CN112858506A - Method for determining bisphenol endocrine disruptors in marine water body and sediments - Google Patents
Method for determining bisphenol endocrine disruptors in marine water body and sediments Download PDFInfo
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Abstract
The invention relates to a method for determining bisphenol endocrine disruptors in marine water and sediments, wherein the bisphenol endocrine disruptors comprise bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A, and the determination method comprises the following steps: (1) adding an extracting agent into a sample to be detected of the marine water body or the marine sediment for liquid-liquid extraction, and then centrifuging to obtain a supernatant; (2) and performing supercritical fluid chromatographic analysis on the supernatant to obtain a supercritical fluid chromatogram of the sample to be detected, and comparing the supercritical fluid chromatogram with a standard supercritical fluid chromatogram of a mixed standard solution containing bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A to judge the type of the bisphenol endocrine disruptors. The invention establishes an analysis method for simultaneously measuring four bisphenol endocrine disruptors of bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A in a marine sample by using a liquid-liquid extraction-supercritical fluid chromatography method, and the method is simple, convenient, rapid, sensitive and accurate and has high selectivity.
Description
Technical Field
The invention belongs to the technical field of marine water body detection, and particularly relates to a method for determining bisphenol endocrine disruptors in a marine water body and sediments.
Background
The organic component pollutants in the marine environment are various and complex, and the research, monitoring and control of the organic pollutants have important significance to a marine ecosystem. Endocrine Disruptors (EDCs) are a class of important exogenous pollutants present in marine environments, also known as environmental hormones, which interfere with the normal functioning of the endocrine system of organisms and thus affect the normal metabolism of the human body. Nowadays, social progress and scientific development make people pay more attention to marine ecological safety, so that research on various endocrine disruptors in marine environment is greatly promoted, and bisphenol compounds (BPs) are generally concerned by people as a typical endocrine disruptor. Bisphenol compounds are formed by bonding two hydroxyphenols through bridging carbon or other chemical structures, are low in cost and stable in chemical properties, and are widely used as raw material monomers in the production of epoxy resins and Polycarbonate (PC) plastics and additives of some polyvinyl chloride (PVC) plastics in industrial production due to good ductility of the bisphenol compounds. In the production and manufacturing processes of various living goods, bisphenol compounds are directly and disorderly discharged, so that industrial wastewater, urban sewage, surface rivers, ocean water and water sediments thereof are polluted greatly. The bisphenol compounds can simulate the activity of estrogen, the long-term exposure, contact or intake of the substances can reduce the fertility of human beings and have extremely adverse effect on the reproductive development of the human beings, and researches show that the bisphenol compounds can also cause malignant diseases such as breast cancer, ovarian cancer, testicular cancer and the like, and have toxicity to the kidney, the nervous system and the like. Therefore, from the viewpoint of human health and social development, it is necessary to strictly analyze and detect bisphenol compounds in marine water and sediments so as to promote the harmonious development of marine ecological environment.
A rapid, efficient and green analysis method is established, and is of great importance for detecting bisphenol endocrine disruptors in marine samples. In the existing research, the analysis methods reported for detecting bisphenol compounds include High Performance Liquid Chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), gas chromatography-mass spectrometry (GC-MS), and the like. These methods are widely used, but still have certain disadvantages. The HPLC method is mature, but the separation and detection of the bisphenol endocrine disruptors usually needs a large amount of toxic and harmful organic solvents as a mobile phase, and has potential adverse effects on the health of operators and the ecological environment; the LC-MS is connected with a mass spectrum detector, so that the method is sensitive and good in selectivity, but the instrument cost and the equipment maintenance cost of the LC-MS are higher, and the LC-MS is difficult to popularize comprehensively; the GC-MS technology generally needs a derivatization step to separate and detect the bisphenol compounds, and the derivatization process is time-consuming and labor-consuming and needs to consume a large amount of harmful solvents; furthermore, the quantitative accuracy of the analyte is often poor (potential analyte loss) when performing the derivatization step. For the detection of bisphenol endocrine disruptors, Supercritical Fluid Chromatography (SFC) can effectively overcome the above disadvantages. The supercritical fluid chromatography is a chromatographic separation technology taking supercritical carbon dioxide fluid as a mobile phase, and the supercritical carbon dioxide fluid has the advantages of both gas and liquid; on one hand, the supercritical carbon dioxide fluid has small viscosity and good diffusivity; on the other hand, the supercritical carbon dioxide fluid has a higher density and a higher dissolving power than the gas.
