Method for simultaneously detecting polychloroprene and polychlorobenzene in biological sample

Abstract

The invention discloses a method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample, which comprises the following steps: extracting the biological sample through ultrasonic extraction, replacing the existing rotary evaporation concentration with rapid evaporation concentration, and combining dynamic multi-reaction monitoring of a gas chromatograph-triple quadrupole mass spectrometer to detect the polychloroprene and polychlorobenzene in the biological sample. Synchronous extraction, impurity removal, purification and quantitative and qualitative analysis of 9 polychlorobutadiene and 11 polychlorobenzene in a biological sample can be realized, and the detection efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental analytical chemistry, and particularly to a method for simultaneously detecting polychloroprene and polychlorobenzene in biological samples. Background Art

[0002] Polychloroprene and polychlorobenzene are persistent organic pollutants widely present in the environment, with persistence, bioaccumulation, long-distance migration, and high toxicity. They can pose risks to human health through exposure routes such as ingestion through the digestive tract, inhalation through the respiratory tract, and skin contact. Therefore, detecting the contents of polychloroprene and polychlorobenzene is of great significance for the risk assessment and control of these two types of compounds.

[0003] Chinese patent document with publication number CN104062369A discloses a method for detecting chlorobenzene in sludge by ultrasonic-assisted dispersive liquid-liquid microextraction-gas chromatography, which includes the following steps: (1) preparation of standard solution; (2) ultrasonic-assisted extraction; (3) dispersive liquid-liquid microextraction; (4) gas chromatographic analysis. This detection method has high sensitivity, short analysis time, and saves the use of a large amount of toxic reagents, and can be used for the detection of a large number of sludge samples. However, this detection method can only detect 6 kinds of chlorobenzenes, namely m-dichlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and 1,2,3,4-tetrachlorobenzene, and cannot simultaneously detect polychloroprene compounds.

[0004] Chinese patent document with publication number CN108152397A discloses a method for simultaneously detecting hexachloroprene, pentachlorobenzene, and hexachlorobenzene in fly ash from waste incineration, which includes the following steps: (1) pretreatment of sample pieces; (2) ultrasonic extraction; (3) purification; (4) gas chromatography-mass spectrometry detection; (5) establishment of standard curve and acquisition of quantitative results. This detection method is simple to operate and has high sensitivity, and can ensure a good recovery rate while removing impurities, making up for the blank of the analysis and detection method of hexachloroprene in fly ash. However, this detection method has fewer types of polychloroprene and polychlorobenzene compounds detected simultaneously and lower efficiency.

[0005] In summary, the existing detection methods for polychloroprene and polychlorobenzene have the following disadvantages: (1) The gas chromatography-mass spectrometry instrument only contains one mass analyzer and cannot perform dynamic multiple reaction monitoring. Since the matrix of biological samples is complex, such detection methods have problems such as low recovery rate, serious interference, and insufficient sensitivity; (2) In the prior art, rotary evaporation concentration is mostly used for sample concentration, and only the extraction solution or the eluate after purification of one sample can be concentrated at a time. If multiple samples need to be detected, using rotary evaporation concentration will consume a large amount of time, and two steps of rotary evaporation concentration are required for detecting one sample; (3) Excessive reagents are consumed during the purification process of the composite chromatography column, so the cost of this technology is relatively high.

[0006] Therefore, there is an urgent need to find a method that can simultaneously detect multiple polychloroprene and polychlorobenzene compounds. Summary of the Invention

[0007] To solve the above technical problems, the present invention provides a method for simultaneously detecting polychloroprene and polychlorobenzene in biological samples. This method can achieve synchronous extraction, impurity removal and purification, and quantitative and qualitative analysis of 9 polychloroprene and 11 polychlorobenzene in biological samples.

