CN111175418A

CN111175418A - Method for simultaneously detecting multiple trace amount persistent halogenated organic pollutants in insect body

Info

Publication number: CN111175418A
Application number: CN202010118652.0A
Authority: CN
Inventors: 刘煜; 吴永明; 涂文清; 邓觅; 杨春燕
Original assignee: Jiangxi Academy Of Sciences
Current assignee: Jiangxi Academy Of Sciences
Priority date: 2020-02-25
Filing date: 2020-02-25
Publication date: 2020-05-19

Abstract

The invention provides a method for simultaneously detecting multiple trace amounts of persistent halogenated organic pollutants in insect bodies. The invention adopts an accelerated solvent to extract a target compound, uses concentrated sulfuric acid and concentrated hydrochloric acid for purification, and utilizes different types of solid phase extraction columns to separate different target compounds, thereby realizing the synchronous extraction and purification process of various POPs; adding the corresponding¹³And C isotope internal standard and deuterium recovery rate indicator are used for performing quality control on pretreatment process and instrument detection errors and performing quantitative analysis on a target compound. And the organic pollutants are detected by a sampling isotope dilution method and a high-resolution gas phase/liquid phase mass spectrometry method, so that a high-sensitivity quantitative detection result is obtained. The method ensures the accuracy and reliability of the determination of the trace persistent organic pollutants contained in the insects, and provides a new technical means for the rapid screening and accurate quantification of the multi-component persistent organic pollutants in the complex matrix。

Description

Method for simultaneously detecting multiple trace amount persistent halogenated organic pollutants in insect body

Technical Field

The invention belongs to the field of environmental protection, and particularly relates to a method for detecting various types of persistent halogenated organic pollutants in insect bodies.

Background

Insects contain abundant proteins and low fat content such as cholesterol, so that the insects have great potential in the aspects of medicine, health-care products and functional food development. Insect traditional Chinese medicines have various pharmacological actions such as immunity enhancement, antibiosis, anti-inflammation, antianaphylaxis, antivirus, anticonvulsant, sedation, analgesia, anticancer and the like, and are clinically used for treating various diseases. Besides disease treatment, insects also have better nutrition and health care effects, and health care products developed by medicinal insects show wide prospects. However, the quality safety problem in the development process restricts the development of Chinese traditional medicine industry. Among these, the problem of residual persistent organic contaminants is of particular concern. When insects are used as traditional Chinese medicines or food by human beings, organic pollutants in the insects also enter human bodies, and when a certain amount of the insects reach a certain amount, the insects can cause the endocrine system disorder of the human bodies and destroy the immune system, thereby influencing the efficacy of the insects and even the health of the human bodies. In addition, insects are also commonly used in environmental detection of pollutants as an indicator organism for environmental pollution.

Typical Halogenated Organic Pollutants (HOPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyl oxides (DDTs), and polybrominated diphenyl ethers (PBDEs), have high biotoxicity, high bioaccumulation, environmental persistence, and long-range migratory ability, have been classified as Persistent Organic Pollutants (POPs), and are prohibited from being produced and used. And novel halogenated organic pollutants, such as Novel Brominated Flame Retardants (NBFRs), Chlorinated Paraffins (CPs), Dacron (DP), and the like, also have characteristics similar to POPs and are easily enriched and amplified in vivo. Most current research monitors the pollution level and toxicity of a single pollutant or a class of pollutants, but in fact, the organic pollutants coexist in organisms or human bodies to form compound pollution of multiple classes of organic pollutants, and further cause combined toxicity. Therefore, it is necessary to simultaneously detect the contamination levels of these typical and novel organic contaminants. However, the composition of new organic contaminants is complex, especially CPs have thousands of homologues and isomers, and are also susceptible to interference from other chlorine-containing compounds (PCBs, DDTs, chlordane, etc.) in the matrix when analyzed. Thus, the detection methods for these novel organic pollutants have disadvantages, and the development of methods for simultaneously detecting typical and novel halogenated organic pollutants is urgently needed.