In addition, for complex marine samples such as seawater and marine sediments, the influence of the sample matrix is very serious, and the analysis result is greatly interfered.
Disclosure of Invention
Based on the above-mentioned disadvantages and shortcomings of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide a method for determining bisphenol endocrine disruptors in marine water and sediments which satisfies one or more of the above-mentioned needs.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for determining bisphenol endocrine disruptors in marine water and sediments, wherein the bisphenol endocrine disruptors comprise bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A, and the determination method comprises the following steps:
(1) adding an extracting agent into a sample to be detected of the marine water body or the marine sediment for liquid-liquid extraction, and then centrifuging to obtain a supernatant;
(2) and performing supercritical fluid chromatographic analysis on the supernatant to obtain a supercritical fluid chromatogram of the sample to be detected, and comparing the supercritical fluid chromatogram with a standard supercritical fluid chromatogram of a mixed standard solution containing bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A to judge the type of the bisphenol endocrine disruptors.
Preferably, in the step (1), the extractant is acetonitrile.
Preferably, in the step (1), anhydrous magnesium sulfate and sodium chloride are added during the liquid-liquid extraction.
Preferably, in the step (1), ultrasound is used for assisting in the liquid-liquid extraction process.
Preferably, in the step (2), the mobile phase used in the supercritical fluid chromatography is supercritical carbon dioxide, and the polar modifier is added.
Preferably, the polar modifier is methanol, and the volume ratio of the methanol to the supercritical carbon dioxide is 10: 90.
preferably, the conditions of the supercritical fluid chromatography include: the flow rate is 1.5-2.4 mL/min, the column temperature is 34-42 ℃, and the back pressure is 10-14 MPa.
Preferably, the conditions of the supercritical fluid chromatography include: the flow rate is 2.0mL/min, the column temperature is 36 ℃, and the back pressure is 12 MPa.
As a preferable scheme, in the step (2), after the supercritical fluid chromatogram of the sample to be detected is obtained, the mass concentration corresponding to each type of bisphenol endocrine disruptors in the sample to be detected is obtained according to a standard curve constructed by the peak area and the mass concentration of the mixed standard solution.
Preferably, the standard curve constructed by the peak area and the mass concentration of the mixed standard solution is constructed by the following steps:
methanol solutions containing bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A are prepared into standard solutions with mass concentrations of 0.10, 0.20, 0.50, 1.0, 2.0, 5.0 and 20.0mg/L respectively, quantification is carried out by an external standard method, and a standard curve is drawn by peak area to mass concentration.
Compared with the prior art, the invention has the beneficial effects that:
the invention establishes an analysis method for simultaneously determining four bisphenol endocrine disruptors, namely bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A in a marine sample by using a liquid-liquid extraction-supercritical fluid chromatography method, can detect the bisphenol endocrine disruptors in the marine sample, has the advantages of simplicity, rapidness, sensitivity, accuracy and high selectivity, and has important significance for distribution, tracking and research of the bisphenol endocrine disruptors in the marine environment.
Drawings
FIG. 1 is a bar graph of the effect of selection of extraction solvent species on extraction recovery in a liquid-liquid extraction process according to an embodiment of the present invention;
FIG. 2 is a bar graph of the effect of ultrasound assisted extraction time on extraction recovery in a liquid-liquid extraction process of an embodiment of the present invention;
FIG. 3 is a bar graph of the effect of methanol volume ratio on retention time of four bisphenol endocrine disruptors in a mobile phase in accordance with an embodiment of the present invention;
FIG. 4 is a bar graph of the effect of column temperature on the retention time of four bisphenol endocrine disruptors in accordance with an embodiment of the present invention;
FIG. 5 is a bar graph of the effect of flow rate on retention time of four bisphenol endocrine disruptors in an embodiment of the invention;
FIG. 6 is a bar graph of the effect of backpressure on the retention time of four bisphenol-type endocrine disruptors in accordance with an embodiment of the invention;
fig. 7 is a supercritical fluid chromatogram of an actual marine sample and a bisphenol compound standard solution according to an example of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following specific examples.