[0008] A method for simultaneously detecting polychloroprene and polychlorobenzene in biological samples includes the following steps:

[0009] (1) Ultrasonic extraction: After freeze-drying and grinding the biological sample into powder, mix the biological sample powder with 13 the C-labeled mixed standard solution, and obtain an extract after ultrasonic extraction;

[0010] (2) Purification and impurity removal: After quickly evaporating and concentrating the extract obtained in step (1), use a solid-phase extraction composite purification column for purification and impurity removal to obtain an eluate, and obtain a concentrated eluate after nitrogen blowing and concentration;

[0011] (3) Detection and data analysis: Use a gas chromatography-triple quadrupole mass spectrometer to detect the concentrated eluate obtained in step (2), and analyze the types and contents of polychloroprene and polychlorobenzene in the biological sample according to the standard curves of polychloroprene and polychlorobenzene established in advance.

[0012] In the present invention, after extraction by ultrasonic extraction, rapid evaporation and concentration are used instead of the existing rotary evaporation concentration, and combined with the dynamic multiple reaction monitoring of the gas chromatography-triple quadrupole mass spectrometer, synchronous extraction, impurity removal and purification, and quantitative and qualitative analysis of 9 polychloroprene and 11 polychlorobenzene in biological samples can be achieved, improving the detection efficiency.

[0013] The biological samples in the present invention can be marine animals such as fish and shrimp, or plants such as leaves and water hyacinths.

[0014] Preferably, in step (1), the 13 C-labeled mixed standard solution includes 13 C-pentachlorobenzene, 13 C-hexachlorobenzene and 13 C-hexachlorobutadiene.

[0015] In the present invention, C-labeled pentachlorobenzene, hexachlorobenzene and hexachlorobutadiene are used as the mixed standard solution. After mixing with the biological sample, extraction, purification and impurity removal are carried out, and a gas chromatography-triple quadrupole mass spectrometer is used for detection. The 13 detected 13The amounts of C-labeled pentachlorobenzene, hexachlorobenzene, and hexachlorobutadiene are determined, and the recovery rate of the detection method is calculated to evaluate the accuracy of the detection method.

[0016] Preferably, in step (1), the temperature of the ultrasonic extraction is 25 - 30 °C, and the time of the ultrasonic extraction is 15 - 20 min.

[0017] Preferably, in step (1), the extraction agent for the ultrasonic extraction is a mixed solution of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane is 1:1.

[0018] Preferably, in step (1), the ultrasonic extraction step is to freeze-dry the biological sample, grind it into powder, sieve it, weigh the biological sample powder and 13 mix it evenly with the C-labeled mixed standard solution, use the mixed solution of dichloromethane and n-hexane as the extraction agent, and extract it under ultrasonic to obtain the extract.

[0019] Preferably, in step (2), the extract is quickly evaporated and concentrated to 3 - 5 mL.

[0020] Preferably, in step (2), the solid-phase extraction composite purification column is filled with acidic silica gel, neutral alumina, and anhydrous sodium sulfate from bottom to top, and the mass ratio of acidic silica gel, neutral alumina, and anhydrous sodium sulfate is 1.5:1.5:1.

[0021] Preferably, in step (2), the eluent used in the purification and impurity removal process is n-hexane.

[0022] Preferably, in step (3), the gas chromatography of the gas chromatography-triple quadrupole mass spectrometry is separated using a DB-5MS fused silica capillary column, with a specification of 60 m × 0.25 mm and a film thickness of 0.25 μm.

[0023] Preferably, in step (3), the injection volume of the gas chromatography is 2 μL, the injector temperature is 250 °C, the carrier gas is 99.999% helium, and the flow rate is 1.0 mL / min.

[0024] Preferably, in step (3), the temperature programming of the gas chromatography is: the initial temperature is 50 °C, lasting for 2 min, rising to 110 °C at a rate of 20 °C / min and holding for 1 min, then rising to 127 °C at a rate of 1 °C / min, subsequently rising to 145 °C at a rate of 18 °C / min and holding for 3 min, and finally rising to 300 °C at a rate of 10 °C / min.

[0025] Preferably, in step (3), the conditions of the triple quadrupole mass spectrometry are as follows: the scan type is selected as the dynamic multiple reaction monitoring mode; the ion source is an electron impact ionization source, the ion source temperature is 250 °C, and the electron energy is 70 eV.