The combined detection of various organic pollutants is a development trend of environmental health detection work in the future. Because insect food or traditional Chinese medicine is very precious, the quantity of the obtained samples is small, and the collected samples can only be pretreated once; meanwhile, the insect components are complex, the content level of persistent organic pollutants is relatively low, the method belongs to trace analysis and is easily interfered by other components, and many methods in the prior art cannot detect the persistent organic pollutants or have large errors. Therefore, there is a need to establish a combined detection method suitable for insect food or traditional Chinese medicine samples and various trace halogenated organic pollutants, so as to realize the concentration levels of various halogenated organic pollutants obtained by one-time analysis of limited sample amount. However, no detection method is available at present which is specific for organic contaminants in insects. Insects are generally dosed as a whole, with their exoskeleton mainly composed of chitin and proteins, which become the main interfering substances during extraction, unlike the fat that is the main interference in other biological samples, and therefore are not easily removed during pretreatment for contaminant detection.

At present, the existing detection methods for organic pollutants such as PCBs, PBDEs, CPs and the like in organisms at home and abroad are all based on that one kind of compounds are taken as a detection target, and other compounds are taken as a part of matrix interference to be removed in the pretreatment process. When the concentration of other pollutants in the sample is detected, another pretreatment method is required to be adopted for purification with the same purpose, so that the workload is greatly increased, the detection time is prolonged, the detection cost is increased, and the bottleneck of the detection of a large number of samples of various organic pollutants is formed.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a pretreatment and detection method for simultaneously detecting trace halogenated organic pollutants, which can meet the detection requirements of various trace organic pollutants in insects, and the specific technical scheme is as follows.

A method for simultaneously detecting multiple trace amounts of persistent halogenated organic pollutants in insect bodies comprises the following steps:

(1) taking a proper amount of insect samples, freeze-drying, grinding into powder, and then weighing a proper amount of powder samples;

(2) adding an internal standard indicator corresponding to a required detection object into a powdery sample, and then performing accelerated solvent extraction by using a dichloromethane/n-hexane solvent with a volume ratio of 1: 1;

(3) measuring the fat content of a sample in one part of the extract obtained in the step (2), adding concentrated sulfuric acid in the other part of the extract, uniformly mixing, centrifuging, removing an organic phase to a Teflon tube, adding concentrated hydrochloric acid, centrifuging again, and removing the organic phase to the Teflon tube;

(4) washing the removed organic phase after twice concentrated acid cleaning to be neutral by using ultrapure water, dewatering by using anhydrous sodium sulfate, concentrating the concentrated constant volume by using a rotary evaporator, and obtaining a detection sample by using normal hexane to obtain the constant volume, wherein the detection sample is divided into two parts;

(5) concentrating a first part of detection samples to a proper volume by using a nitrogen blow dryer, passing through a Florisil solid phase extraction purification small column, eluting by using a proper amount of n-hexane to obtain first test components aiming at DDTs, PCBs, DP, PBBs, PBDEs and OBFRs, eluting by using a proper amount of dichloromethane to obtain a second test component aiming at CPs, diluting the first test component and the second test component to a constant volume by using isooctane, and then respectively adding recovery rate indicators corresponding to a required test object for GC/MS detection;

(6) and concentrating a second part of detection samples to a proper volume by using a nitrogen blow dryer, separating and purifying the second part of detection samples by using a silica gel solid phase extraction column, pre-leaching the second part of detection samples by using n-hexane and a n-hexane/dichloromethane mixed solvent with the volume ratio of 1: 1, leaching the second part of detection samples by using a certain amount of the n-hexane/dichloromethane mixed solvent, collecting leacheate to obtain a third test component aiming at TBBPA and HBCDs, adding a recovery rate indicator by blowing nitrogen, fixing the volume by using methanol, filtering the mixture by using a microporous filter membrane, and performing HPLC/MS detection.

Further, the addition amount of the internal standard indicator in the step (2), the addition amount of the recovery rate indicator in the step (5) and the addition amount of the recovery rate indicator in the step (6) are 10-100ng/1g of dry weight sample; the extraction dosage of dichloromethane/n-hexane solvent is 20-200ml/1g dry weight sample, the extraction time of solvent is accelerated to 5min, and the cycle is 2 times.