The method for determining the bisphenol endocrine disruptors in the marine water body and the sediments establishes a supercritical fluid chromatography method for analyzing four bisphenol endocrine disruptors including bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A in the marine water body and the sediments, firstly extracts and purifies a sample to be detected of the marine water body or the marine sediments through liquid-liquid extraction pretreatment, and then optimizes the supercritical fluid chromatography condition to realize the simultaneous separation and detection of the four bisphenol compounds, so that the method is rapid and efficient, and has important significance for the distribution, tracking and research of the endocrine disruptors in the field of marine environment.
Reagent and instrument adopted by method for determining bisphenol endocrine disruptors in marine water and sediments
The supercritical fluid chromatograph adopts a Nexera UC supercritical fluid chromatographic system under the flag of Shimadzu corporation of Japan and adopts an ultraviolet detection method; SBL-5DTS ultrasonic constant temperature cleaning machine (Ningbo Xinzhi Biotechnology GmbH); LG16B high speed centrifuge (leber, beijing); millipore silicon ultrapure water machine (Millipore corporation, USA)
Bisphenol standard: bisphenol a (purity 99.0%, BPA), bisphenol AF (purity 98.0%, BPAF), bisphenol C (98.0%, BPC), tetrabromobisphenol a (purity 98.0%, TBBPA) were purchased from alatin chemicals (china) and the chemical structure was as follows:
HPLC-pure grades of the desired organic solvents, such as methanol, acetonitrile, etc., were purchased from Tedia, Inc. (USA). Sodium chloride (analytically pure), anhydrous magnesium sulfate (analytically pure) was purchased from alatin chemicals (china). Inventive example the water used was secondary deionized water purified by a Millipore water purifier (usa). Samples of seawater and sediments in different waters were kept in a refrigerator for future use.
Preparing a methanol stock solution (200mg/L) containing 4 bisphenol compounds: accurately weighing a proper amount of bisphenol standard substances, adding a proper amount of methanol until the standard substances are completely dissolved, transferring the standard substances into a 100mL volumetric flask, metering the volume to the scale with the methanol, preparing 200mg/L standard stock solution, and storing the standard stock solution at a low temperature for later use after ultrasonic treatment.
Preparing a mixed standard working solution containing 4 bisphenols: diluting the standard stock solution with methanol step by step to obtain mixed standard working solutions with different concentrations, storing at low temperature, and preparing for use.
The specific process of the method for determining bisphenol endocrine disruptors in the marine water body and sediments provided by the embodiment of the invention comprises the following steps:
(1) sample pretreatment
In the embodiment of the invention, the extraction and purification of the ocean sample are mainly completed by a liquid-liquid extraction method, and in the liquid-liquid extraction process, the selection of the type of the extraction solvent and the optimization of the ultrasonic extraction time are of great importance to the influence of the final extraction effect.
In the embodiment of the invention, the extraction effects of four extraction solvents, namely methanol, ethanol, acetonitrile and acetone, are respectively studied, and the recovery rates of the four extraction solvents for four bisphenol substances, namely BPA, BPC, BPAF and the like are shown in FIG. 1, wherein acetonitrile, acetone, methanol and ethanol are sequentially arranged in each row from left to right. In the extraction process of the embodiment of the invention, 1.0g of anhydrous magnesium sulfate and 1.0g of sodium chloride are added to generate salting-out effect to promote the distribution of bisphenol substances in two phases, and when acetonitrile is selected as an extraction phase solvent, the extraction efficiency of the bisphenol target substances in an actual sample is highest, so that the acetonitrile is selected as an optimal extraction solvent. In addition, the liquid-liquid extraction process is carried out under the assistance of ultrasound, and the periodic sound wave frequency of the ultrasound can accelerate the mass transfer process of molecules, shorten the extraction time and improve the extraction efficiency. The embodiment of the invention researches the extraction effect of acetonitrile on a target object in an ultrasonic extraction time range of 2-20 min, and the result is shown in figure 2, wherein each column sequentially comprises 2min, 5min, 10min, 15min and 20min from left to right, and the result shows that when the extraction time reaches 5min, the extraction recovery rate of 4 bisphenols is better, so that 5min of ultrasonic-assisted extraction time is selected.
The embodiment of the invention selects the combination of anhydrous magnesium sulfate and sodium chloride for the following reasons:
1) the anhydrous magnesium sulfate and the sodium chloride have water absorption, and can effectively separate and remove part of water in the acetonitrile extraction process.