[0026] Preferably, in step (3), the detection and data analysis steps are as follows: the concentrated eluate obtained in step (2) is detected using a gas chromatography-triple quadrupole mass spectrometry instrument.

[0027] The conditions of the chromatography are as follows: the separation is carried out using a DB-5MS fused silica capillary column with a specification of 60 m × 0.25 mm and a film thickness of 0.25 μm; the injection volume is 2 μL; the injector temperature is 250 °C; the carrier gas is high-purity helium (99.999%), and the flow rate is 1.0 mL / min; the temperature programming is as follows: the initial temperature is 50 °C, which is maintained for 2 min, then it is increased to 110 °C at a rate of 20 °C / min and held for 1 min, then it is increased to 127 °C at a rate of 1 °C / min, subsequently it is increased to 145 °C at a rate of 18 °C / min and held for 3 min, and finally it is increased to 300 °C at a rate of 10 °C / min.

[0028] The conditions of the mass spectrometry are as follows: the scan type is selected as the dynamic multiple reaction monitoring mode; the ion source is an electron impact ionization source, the ion source temperature is 250 °C, and the electron energy is 70 eV.

[0029] Establish a standard curve for the peak areas of polychlorobutadienes and polychlorobenzenes and their corresponding concentrations of polychlorobutadienes and polychlorobenzenes. Identify the types of polychlorobutadienes and polychlorobenzenes in the biological sample based on the retention time, and calculate the contents of polychlorobutadienes and polychlorobenzenes according to the standard curve of the relationship between the peak area and the concentration.

[0030] Preferably, in step (3), the polychlorobutadienes include hexachlorobutadiene (HCBD), 1,1,2,3,4-pentachlorobutadiene (1,1,2,3,4-PeCBD), 1,1,2,4,4-pentachlorobutadiene (1,1,2,4,4-PeCBD), cis-1,1,3,4-tetrachlorobutadiene ((Z)-1,1,3,4-TeCBD), trans-1,1,3,4-tetrachlorobutadiene ((E)-1,1,3,4-TeCBD), 1,1,2,4-tetrachlorobutadiene (1,1,2,4-TeCBD), 1,1,2,3-tetrachlorobutadiene (1,1,2,3-TeCBD), 1,2,3,4-tetrachlorobutadiene (1,2,3,4-TeCBD), 1,1,4,4-tetrachlorobutadiene (1,1,4,4-TeCBD).

[0031] In the present invention, the structure of the polychlorobutadiene is shown as follows:

[0032]

[0033] Preferably, in step (3), the polychlorobenzenes include hexachlorobenzene (HCB), pentachlorobenzene (PeCB), 1,2,3,5 - tetrachlorobenzene (1,2,3,5 - TeCB), 1,2,4,5 - tetrachlorobenzene (1,2,4,5 - TeCB), 1,2,3,4 - tetrachlorobenzene (1,2,3,4 - TeCB), 1,3,5 - trichlorobenzene (1,3,5 - TrCB), 1,2,4 - trichlorobenzene (1,2,4 - TrCB), 1,2,3 - trichlorobenzene (1,2,3 - TrCB), 1,2 - dichlorobenzene (1,2 - DiCB), 1,3 - dichlorobenzene (1,3 - DiCB), 1,4 - dichlorobenzene (1,4 - DiCB).

[0034] In the present invention, the structure of the polychlorobenzenes is as follows:

[0035]

[0036] Preferably, the method for establishing the standard curves of polychlorobutadienes and polychlorobenzenes is as follows: The standard substances of polychlorobutadienes and polychlorobenzenes are respectively prepared into standard working solutions with concentrations of 0.5 - 20 ppb, and detected by gas chromatography - triple quadrupole mass spectrometry. Taking the chromatographic peak area of the quantitative ion of polychlorobutadiene or polychlorobenzene as the ordinate and the corresponding concentration of polychlorobutadiene or polychlorobenzene as the abscissa, the standard curves are plotted.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] After the biological samples are extracted by ultrasonic extraction in the present invention, rapid evaporation concentration is used to replace the existing rotary evaporation concentration, and combined with the dynamic multiple reaction monitoring of gas chromatography - triple quadrupole mass spectrometry, the synchronous extraction, impurity removal and purification, and quantitative and qualitative analysis of 9 polychlorobutadienes and 11 polychlorobenzenes in biological samples can be realized, improving the detection efficiency. Description of the Drawings

[0039] Figure 1 It is the separation chromatogram of Example 1. Detailed Embodiments

[0040] The following combines examples to further elaborate on the present invention in detail, but the embodiments of the present invention are not limited to the following examples only.