Further, the adding volume ratio of the extract liquid of the concentrated acid pickling in the step (3) to the concentrated sulfuric acid and the concentrated hydrochloric acid is 9: 1; and (4) the volume of the constant volume is 2 times of that of the concentrated acid cleaning extract liquor.

Further, the specification of the Florisil solid phase extraction purification cartridge in the step (5) is 6mL and 1000mg, and the dosage is 1 per 1mL of detection sample; detecting a sample with the dosage of n-hexane being 3-5mL/1 mL; the dosage of n-hexane/dichloromethane is 3-5mL/1mL of detection sample.

Further, the specification of the silica gel solid phase extraction column in the step (6) is 6mL and 1000mg, and the dosage is 1 per 1mL of detection sample; pre-washing the detection sample with the amount of n-hexane being 3-5mL/1 mL; pre-leaching a detection sample with the dosage of n-hexane/dichloromethane of 1-3mL/1 mL; collecting a detection sample with the use amount of leached n-hexane/dichloromethane being 6-10mL/1 mL; the filter diameter of the microporous filter membrane is less than or equal to 0.22 mu m.

Further, specific reference is made to fig. 2 for the above substances and their corresponding internal standard indicators, recovery indicators and detection methods.

Further, the detection method for various substances is as follows:

the analysis method of PCBs and DDTs is Agilent gas chromatography-mass spectrometer (Agilent 7890 GC-5975BMS), and a selective ion detection (SIM) mode is adopted under an electron impact ion source (EI). The carrier gas is helium, the flow rate is 1.1mL/min, the pulse is not divided into the flow sample injection, the sample injection amount is 1 muL. The chromatographic column was DB-5MS (60 m.times.250 μm i.d.. times.0.25 μm), the injection port temperature was 290 ℃ and the ion source temperature was 260 ℃. GC temperature program: the initial temperature is 120 ℃, the temperature is increased to 180 ℃ at the speed of 6 ℃/min, then the temperature is increased to 240 ℃ at the speed of 1 ℃/min and is kept for 1min, then the temperature is increased to 290 ℃ at the speed of 6 ℃/min and is kept for 15min, and finally the temperature is increased to 310 ℃ at the speed of 5 ℃/min and is kept for 5 min.

The analysis of low-brominated PBDEs (3-7 brominated monomers), DP and OBFRs is completed by selecting a SIM mode under Negative Chemical Ionization (NCI) by adopting an Agilent6890GC-5975 MS. Separation was performed using a DB-XLB column (30 m.times.250 μm i.d.. times.0.25 μm) with column flow rateIs 1 mL/min. The pressure of the ion source is 2.5X 10^-3Pa, adopting no-shunt sampling, wherein the sampling amount is 1 mu L, the temperatures of a sampling port and an ion source are 290 ℃ and 200 ℃ respectively, and the temperature of an interface (mass spectrum connecting line) is 280 ℃. GC temperature program: the initial temperature is 110 ℃ and kept for 1min, the temperature is raised to 180 ℃ at 8 ℃/min and kept for 1min, then the temperature is raised to 240 ℃ at 2 ℃/min and kept for 5min, then the temperature is raised to 280 ℃ at 2 ℃/min and kept for 15min, and finally the temperature is raised to 300 ℃ at 10 ℃/min and kept for 15 min.

The analysis of high-brominated PBDEs (8-10 brominated monomers) and DBDPE is completed by adopting Shimadzu gas chromatography-mass spectrometer (Shimadzu QP2010 GC-MS) and selecting a SIM mode under NCI. The separation was carried out using a DB-5HT chromatography column (15 m.times.0.25 mm i.d.. times.0.10 μm) at a column flow rate of 1 mL/min. GC temperature program: the initial temperature is 110 ℃ and kept for 5min, the temperature is raised to 200 ℃ at 20 ℃/min and kept for 4.5min, and then the temperature is raised to 310 ℃ at 20 ℃/min and kept for 20 min.