2) In the extraction process, the salting-out action of the anhydrous magnesium sulfate and the sodium chloride increases the salt content of the water phase and also increases the density of the water phase, so that the target compound has a higher distribution coefficient between the salt-containing water phase and the acetonitrile phase, and a more thorough separation effect is achieved.
3) The water phase containing anhydrous magnesium sulfate and sodium chloride has polarity obviously higher than that of acetonitrile phase, so that polar impurities in the sample solution can be effectively extracted to achieve the purification effect.
Through comparison experiments, it can be found that a) anhydrous magnesium sulfate is respectively adopted; b) sodium chloride; c) anhydrous magnesium sulfate + sodium chloride; d) the method is characterized by comprising four experimental conditions without salt, wherein the extraction effect of the target substance is obviously superior to that of the other three conditions by adding anhydrous magnesium sulfate and sodium chloride.
Accurately measuring 5.0mL of the marine water sample by using a pipette gun, adding 5mL of acetonitrile, uniformly mixing, adding 1.0g of anhydrous magnesium sulfate and 1.0g of sodium chloride into the solution, carrying out ultrasonic-assisted extraction for 5min, centrifuging at 10000rpm for 5min, transferring the supernatant into an automatic sample injection sample bottle, and carrying out quantitative external standard method after SFC sample injection analysis.
If the sample is a marine sediment sample, 5.0g of the sample is weighed by using a balance, and the operation process is the same as the above.
(2) Supercritical chromatographic analysis conditions
The embodiment of the invention adopts a Nexera UC SFC system to carry out the analysis of the supercritical fluid chromatography-ultraviolet detector method. The system consists of a supercritical fluid delivery pump (LD-30ADSF), a modifier delivery pump (LC-20ADXR), a degassing unit (DGU-20A5R), an autosampler (SIL-30A), a column incubator (CTO-20AC), a back pressure regulator (SFC-30A) and a system controller (CBM-20A). The bisphenols were separated by WodaCract ODS-2 column (5 μm, 4.6 mm. times.250 mm, Shimadzu, Japan) with supercritical CO as the mobile phase2+10％(v/v)CH3Performing isocratic elution on OH, wherein the total flow rate is 2.0mL/min, the column temperature is 36 ℃, the back pressure is 12MPa, and the detection wavelength is 230 nm. To prevent column saturation, the sample size was 5 μ L.
According to the embodiment of the invention, the bisphenol endocrine disruptors are separated by a supercritical fluid chromatography method, and the separation conditions of the supercritical fluid chromatography are optimized. Bisphenol compounds are separated on a supercritical fluid chromatogram through a Wonda Cract ODS-2 chromatographic stationary phase, and when single nonpolar supercritical carbon dioxide is used as a mobile phase, the elution capacity of the bisphenol compounds is weak, so that the elution effect of the mobile phase is enhanced by adding a certain proportion of polar modifier, and meanwhile, in order to obtain the best separation effect of the bisphenol compounds on the supercritical fluid chromatogram, the supercritical fluid chromatogram parameters such as column temperature, flow rate, back pressure and the like are optimized. By investigating the influence of the proportion of the polar modifier and parameters such as column temperature, flow rate, back pressure and the like on the separation effect of the bisphenol compound, the supercritical carbon dioxide/methanol is obtained by mixing 90 parts of the bisphenol compound under the conditions of the flow rate of 2.0mL/min, the column temperature of 36 ℃ and the back pressure of 12 MPa: the four bisphenol compounds obtain the optimal chromatographic peak and response value when the mobile phase is 10 (v/v).
The supercritical carbon dioxide is of a nonpolar structure, has strong hydrophobicity, is suitable for eluting nonpolar compounds, is difficult to directly separate bisphenol analogues with polarity, and therefore, a small amount of polarity modifier is required to be added to enhance the polarity of a mobile phase. In the embodiment of the invention, methanol is used as a polar modifier, the influence of different flow matching ratios on the separation effect is considered, when the volume ratio of the methanol is between 8% and 10%, the retention time of four bisphenol endocrine disrupters is shown in figure 3, so that the elution capacity of the flow relative to the four bisphenol compounds is gradually enhanced along with the increase of the methanol ratio, the separation degree and the chromatographic peak shape are comprehensively considered, and finally methanol/carbon dioxide (10/90, v/v) is selected as a mobile phase. Wherein, compared with polar modifiers such as ethanol, isopropanol, acetonitrile and the like, methanol can effectively separate bisphenol compounds, and the other three types are not feasible. The non-covalent bond effect of the methanol and the bisphenol in the mobile phase and the hydrogen bond effect between the methanol and the oxygen-containing silane bond of the stationary phase in the mobile phase are considered to generate a competition relationship with the bisphenol, so that the bisphenol is orderly eluted from the stationary phase.