[0041] The raw materials used in the present invention are all commercially available.

[0042] Establishment of Standard Curves

[0043] Hexachlorobutadiene (HCBD), 1,1,2,3,4-pentachlorobutadiene (1,1,2,3,4-PeCBD), 1,1,2,4,4-pentachlorobutadiene (1,1,2,4,4-PeCBD), cis-1,1,3,4-tetrachlorobutadiene ((Z)-1,1,3,4-TeCBD), trans-1,1,3,4-tetrachlorobutadiene ((E)-1,1,3,4-TeCBD), 1,1,2,4-tetrachlorobutadiene (1,1,2,4-TeCBD), 1,1,2,3-tetrachlorobutadiene (1,1,2,3-TeCBD), 1,2,3,4-tetrachlorobutadiene (1,2,3,4-TeCBD), 1,1,4,4-tetrachlorobutadiene (1,1,4,4-TeCBD), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), 1,2,3,5-tetrachlorobenzene (1,2,3,5-TeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB), 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), 1,3,5-trichlorobenzene (1,3,5-TrCB), 1,2,4-trichlorobenzene (1,2,4-TrCB), 1,2,3-trichlorobenzene (1,2,3-TrCB), 1,2-dichlorobenzene (1,2-DiCB), 1,3-dichlorobenzene (1,3-DiCB), 1,4-dichlorobenzene (1,4-DiCB), 13 C-pentachlorobenzene ( 13 C6-PeCB), 13 C-hexachlorobenzene ( 13 C6-HCB) and 13 C-hexachlorobutadiene ( 13 C4-HCBD) standard products were respectively prepared into standard working solutions of 0.5, 1, 2, 5, 10, 20 ppb, and detected by gas chromatography-triple quadrupole mass spectrometry. The conditions are as follows:

[0044] Chromatographic conditions: The separation was carried out using a DB-5MS fused silica capillary column (60 m × 0.25 mm, film thickness 0.25 μm, Agilent Technologies, USA); the injection volume was 2 μL; the injector temperature was 250 °C; the carrier gas was high-purity helium (99.999%), and the flow rate was 1.0 mL / min; the temperature programming was: the initial oven temperature was maintained at 50 °C for 2 minutes, then increased to 110 °C at a rate of 20 °C / min and held for 1 minute, then increased to 127 °C at a rate of 1 °C / min, increased to 145 °C at a rate of 18 °C / min and held for 3 minutes, and finally increased to 300 °C at a rate of 10 °C / min;

[0045] Mass spectrometry conditions: When collecting data, the scan type was selected as the dynamic multiple reaction monitoring mode (dMRM); the EI ion source temperature was set at 250 °C, and the electron energy was 70 eV.

[0046] Taking the chromatographic peak area of the quantitative ion of polychloroprene or polychlorobenzene as the ordinate and the corresponding concentration of polychloroprene or polychlorobenzene as the abscissa, a standard curve was plotted, and the results are shown in Table 1.

[0047] Table 1: Standard curve equations and R of polychloroprene and polychlorobenzene 2 results

