present embodiment, the object to be detected is the first solid waste, which includes, but is not limited to, ash, sludge, and the like in the present embodiment; a sample of the first solid waste is collected and prepared in accordance with the relevant specifications of the technical Specification for sampling and preparing Industrial solid waste (HJ/T20-1998); correspondingly, the environmental endocrine disruptors are in this embodiment: bisphenols and alkylphenols; accordingly, bisphenol compounds are commonly used in food containers, medical devices, and building materials, which are often exposed to the living environment of humans; alkylphenol compounds are fine chemical raw materials, are widely used in industrial production such as oil refining, papermaking and the like, and can be converted into environmental media along with materials such as coating, detergent, textile and the like as degradation products of APEOs; the carry-over of the two compounds in the environment will generate great potential hazard to human ecological environment, most detection methods in the prior art are concentrated on food containers, water quality and soil, and no related methods for detecting bisphenol and alkylphenol compounds in solid waste exist, so the method is designed and mainly used for detecting the compounds in the solid waste, the defects of the prior art are overcome, the method does not need to be derived, and bisphenol and alkylphenol compounds with different structures can be effectively separated and detected through related samples configured in the method, set related parameters and independently developed detection flows, the detection difficulty is low, and the use instrument is simple and has strong popularity;
specifically, the first sample includes: a first compound, a first mixed solvent, a first replacement solvent, a second compound, a third compound, and a fourth compound; the second sample comprises a first mixed standard solution;
specifically, the configuring step of the first sample further includes: setting a first purity, and configuring the second, third, and fourth compounds according to the first purity; in this example, the first purity is chromatographic purity, the second compound is dichloromethane, the third compound is n-hexane, and the fourth compound is acetonitrile; in this example, the first sample also included acetone, which was likewise chromatographically pure; the acetone and the dichloromethane are used for preparing an extraction solvent, namely the first mixed solvent, namely the dichloromethane-acetone mixed solvent with the volume ratio of 1:1; in this embodiment, the first replacement solvent is the third compound;
specifically, setting a second purity, a first baking temperature and a first baking time period, configuring a first compound to be treated according to the second purity, and baking the first compound to be treated according to the first baking temperature and the first baking time period to obtain the first compound; in this example, the second purity is anhydrous Na 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The second purity is superior purity, the first baking temperature is 400 ℃, the first baking time is 4 hours, and correspondingly, the first compound is anhydrous Na baked in a muffle furnace at 400 ℃ for 4 hours 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the In all the processes of the method, all the water is UP water;
specifically, in this embodiment, the configuring step of the second sample further includes: preparing a standard solution proportioning compound, and carrying out dissolution and dilution treatment on the standard solution proportioning compound based on the fourth compound to obtain the first mixed standard solution; in this embodiment, the standard solution mixture ratio compound is a mixed standard stock solution of 11 bisphenol and alkylphenol compounds, and in this embodiment, the standard solution mixture ratio compound includes: bisphenol F, bisphenol A, 4-tert-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-tert-octylphenol, 4-n-heptylphenol, nonylphenol, 4-n-octylphenol and 4-n-nonylphenol standard having a specification of 50 mg/L; the dissolving and diluting treatment is as follows: dissolving the compound in the standard solution proportion by using the acetonitrile, diluting and preparing, and preserving the finally obtained mixed product at the temperature of 4 ℃ for the subsequent analysis step;
correspondingly, in this embodiment, the sample extraction parameter, the sample purification parameter and the sample measurement parameter are flow reference parameters corresponding to each step respectively, and the parameter setting can be adaptively adjusted according to different specifications of the detected object or different specifications of the sample and the sample.