CPs are analyzed by an Agilent gas chromatography-mass spectrometer (Agilent6890GC-5975MS) under electron capture negative chemical ionization (ENCI) and SIM mode is selected. The separation was performed using a DB-5HT chromatography column (15 m.times.250 μm i.d.. times.0.1 μm) at a column flow rate of 1.5 mL/min. The non-split flow sample injection is adopted, the sample injection amount is 1 mu L, the sample injection port and the ion source temperature are respectively 250 ℃ and 200 ℃, and the interface temperature is 280 ℃. GC temperature program: the initial temperature is 80 ℃ and kept for 3min, the temperature is increased to 160 ℃ at 25 ℃/min and kept for 6min, and then the temperature is increased to 300 ℃ at 20 ℃/min and kept for 15 min.

The analysis of HBCDs and TBBPA is completed by adopting an Agilent liquid chromatography-mass spectrometer (Agilent 1200LC-6410MS) and selecting a multi-reaction monitoring mode (MRM) under an ESI negative ion mode. Using XDB-C₁₈The column (50 mm. times.4.6 mm i.d.. times.1.8 mm) was used for separation at a column flow rate of 0.3mL/min, a column temperature of 35 ℃ and a sample volume of 10. mu.L. Mobile phase a was aqueous methanol (1: 9), mobile phase B was acetonitrile, elution gradient 0min 70% a and 30% B, 5min 10% a and 90% B, 10min 70% a and 30% B.

The invention provides a method for simultaneously detecting multiple trace amounts of persistent halogenated organic pollutants in insect bodies. The invention adopts the accelerated solvent to extract the target compound,concentrated sulfuric acid and concentrated hydrochloric acid are used for cleaning at the same time, different types of solid phase extraction small columns are used for separating different target compounds, and the synchronous extraction and purification processes of various POPs are realized; adding the corresponding¹³And C isotope internal standard and deuterium recovery rate indicator are used for performing quality control on pretreatment process and instrument detection errors and performing quantitative analysis on a target compound. And the organic pollutants are detected by a sampling isotope dilution method and a high-resolution gas phase/liquid phase mass spectrometry method, so that a high-sensitivity quantitative detection result is obtained. The method ensures the accuracy and reliability of the determination of the persistent organic pollutants in the insects, and provides a new technical means for the rapid screening and accurate quantification of the multi-component persistent organic pollutants in the complex matrix.

Drawings

FIG. 1 is a process technical roadmap of the present invention;

FIG. 2 is a diagram of specific species of POPs and their corresponding internal standard indicators, recovery indicators, and detection methods;

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

in this example, insect samples collected from a certain farmland in Qingyuan, Guangdong province, including locusts (Chinese rice locusts and short negative locusts), crickets (Chinese crickets) and mole crickets (oriental mole crickets) were selected and used as Chinese herbs.

Locust, cricket and mole cricket are collected by adopting a method of net sweeping and black light lamp trapping. All insect samples are collected and then subjected to species identification, the insect samples are washed by distilled water and dried, wet weights are weighed on an electronic balance, and the insect samples are wrapped by tinfoil paper and stored in a refrigerator at the temperature of-20 ℃ for analysis.

Target compound: dichlorodiphenyl (DDTs), polychlorinated biphenyls (PCBs), Dacron (DP), polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), Pentabromotoluene (PBT), Pentabromoethylbenzene (PBEB), Hexabromobenzene (HBB), decabromodiphenylethane (DBDPE), tetrabromobisphenol A (TBBPA), Hexabromocyclododecane (HBCDs), chlorinated paraffins (SCCPs and MCCPs).

Reagents and materials:

(1) mixing DDTs: mixed standards containing p, p ' -DDE, p ' -DDD and p, p ' -DDT were purchased from Ultrascientific, USA.

(2) PCBs mixed standard and single standard: PCBs Mix Standard Mix 1# to Mix 9# (covering 209 PCB monomers) were purchased from Ultrascientific (USA); PCB single labels (CB 24, 30, 65, 82, 198 and 204) were purchased from AccuStandard (USA) corporation.

(3) PBDE mixed and single label: PBDEs low-brominated monomer mixture of 10 (BDE 28, 47, 66, 85, 99, 100, 138, 153, 154 and 183), high-brominated monomer mixture of 9 (BDE 196, 197, 202, 203, 205, 206, 207, 208 and 209) and single BDE77, 118, 128 and 181, 4-F-BDE67, 3-F-BDE153 and 181¹³C-BDE 209 was purchased from AccuStdandards (USA).