The embodiment of the invention optimizes the chromatographic parameters of the supercritical fluid such as column temperature, flow velocity, back pressure and the like besides the influence on the stationary phase and the mobile phase. In general, changes in column temperature, flow rate and back pressure change the density of the mobile phase, which in turn affects the solvating power and elution power of the flow phase relative to the target components, and their effects on the separation of bisphenols are shown in fig. 4, fig. 5 and fig. 6, respectively. As shown in fig. 4, in the separation of 4 bisphenols, the column temperature increase prolongs the separation time, but this effect is not linear, and when the column temperature is higher than 36 ℃, the effect of the flow on the elution ability of the target compound gradually decreases. As the flow rate of the mobile phase increases, the density and elution ability of the mobile phase become greater, and the retention time of the target on the stationary phase is shortened, as shown in fig. 5. As shown in FIG. 6, the elution time of the 4 bisphenol analogs was gradually shortened as the back pressure of the system was increased. The separation degree and the separation time of the bisphenol compounds are comprehensively considered, 36 ℃ is finally selected as the column temperature in the experiment, 2.0mL/min is selected as the flow rate, 12MPa is selected as the back pressure, and the rapid and complete separation of the bisphenol compounds within 5min is realized.
A series of mixed standard solutions with mass concentrations of 0.10, 0.20, 0.50, 1.0, 2.0, 5.0 and 20.0mg/L are prepared from methanol solutions of 4 bisphenol compounds, quantification is carried out by an external standard method, a standard curve is drawn by peak area (Y) to mass concentration (X, mg/L), and results such as linear range, linear correlation coefficient, detection limit and reproducibility are shown in Table 1. As can be seen from Table 1, the 4 bisphenol compounds have good linearity in the linear range, the linear correlation coefficient is not lower than 0.9989, the detection limit is between 0.03 and 0.06mg/L, and the method has good reproducibility (RSD is less than or equal to 10.3%).
TABLE 1 Linearity, correlation coefficient, detection limit and quantitation limit for four bisphenol targets (n. 5)
(3) Analysis of actual samples
In the embodiment of the invention, the marine water bodies and marine sediments in three sea areas are selected as actual samples for investigation, the samples are treated according to the liquid-liquid extraction method in the step (1), and then the samples are measured according to the supercritical fluid chromatographic conditions in the step (2), and the results show that bisphenol A can be detected in the seawater samples and the sediment samples in the sea area 1, wherein the contents of bisphenol A are 0.086 mu g/mL and 0.095 mu g/mL respectively, but bisphenol AF, bisphenol C and tetrabromobisphenol A are not detected; four bisphenol compounds in the seawater sample and the sediment sample in the sea area 2 are not detected; the seawater sample in Hai 3 was able to detect bisphenol A at a level of 0.102. mu.g/mL, but none of the four bisphenols were detected in the sediment sample. Wherein the chromatogram of the sediment sample of sea area 1 is shown in FIG. 7, and 4 bisphenol endocrine disruptors can be effectively separated and analyzed within 5min by supercritical fluid chromatography.
(4) Method recovery and precision
The embodiment of the invention inspects the recovery rate of the measuring method, and comprises the following specific operations: and (3) carrying out standard addition recovery rate experiments of three concentration levels of 0.10mg/L, 0.20mg/L and 0.50mg/L on an empty real sample, measuring each concentration level in parallel for 3 times, processing the standard addition sample according to the liquid-liquid extraction method in the step (1), then measuring according to the supercritical fluid chromatographic condition in the step (2), calculating the recovery rate of the method, and obtaining the result shown in Table 2, wherein the standard addition recovery rate of the method is 85.7-112.0%.