S200, a sample extraction step, specifically comprising the following steps:
s210, carrying out sample extraction operation to be purified based on the first sample, the sample extraction parameters and the first solid waste to obtain a sample to be purified; in this embodiment, based on the present sample extraction step, bisphenol compounds and alkylphenol compounds with different structures can be effectively separated, and the specific steps are as follows:
specifically, the sample extraction parameters include: a first proportioning parameter, a first ultrasonic extraction parameter and a first centrifugal processing parameter; the first proportioning parameters comprise: a first grammage, a second grammage, and a first dose; in this example, the first gram weight is 5.0g, the second gram weight is 1.0g, and the first dose is 20ml; when the first gram weight changes, the second gram weight and the first dose are subjected to adaptive adjustment; the first ultrasound extraction parameters include: a first extraction temperature and a first extraction duration; in this example, the first extraction temperature was 30 ℃, and the first extraction time period was 20 minutes; the first centrifugation parameters include: a first rotational speed and a first centrifugation duration, in this embodiment, the first rotational speed is 5000 r/min, and the first centrifugation duration is 5 min;
specifically, the sample extraction operation to be purified includes: setting the repetition number, and performing ultrasonic-assisted extraction processing based on the first proportioning parameter, the first ultrasonic extraction parameter, the first centrifugal processing parameter, the first compound, the first mixed solvent, the first solid waste and the repetition number to obtain a plurality of first supernatants corresponding to the repetition number; in this example, the number of repetitions was 2, to obtain two supernatants; combining the two first supernatants to obtain a combined supernatant; concentrating the combined supernatant to near dryness to obtain a first primary concentrate; and introducing the first primary concentrated solution into a concentration bottle, and adopting the first replacement solvent as the solvent of the first primary concentrated solution, namely replacing the solvent with n-hexane and concentrating the first primary concentrated solution again, wherein in the embodiment, the concentration is to 1ml, so as to obtain the sample to be purified.
Specifically, the step of ultrasonic-assisted extraction processing further includes: executing a first extraction step according to the repetition number;
specifically, the first extraction step includes: performing first mixing treatment according to the first solid waste with the first gram weight, the first compound with the second gram weight and the first mixed solvent with the first dose to obtain a first mixture to be extracted; the specific first mixing treatment is that 5.0g of first solid waste is placed into a 50ml centrifuge tube, then 1.0g of anhydrous Na2SO4 is added, and then 20ml of dichloromethane-acetone mixed solvent is added, SO that the first mixture to be extracted is obtained; performing ultrasonic extraction on the first mixture to be extracted according to the first extraction temperature and the first extraction duration to obtain an extraction product; centrifuging the extracted product according to the first rotating speed and the first centrifuging time length to obtain a centrifuged product; taking the supernatant of the centrifugation product as the first supernatant; specifically, ultrasonic extraction is that the first mixture to be extracted is subjected to ultrasonic extraction for 20 minutes at 30 ℃; centrifuging at 5000 r/min for 5 min; in this example, the ultrasonic extraction was done by a KQ-500DE type numerical control ultrasonic cleaner and the centrifugation was done by a TGL-10B type high speed bench centrifuge; the concentration treatment in the method is completed by an MPE type high-flux vacuum parallel concentrator; in this embodiment, the design of the above extraction process and the preset extraction solvent, extraction temperature, extraction time and extraction times are critical, and based on the above parameters and logic, the accurate and effective extraction of the sample can be finally satisfied, and the subsequent analysis precision is improved.
S300, a sample purifying step, specifically comprising the following steps:
s310, performing sample purification operation based on the first sample, the sample purification parameters and the sample to be purified to obtain a sample to be measured;
specifically, the sample purification parameters include: a second dose, a third dose, a fourth dose, a fifth dose, a first duration of vacuum treatment, a first concentration parameter, and a second concentration parameter; in this example, the second dose was 4ml, the third dose was 10ml, the fourth dose was 3ml, the fifth dose was 6ml, the first vacuum treatment duration was 15 minutes, the first concentration parameter was 1ml, and the second concentration parameter was 1ml or less;
specifically, the sample purification operation includes: activating a solid phase extraction column with the second dose of the second compound and the third dose of the third compound to obtain a first extraction column; in this example, for 4ml of dichloromethane and 10ml of n-hexane, the solid phase extraction column was subjected to activation treatment in sequence, and the activated effluent was discarded, resulting in a first extraction column; transferring the sample to be purified into the first extraction column to obtain a second extraction column; washing the carrying container of the sample to be purified by adopting the third compound with the fourth dosage to obtain a first washing liquid; in this example, the washing treatment was performed by washing the above-mentioned concentrated bottle with 3ml of n-hexane 3 times, and the whole of the washing liquid obtained in the process was the first washing liquid; so = transferring the first wash liquid into the second extraction column to obtain a third extraction column; and carrying out an extraction purification step based on the second compound, the third compound, the fourth compound, the third dose, the fourth dose, the fifth dose, the first vacuum treatment duration, the first concentration parameter, the second concentration parameter and the third extraction column to obtain the sample to be determined.