(4) HBCD mixed standard is alpha-HBCD, β -HBCD, gamma-HBCD,¹³C-α-HBCD，¹³C-β-HBCD，¹³C-γ-HBCD，¹⁸d-α-HBCD，¹⁸d- β -HBCD and¹⁸the d-gamma-HBCD blendstocks are available from Wellington Laboratories (Guelph, Canada)

(5) CP mixing standard: SCCPs having a chlorine content of 52.5%, 55.5%, 63% and MCCPs of 42%, 52%, 57% were purchased from Dr. Ehrenstontorfer, Germany, as a mixed standard.

(6)¹³C-trans-chloredan, ε -HCH, syn-DP, anti-DP, PBT, PBEB, HBB, PBB153, PBB209, TBBPA and DBDPE are available from Wellington Laboratories (Guelph, Canada) as a single standard.

(7) Both flory solid phase extraction column and silica gel solid phase extraction column were purchased from Agilent.

The pretreatment method comprises the following steps: since the insect individuals are small and not suitable for anatomical analysis, the insect samples are treated in a whole sample, and a plurality of individuals are mixed into a mixed sample. The insect mixed sample is cooled for 72 hoursFreeze drying, grinding to powder, weighing 1.0g dry weight sample, adding 50 ng internal standard indicator (CB 24, CB30, CB65, etc.),¹³C-trans-chlordane、BDE 77、BDE 181、BDE 205、¹³C-BDE 209、¹³C- α -, β -, gamma-HBCD and¹³C-labeledTBBPA), then the residue was washed with 50mL of dichloromethane/n-hexane (1: 1, V/V) solvent accelerated solvent extraction for 5 minutes (min) for 2 cycles. Taking 5ml of sample extract to measure fat content, adding 5m1 concentrated sulfuric acid into the residual solution to remove impurities such as fat, protein and the like, transferring an organic phase, placing the organic phase in a Teflon (Teflon) tube, adding 5ml concentrated hydrochloric acid to remove impurities such as chitin and the like, centrifuging, transferring the organic phase, and placing the organic phase in the Teflon tube. The organic phase was washed with ultrapure water to neutrality, and dehydrated with anhydrous sodium sulfate, concentrated to a volume of 10mL, and then divided into two portions.

A first portion of the samples was used for analytical testing of DDTs, PCBs, CPs, DP, PBBs, PBDEs, PBT, PBEB, HBB and DBDPE. The sample is concentrated to 1mL, then passes through a Florisil solid phase extraction purification cartridge (6mL, 1000mg), and is eluted with 10mL of n-hexane to obtain a first component of DDTs, PCBs, DP, PBBs, PBDEs, PBT, PBEB, HBB and DBDPE, and then is eluted with 10mL of dichloromethane to obtain a second component of CPs. And finally, the volume of the eluent is up to 300 mu L, the first component is added with injection internal standards (4-F-BDE 67, 3-F-BDE153 and BDE 128), and the second component is added with the injection internal standards (epsilon-HCH) and then is detected by GC/MS.

A second portion of the sample was used for analytical detection of TBBPA and HBCDs. After the sample is concentrated to 1mL, the sample is separated and purified by a silica gel solid phase extraction column (6mL, 1000mg), 3mL of n-hexane and 3mL of n-hexane/dichloromethane mixed solvent (1: 1, V/V) are firstly used for leaching, the component is discarded, 10mL of n-hexane/dichloromethane mixed solvent is used for leaching, and TBBPA and HBCD components are collected. Nitrogen blowing label (A)¹⁸d-α-HBCD、¹⁸d- β -HBCD and¹⁸d-gamma-HBCD), adding methanol to a constant volume of 300 mu L, filtering with 0.22um microporous membrane (PTFE), and detecting by HPLC/MS.