[0048] Compound Linear equation <![CDATA[R 2 > 1,2-DiCB y = 0.4831x + 0.0177 0.9993 1,3-DiCB y = 1.1418x + 0.0228 0.9996 1,4-DiCB y = 0.7413x + 0.0424 0.9983 1,1,2,3-TeCBD y = 0.4553x + 0.0091 0.9996 (E)-1,1,3,4-TeCBD y = 0.3406x + 0.0052 0.9999 1,1,4,4-TeCBD y = 0.2105x + 0.0027 0.9997 1,1,2,4-TeCBD y = 0.3209x + 0.0058 0.9988 (Z)-1,1,3,4-TeCBD y = 0.1682x + 0.002 0.9999 1,2,3,4-TeCBD y = 0.3765x + 0.0064 0.9997 1,2,3-TrCB y = 0.6573x + 0.0165 0.9994 1,2,4-TrCB y = 0.6503x + 0.0386 0.9994 1,3,5-TrCB y = 0.7044x + 0.0112 0.9997 1,1,2,3,4-PeCBD y = 0.1566x + 0.0038 0.9990 1,1,2,4,4-PeCBD y = 0.154x + 0.0017 0.9994 1,2,3,4-TeCB y = 0.411x + 0.007 0.9998 1,2,3,5-TeCB y = 0.3868x + 0.0169 0.9968 1,2,4,5-TeCB y = 0.4502x + 0.0042 0.9991 HCBD y = 0.4528x + 0.0212 0.9995 <![CDATA 13 C4-HCBD]]> y = 0.5166x + 0.0121 0.9995 PeCB y = 0.3236x + 0.006 0.9997 <![CDATA 13 C6-PeCB]]> y = 0.261x + 0.0046 0.9998 HCB y = 0.3922x + 0.0058 0.9996 <![CDATA 13 C6-HCB]]> y = 0.2877x + 0.0037 0.9991

[0049] Example 1

[0050] (1) The biological sample was freeze-dried, ground into powder, and passed through an 80-mesh sieve; 1 g of the sieved powder was weighed and mixed with 10 ng 13 14C-labeled mixed standard solution ( 13 14C-pentachlorobenzene, 13 14C-hexachlorobenzene and 13 14C-hexachlorobutadiene), and extracted with 30 mL of a mixed solution of dichloromethane and n-hexane (1:1, v / v) in a 30 °C ultrasonic bath for 15 minutes. The extraction was repeated once, and then the extraction solutions from the two extractions were combined;

[0051] (2) The extraction solution obtained in step (1) was concentrated to 3 - 5 mL using a rapid evaporator (LABCONCO, USA); it was purified using a 6 mL solid-phase extraction composite purification column, which was filled with 1.5 g of acidic silica gel, 1.5 g of activated neutral alumina, and 1 g of activated anhydrous sodium sulfate from bottom to top. Before purification, the purification column was rinsed with 5 mL of n-hexane, then the concentrated extraction solution was loaded onto the purification column, and then eluted with 10 mL of n-hexane to obtain an eluate, which was concentrated to 0.5 mL under a gentle nitrogen stream;

[0052] (3) 10 ng of phenanthrene -d10 (Ph -d10 ) was added to the concentrated eluate obtained in step (2) as an injection internal standard. After mixing, it was analyzed using a gas chromatograph (Agilent 8890, USA) and a triple quadrupole mass spectrometer (Agilent 7000D, USA) in combination. The instrument operating conditions were set as follows:

[0053] Chromatographic conditions: Separation was carried out using a DB-5MS fused silica capillary column (60 m × 0.25 mm, film thickness 0.25 μm, Agilent Technologies, USA); the injection volume was 2 μL; the injector temperature was 250 °C; the carrier gas was high-purity helium (99.999%), and the flow rate was 1.0 mL / min; the temperature program was as follows: the initial oven temperature was maintained at 50 °C for 2 minutes, then it was raised to 110 °C at a rate of 20 °C / min and held for 1 minute, then it was raised to 127 °C at a rate of 1 °C / min, raised to 145 °C at a rate of 18 °C / min and held for 3 minutes, and finally raised to 300 °C at a rate of 10 °C / min;

[0054] Mass spectrometry conditions: When collecting data, the scan type was selected as the dynamic multiple reaction monitoring mode (dMRM); the EI ion source temperature was set at 250 °C, and the electron energy was 70 eV.