Specifically, the extraction and purification step comprises the following steps: leaching the third extraction column by adopting the third dose of the third compound, and carrying out vacuum drying treatment on the third extraction column according to the first vacuum treatment duration after leaching to obtain a fourth extraction column; specifically, leaching the third extraction column by adopting 10ml of normal hexane, and vacuum-pumping the third extraction column for 15 minutes after leaching to obtain a fourth extraction column; eluting the fourth extraction column by adopting the fifth dose of the second compound to obtain a first eluent; specifically, 6ml of dichloromethane is adopted to elute the extraction column after vacuum pumping, and the eluent is collected and concentrated to about 1ml, namely the first eluent; concentrating the first eluent according to the first concentration parameter to obtain a first concentrated eluent; adding the fourth compound in the fourth dose to the first concentrated eluent to obtain a second concentrated eluent; concentrating the second concentrated eluent according to the second concentration parameter to obtain a third concentrated eluent; the fourth compound is used as a solvent of the third concentrated eluent to carry out constant volume on the third concentrated eluent, so as to obtain the sample to be measured; the process comprises the steps of adding 3ml of acetonitrile into concentrated eluent after concentrating the eluent, concentrating the eluent again to below 1ml, completely replacing the solvent with acetonitrile, and adopting acetonitrile to fix the volume to 1ml to obtain a sample to be measured; in this embodiment, step S300 is performed based on a Visiprep DL-type solid phase extraction device; the innovation points of the step S200 and the step S300 are that in the process, the setting of different extraction or purification parameters, the relation between different parameters and corresponding compounds and the use logic of the compounds are adopted, and in the step S300, the technical characteristics capable of realizing the technical effects of the method are mainly based on the selection of a specific solid-phase extraction column and the selection of an eluting solvent of the extraction column; correspondingly, the solid phase extraction column selects an SPE purifying small column (the parameters of the extraction column are LC-C18, 6mL/500 mg); the weighing equipment in the method can be an AUW120 type analytical balance, and has extremely strong universality.
S400, chromatographic analysis, specifically comprising the following steps:
s410, performing chromatographic analysis operation based on the second sample, the sample measurement parameters and the sample to be measured; in this embodiment, the chromatographic analysis step is used as the final measurement means, and the sample measurement parameters are mainly innovative analysis conditions;
specifically, the sample measurement parameters include: a first chromatographic condition parameter, a first concentration step parameter, and a first analysis order;
specifically, in this embodiment, the first chromatographic condition parameters include: a first chromatographic column parameter, a first mobile phase parameter, a first column temperature, a first sample injection amount parameter, a first flow rate and a first ultraviolet detection wavelength parameter; the first chromatographic column parameter is a Shim-pack GIST C18 chromatographic column (specific parameter is 250 mm*4.6 mm,5.0 mu m), the first mobile phase parameter is acetonitrile-water with the volume ratio of 70:30 is adopted as the mobile phase, the first column temperature is set to 35 ℃, the first sample injection amount parameter is 30 mu L, wherein the first flow rate is 1.0 ml/min, the first ultraviolet detection wavelength parameter is 225nm, and 225nm corresponds to the wavelength of an ultraviolet detector; correspondingly, the first concentration step parameter is a concentration specification increasing from small to large in sequence, and in the embodiment, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L increasing from small to large in sequence; correspondingly, the first analysis sequence is the sequence from low to high according to the concentration in the embodiment;
specifically, the chromatographic analysis operation includes: configuring a plurality of first to-be-measured liquids matched with the first concentration step parameters based on the to-be-measured sample and the first mixed standard liquid; specifically, a plurality of first mixed standard solutions prepared in advance in the embodiment are quantitatively extracted and placed in a sample to be measured, and the first mixed standard solutions are prepared into solvents with the concentrations of 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L respectively, namely a plurality of first to-be-measured solutions; based on the first chromatographic condition parameters, sequentially carrying out chromatographic analysis on a plurality of first liquids to be detected according to the first analysis sequence to obtain analysis results; specifically, a plurality of first to-be-measured liquids are respectively subjected to chromatographic analysis by adopting a high performance liquid chromatograph and an ultraviolet detector based on the set first chromatographic condition parameters, in the embodiment, 30ul of the first to-be-measured liquids of 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L are respectively weighed, and the peak areas obtained by analysis results are respectively subjected to sample injection analysis according to the sequence from low concentration to high concentration; finally, the first concentration step parameters, namely 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L are used as first coordinates, the analysis result is used as second coordinates, a result graph is drawn, in the embodiment, the first coordinates are horizontal coordinates, the second coordinates are vertical coordinates, when the first coordinates are vertical coordinates, the second coordinates are necessarily horizontal coordinates, and the specific result graph is shown in fig. 3; analyzing interfering substance measurement data based on the result graph; correspondingly, in fig. 3, the compounds represented by the reference numerals are as follows: 1 represents bisphenol F;2 represents bisphenol a;3 represents 4-tertbutylphenol; 4 represents 4-n-butylphenol; 5 represents 4-n-pentylphenol; 6 represents 4-n-hexylphenol; 7 represents 4-tert-octylphenol; 8 represents 4-n-heptyl phenol; 9 represents nonylphenol; 10 represents 4-n-octylphenol; 11 represents 4-n-nonylphenol.