For a sample to be detected, the following detection method and steps are adopted:

The analysis of low-brominated PBDEs (3-7 brominated monomers), DP and OBFRs is completed by selecting a SIM mode under Negative Chemical Ionization (NCI) by adopting an Agilent6890GC-5975 MS. The separation was performed using a DB-XLB column (30 m.times.250 μm i.d.. times.0.25 μm) with a column flow rate of 1 mL/min. Ion source pressure of 2.5 x 10-³Pa, adopting no-shunt sampling, wherein the sampling amount is 1 mu L, the temperatures of a sampling port and an ion source are 290 ℃ and 200 ℃ respectively, and the temperature of an interface (mass spectrum connecting line) is 280 ℃. GC temperature program: the initial temperature is 110 ℃ and kept for 1min, the temperature is raised to 180 ℃ at 8 ℃/min and kept for 1min, then the temperature is raised to 240 ℃ at 2 ℃/min and kept for 5min, then the temperature is raised to 280 ℃ at 2 ℃/min and kept for 15min, and finally the temperature is raised to 300 ℃ at 10 ℃/min and kept for 15 min.

TABLE 1 concentration levels (ng/g lw) of chlorinated organic contaminants (PCBs, DPs, DDTs) in different insect species

^aNo detection or below the method detection limit (no detection).

TABLE 2 concentration levels (ng/g lw) of brominated flame retardants (PBBDEs, HBCDs, DBDPE, TBBPA, PBT, HBB, PBEB, HBB, PBBs) in different insect species

TABLE 3 concentration levels (ng/g 1w) of chlorinated paraffins (SCCPs and MCCPs) in different insect species

TABLE 4 detection rates of target Compounds in actual samples

TABLE 5 recovery of internal standard in actual samples

The detection result shows that the recovery rate of the internal standard of the 9 types of persistent organic pollutants in the insect sample can reach 72-126% (see table 5). Besides TBBPA, various other contaminants were detected in the actual insect samples (see Table 4), especially the detection rate of CPs, which is a novel contaminant, is 100%, and the concentration is as high as 14.7. mu.g/g 1w (see Table 3). The experimental data fully show that the method has good detection precision, and has the advantages of batch operation, short time consumption, high detection efficiency and the like.

Although the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present patent within the knowledge of those skilled in the art.

Claims

1. A method for simultaneously detecting multiple trace amount persistent halogenated organic pollutants in insect bodies is characterized by comprising the following steps: the method comprises the following steps:

(4) washing the removed organic phase after twice concentrated acid cleaning to be neutral by using ultrapure water, removing water by using anhydrous sodium sulfate, concentrating by using a rotary evaporator, and performing constant volume by using normal hexane to obtain a detection sample, wherein the detection sample is divided into two parts;

2. The method of claim 1, wherein the method comprises the steps of: the addition amount of the internal standard indicator in the step (2) and the addition amount of the recovery rate indicators in the steps (5) and (6) are 10-100ng/lg dry weight sample; the extraction dosage of dichloromethane/n-hexane solvent is 20-200 ml/g dry weight sample, the extraction time of solvent is accelerated to 5min, and the circulation is carried out for 2 times.

3. The method of claim 1, wherein the method comprises the steps of: the adding volume ratio of the extract liquid of the concentrated acid pickling in the step (3) to the concentrated sulfuric acid and the concentrated hydrochloric acid is 9: 1; and (4) the volume of the constant volume is 2 times of that of the concentrated acid pickling extract liquor.

4. The method of claim 1, wherein the method comprises the steps of: the specification of the Florisil solid phase extraction purification cartridge in the step (5) is 6mL and 1000mg, and the dosage is 1 per 1mL of detection sample; detecting a sample with the dosage of n-hexane being 3-5mL/1 mL; the dosage of n-hexane/dichloromethane is 3-5mL/1mL of detection sample.

5. The method of claim 1, wherein the method comprises the steps of: in the step (6), the specification of the silica gel solid phase extraction column is 6mL and 1000mg, and the dosage is 1 per 1mL of detection sample; pre-washing the detection sample with the amount of n-hexane being 3-5mL/1 mL; pre-leaching a detection sample with the dosage of n-hexane/dichloromethane of 1-3mL/1 mL; collecting a detection sample with the use amount of leached n-hexane/dichloromethane being 6-10mL/1 mL; the filter diameter of the microporous filter membrane is less than or equal to 0.22 mu m.