[0055] The results are as Figure 1 shown in

[0056] Table 2: Quantitative and qualitative analysis ions of polychlorobutadiene and polychlorobenzene, and their corresponding peak numbers Figure 1 in

[0057]

[0058]

[0059] Table 3: Recovery rate, RSD and method detection limit (MDL) when adding 10 ng standard solution in Example 1

[0060]

[0061]

[0062] As can be seen from Table 3, the recovery rates of polychlorobutadiene and polychlorobenzene after spiking were 48% - 85%, and the detection limits of the detection method were in the range of 0.03 - 0.84 ng / g.

[0063] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample, characterized in that, It includes the following steps: (1) Ultrasonic extraction: After freeze-drying and grinding the biological sample into powder, mix the biological sample powder with 13 the C-labeled mixed standard solution, and obtain the extract after ultrasonic extraction; (2) Purification and impurity removal: After quickly evaporating and concentrating the extraction solution obtained in step (1), it is purified and the impurities are removed using a solid-phase extraction composite purification column to obtain an eluate, and after nitrogen blowing and concentrating, a concentrated eluate is obtained; (3) Detection and data analysis: The concentrated eluate obtained in step (2) is detected using a gas chromatography-triple quadrupole mass spectrometer, and according to the standard curves of polychlorobutadiene and polychlorobenzene established in advance, the types and contents of polychlorobutadiene and polychlorobenzene in the biological sample are analyzed.

2. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (1), the 13 C-labeled mixed standard solution includes 13 C-pentachlorobenzene, 13 C-Hexachlorobenzene and 13 C-hexachlorobutadiene.

3. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (1), the temperature of the ultrasonic extraction is 25-30 °C, and the time of the ultrasonic extraction is 15-20 min.

4. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (1), the extraction agent for the ultrasonic extraction is a mixed solution of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane is 1:

1.

5. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (2), the solid-phase extraction composite purification column is filled with acidic silica gel, neutral alumina and anhydrous sodium sulfate from bottom to top, and the mass ratio of the acidic silica gel, neutral alumina and anhydrous sodium sulfate is 1.5:1.5:

1.

6. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (3), the gas chromatography of the gas chromatography-triple quadrupole mass spectrometer is separated using a DB-5MS fused silica capillary column, with a specification of 60 m × 0.25 mm and a film thickness of 0.25 μm; the injection volume of the gas chromatography is 2 μL, the injector temperature is 250 °C, the carrier gas is 99.999% helium, and the flow rate is 1.0 mL / min.

7. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (3), the temperature programming of the gas chromatography is: the initial temperature is 50 °C, lasting for 2 min, rising to 110 °C at a rate of 20 °C / min and holding for 1 min, then rising to 127 °C at a rate of 1 °C / min, subsequently rising to 145 °C at a rate of 18 °C / min and holding for 3 min, and finally rising to 300 °C at a rate of 10 °C / min.

8. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein, In step (3), the conditions of the triple quadrupole mass spectrometer are: the scan type is selected as the dynamic multiple reaction detection mode; the ion source is an electron impact ionization source, the ion source temperature is 250 °C, and the electron energy is 70 eV.

9. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein, In step (3), the polychlorobutadiene includes hexachlorobutadiene, 1,1,2,3,4-pentachlorobutadiene, 1,1,2,4,4-pentachlorobutadiene, cis-1,1,3,4-tetrachlorobutadiene, trans-1,1,3,4-tetrachlorobutadiene, 1,1,2,4-tetrachlorobutadiene, 1,1,2,3-tetrachlorobutadiene, 1,2,3,4-tetrachlorobutadiene, 1,1,4,4-tetrachlorobutadiene; The polychlorobenzene includes hexachlorobenzene, pentachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene.

10. The method for simultaneously detecting polychloroprene and polychlorobenzene in a biological sample according to claim 1, wherein In step (3), the method for establishing the standard curves of polychloroprene and polychlorobenzene is as follows: Prepare standard working solutions of polychloroprene and polychlorobenzene with concentrations ranging from 0.5 to 20 ppb respectively, and detect them using a gas chromatography-triple quadrupole mass spectrometer. Plot the standard curves with the chromatographic peak area of the quantitative ion of polychloroprene or polychlorobenzene as the ordinate and the corresponding concentration of polychloroprene or polychlorobenzene as the abscissa.

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