In this embodiment, the following verification results are attached to prove the efficiency and accuracy of the method:
according to the requirements of environmental monitoring analysis method standard preparation technical guidelines (HJ 168-2020), carrying out 9 times of repeated measurement on blank standard-added samples with a scalar which is 3-5 times of the detection limit of the estimation method according to the whole program measurement step of sample analysis, calculating the detection limit of the method according to a formula LD=2.896×S, and calculating the quantitative lower limit by 4 times of the detection limit, wherein S is the standard deviation of 9 times of parallel measurement results; the results show that 11 bisphenol compounds and alkylphenol compounds have good linear relation in the concentration range of 0.1-2.0 mg/L, and the correlation coefficient R is more than 0.999; the detection limit range of the method is 4.26-8.37 mug/kg, and the detection lower limit is 17.0-33.5 mug/kg, so that the detection requirement of a solid waste sample in the environment can be met.
In summary, in the method, 11 bisphenols and alkylphenols in the solid waste can be rapidly determined with high convenience, high accuracy and high efficiency based on unique processing conditions and parameters, sample extraction steps, sample purification extraction steps and chromatographic analysis parameters, and the principle and the concept reflected by the method have extremely high expansibility and popularity, meet the detection requirements of laboratories, and improve the detection diversity.
The foregoing embodiment of the present invention has been disclosed with reference to the number of embodiments for the purpose of description only, and does not represent the advantages or disadvantages of the embodiments.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (5)
1. The method for detecting the environmental endocrine disruptors for the solid waste is characterized by comprising the following steps of:
an initial configuration step: configuring a first sample and a second sample; setting a sample extraction parameter, a sample purification parameter and a sample measurement parameter; collecting first solid waste;
sample extraction: carrying out sample extraction operation to be purified based on the first sample, the sample extraction parameters and the first solid waste to obtain a sample to be purified;
sample purification: performing sample purification operation based on the first sample, the sample purification parameters and the sample to be purified to obtain a sample to be measured;
chromatographic analysis: performing a chromatographic analysis operation based on the second sample, the sample measurement parameter and the sample to be measured;
the first sample includes: a first compound, a first mixed solvent, and a first replacement solvent; the sample extraction parameters include: a first proportioning parameter, a first ultrasonic extraction parameter and a first centrifugal processing parameter;
the sample extraction operation to be purified comprises: setting the repetition number, and performing ultrasonic-assisted extraction processing based on the first proportioning parameter, the first ultrasonic extraction parameter, the first centrifugal processing parameter, the first compound, the first mixed solvent, the first solid waste and the repetition number to obtain a plurality of first supernatants corresponding to the repetition number; combining a plurality of the first supernatants to obtain a combined supernatant; concentrating the combined supernatant to near dryness to obtain a first primary concentrate; concentrating the first preliminary concentrated solution by adopting the first replacement solvent as a solvent of the first preliminary concentrated solution to obtain the sample to be purified;
the sample extraction operation to be purified specifically comprises the following steps: performing two extraction steps, the extraction steps comprising: placing 5.0g of the first solid waste into a centrifuge tube, adding 1.0g anhydrous sodium sulfate, adding 20mL methylene dichloride-acetone mixed solvent with the volume ratio of 1:1, performing ultrasonic extraction treatment at 30 ℃ for 20 min, and performing centrifugation treatment at a rotation speed of 5000 r/min for 5min to obtain a supernatant of a product; the supernatant fluid of the two extraction steps is placed in a concentration bottle to be combined and concentrated to be near dryness; then the solvent is replaced by n-hexane and concentrated again to 1mL;
the first sample further comprises: a second compound, a third compound, and a fourth compound; the sample purification parameters include: a second dose, a third dose, a fourth dose, a fifth dose, a first duration of vacuum treatment, a first concentration parameter, and a second concentration parameter; the second compound is dichloromethane, the third compound is n-hexane, and the fourth compound is acetonitrile;
the sample purification operation includes: activating a solid phase extraction column with the second dose of the second compound and the third dose of the third compound to obtain a first extraction column; transferring the sample to be purified into the first extraction column to obtain a second extraction column; washing the carrying container of the sample to be purified by adopting the third compound with the fourth dosage to obtain a first washing liquid; transferring the first washing liquid into the second extraction column to obtain a third extraction column; performing an extraction purification step based on the second compound, the third compound, the fourth compound, the third dose, the fourth dose, the fifth dose, the first vacuum treatment duration, the first concentration parameter, the second concentration parameter and the third extraction column to obtain the sample to be determined;