Table 2 recovery of four bisphenols in a blank sample of actual seawater (n ═ 3)
In addition, a comparative experiment proves that the anhydrous magnesium sulfate and the sodium chloride are added in batches and equivalently in the extraction process, as shown in table 3, wherein the extraction effect of adding in batches and equivalently is better than that of adding in one time, adding in batches and equivalently, adding in four times and equivalently, adding in five times and equivalently and the like; the accuracy of the corresponding mass concentration of each type of bisphenol endocrine disruptors in the finally obtained sample to be detected is higher.
TABLE 3 Effect of batchwise addition of anhydrous magnesium sulfate and sodium chloride on spiking recovery and reproducibility
| Mode of addition | Recovery rate of added standard | Repeatability of |
| Adding into one batch | 100.3％ | 2.9％ |
| Adding in two batches | 97.9％ | 2.4％ |
| Adding in three batches | 102.2％ | 4.1％ |
| Adding in four batches | 98.5％ | 3.5％ |
| Adding in five batches | 99.0％ | 5.9％ |
Therefore, the invention establishes an analysis method for simultaneously measuring four bisphenol endocrine disruptors, namely bisphenol AF, bisphenol A, bisphenol C and tetrabromobisphenol A, in marine water and sediments by using a supercritical fluid chromatography, the four bisphenol compounds have good linearity in a linear concentration range, the linear correlation coefficients of the four bisphenol compounds are all larger than 0.9989, the detection limit of the method is 0.03-0.06 mg/L, the recovery rate of the measuring method is between 85.7-112.0%, and the method has good reproducibility. The determination method provided by the invention realizes simultaneous and rapid detection of common bisphenol endocrine disruptors in marine water and sediments, has the characteristics of good selectivity, high precision, high recovery rate, rapid and efficient method and the like, and can be widely applied to monitoring, tracking, risk research and evaluation of bisphenol endocrine disruptors in marine environment and other works.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. A method for measuring bisphenol endocrine disruptors in marine water and sediments, wherein the bisphenol endocrine disruptors comprise bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A, and the method comprises the following steps:
(1) adding an extracting agent into a sample to be detected of the marine water body or the marine sediment for liquid-liquid extraction, and then centrifuging to obtain a supernatant;
(2) and performing supercritical fluid chromatographic analysis on the supernatant to obtain a supercritical fluid chromatogram of the sample to be detected, and comparing the supercritical fluid chromatogram with a standard supercritical fluid chromatogram of a mixed standard solution containing bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A to judge the type of the bisphenol endocrine disruptors.
2. The method according to claim 1, wherein the extractant in step (1) is acetonitrile.
3. The method for determining bisphenol endocrine disruptors in marine water and sediments according to claim 1, wherein anhydrous magnesium sulfate and sodium chloride are added during the liquid-liquid extraction in step (1).
4. The method according to claim 1, wherein in step (1), the liquid-liquid extraction process is assisted by ultrasound.
5. The method according to claim 1, wherein in the step (2), the mobile phase used in the supercritical fluid chromatography is supercritical carbon dioxide, and a polar modifier is added.
6. The method according to claim 5, wherein the polar modifier is methanol, and the volume ratio of methanol to supercritical carbon dioxide is 10: 90.
7. the method according to claim 1, 5 or 6, wherein the conditions of the supercritical fluid chromatography comprise: the flow rate is 1.5-2.4 mL/min, the column temperature is 34-42 ℃, and the back pressure is 10-14 MPa.
8. The method according to claim 7, wherein the conditions of the supercritical fluid chromatography comprise: the flow rate is 2.0mL/min, the column temperature is 36 ℃, and the back pressure is 12 MPa.
9. The method according to any one of claims 1 to 6, wherein in the step (2), after the supercritical fluid chromatogram of the sample to be detected is obtained, the mass concentration corresponding to each type of bisphenol endocrine disruptors in the sample to be detected is obtained according to a standard curve constructed by peak area and mass concentration of the mixed standard solution.
10. The method according to claim 9, wherein the standard curve of peak area and mass concentration of the mixed standard solution is constructed by the following steps:
methanol solutions containing bisphenol A, bisphenol AF, bisphenol C and tetrabromobisphenol A are prepared into standard solutions with mass concentrations of 0.10, 0.20, 0.50, 1.0, 2.0, 5.0 and 20.0mg/L respectively, quantification is carried out by an external standard method, and a standard curve is drawn by peak area to mass concentration.
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