the extraction and purification step comprises the following steps: leaching the third extraction column by adopting the third dose of the third compound, and carrying out vacuum drying treatment on the third extraction column according to the first vacuum treatment duration after leaching to obtain a fourth extraction column; eluting the fourth extraction column by adopting the fifth dose of the second compound to obtain a first eluent; concentrating the first eluent according to the first concentration parameter to obtain a first concentrated eluent; adding the fourth compound in the fourth dose to the first concentrated eluent to obtain a second concentrated eluent; concentrating the second concentrated eluent according to the second concentration parameter to obtain a third concentrated eluent; the fourth compound is used as a solvent of the third concentrated eluent to carry out constant volume on the third concentrated eluent, so as to obtain the sample to be measured;
the second sample comprises a first mixed standard solution;
the sample measurement parameters include: a first chromatographic condition parameter, a first concentration step parameter, and a first analysis order;
the chromatographic analysis operation includes: configuring a plurality of first to-be-measured liquids matched with the first concentration step parameters based on the to-be-measured sample and the first mixed standard liquid; based on the first chromatographic condition parameters, sequentially carrying out chromatographic analysis on a plurality of first liquids to be detected according to the first analysis sequence to obtain analysis results; drawing a result graph by taking the first concentration step parameter as a first coordinate and the analysis result as a second coordinate; analyzing interfering substance measurement data based on the result graph;
the first chromatographic condition parameters include: a first chromatographic column parameter, a first mobile phase parameter, a first column temperature, a first sample injection amount parameter, a first flow rate and a first ultraviolet detection wavelength parameter;
the first chromatographic column parameter is a Shim-pack GIST C18 chromatographic column, 5 μm,250 mm by 4.6 mm inner diameter; the first mobile phase parameter is acetonitrile-water with the volume ratio of 70:30; the first column temperature is 35 ℃, the first sample injection amount parameter is 30 mu L, the first flow rate is 1.0 ml/min, and the first ultraviolet detection wavelength parameter is 225nm.
2. The method for detecting an environmental endocrine disrupting material for solid waste as claimed in claim 1, wherein:
the first proportioning parameters comprise: a first grammage, a second grammage, and a first dose;
the first ultrasound extraction parameters include: a first extraction temperature and a first extraction duration;
the first centrifugation parameters include: a first rotational speed and a first centrifugation duration;
the step of ultrasound-assisted extraction processing further comprises: executing a first extraction step according to the repetition number;
the first extraction step includes:
performing first mixing treatment according to the first solid waste with the first gram weight, the first compound with the second gram weight and the first mixed solvent with the first dose to obtain a first mixture to be extracted;
performing ultrasonic extraction on the first mixture to be extracted according to the first extraction temperature and the first extraction duration to obtain an extraction product;
centrifuging the extracted product according to the first rotating speed and the first centrifuging time length to obtain a centrifuged product;
taking the supernatant of the centrifugal product as the first supernatant.
3. The method for detecting an environmental endocrine disrupting material for solid waste as claimed in claim 1, wherein:
the configuring step of the first sample further includes:
setting a first purity, and configuring the second compound, the third compound, and the fourth compound in accordance with the first purity;
setting a second purity, a first baking temperature and a first baking time period, configuring a first compound to be treated according to the second purity, and baking the first compound to be treated according to the first baking temperature and the first baking time period to obtain the first compound.
4. The method for detecting an environmental endocrine disrupting material for solid waste as claimed in claim 1, wherein:
the configuring step of the second sample further includes:
preparing a standard solution proportioning compound, and carrying out dissolution and dilution treatment on the standard solution proportioning compound based on the fourth compound to obtain the first mixed standard solution.
5. The method for detecting an environmental endocrine disrupting material for solid waste according to any of claims 1 to 4, wherein:
the sample extraction step and the sample purification step are performed based on the interaction between a numerical control ultrasonic cleaner, a high-speed table centrifuge, a high-throughput vacuum parallel concentrator and a solid phase extraction device;
the chromatographic step is based on the interaction between a high performance liquid chromatograph and an ultraviolet detector.
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