6. The method of claim 1, wherein the method comprises the steps of:

the DDTs include p, p ' -DDE, p ' -DDDp and p ' -DDT, the PCBs include CB18, CB28/31, CB49, CB52, CB74, CB87/115, CB95, CB99, CB101, CB105, CB110, CB118, CB128, CB138, CB146/161, CB149/139, CB153/132, CB156, CB164/163, CB167, CB170/190, CB174/181, CB180/193, CB183, CB187, CB189, CB194, CB203/196, CB206 and CB 209; recovery rate indicators corresponding to the DDTs and the PCBs are CB82, CB198 and CB204, internal standard indicators are CB24, CB30 and CB65, and the detection method is an Agilent gas chromatography-mass spectrometer;

the PBDEs comprise BDE28, BDE47, BDE100, BDE99, BDE154, BDE153, BDE183, BDE202, BDE197, BDE203, BDE196, BDE208, BDE207, BDE206 and BDE 209; the corresponding recovery indicators were BDE77, BDE181 and BDE205, and the internal standard indicators were 4-F-BDE67, BDE118, BDE128, 3-F-BDE153 and¹³C-BDE 209, detection method: the Agilent gas chromatography-mass spectrometer is used for BDEs with low bromination of BDE28-183, and the Shimadzu gas chromatography-mass spectrometer is used for BDEs with high bromination of BDE 196-209;

the DP comprises syn-DP and anti-DP; the DBDPE comprises DBDPE; the recovery rate indicator corresponding to the DP and the DBDPE is BDE205, and the internal standard indicator is¹³C-BDE 209, the detection method adopts an Shimadzu gas chromatography-mass spectrometer;

the HBCDs include α -HBCD, β -HBCD and gamma-HBCD, and the corresponding recovery rate indicator is¹⁸d-α-HBCD、¹⁸d- β -HBCD and¹⁸d-gamma-HBCD, the internal standard indicator is¹³C-α-HBCD、¹³C- β -HBCD and¹³C-gamma-HBCD, wherein the detection method adopts an Agilent liquid chromatography-mass spectrometer;

the TBBPA comprises TBBPA and the corresponding recovery indicator is¹⁸d- α -HBCD, the internal standard indicator is¹³C-TBBPA, the detection method adopts an Agilent liquid chromatography-mass spectrometer;

the CPs include SCCPs (C)_10-13Cl_5-10)、MCCPs(C_14-17Cl_5-10) The corresponding recovery indicator is ε -HCH and the internal standard indicator is¹³C-trans-chrdane, wherein the detection method adopts an Agilent gas chromatography-mass spectrometer;

the OBFRs comprise PBT, PBEB, HBB, PBB153 and PBB209, corresponding recovery rate indicators are BDE77, BDE181 and BDE205, internal standard indicators are 4-F-BDE67, BDE118, BDE128 and 3-F-BDE153, and the detection method adopts an Agilent gas chromatography-mass spectrometer.

7. The method of claim 6, wherein the method comprises the steps of:

the PCBs and the DDTs are analyzed by an Agilent gas chromatography-mass spectrometer in a selective ion detection (SIM) mode under an electron impact ion source (EI); helium is used as carrier gas, the flow rate is 1.1mL/min, the pulse is not divided and the sample injection is carried out, and the sample injection amount is 1 mu L; the chromatographic column is DB-5MS (60m × 250 μm i.d.. times.0.25 μm), the injection inlet temperature is 290 ℃, and the ion source temperature is 260 ℃; GC temperature program: the initial temperature is 120 ℃, the temperature is increased to 180 ℃ at the speed of 6 ℃/min, then the temperature is increased to 240 ℃ at the speed of 1 ℃/min and is kept for 1min, then the temperature is increased to 290 ℃ at the speed of 6 ℃/min and is kept for 15min, and finally the temperature is increased to 310 ℃ at the speed of 5 ℃/min and is kept for 5 min.

8. The method of claim 6, wherein the method comprises the steps of:

3-7, analyzing low-brominated PBDEs, DP and OBFRs of brominated monomers by adopting an Agilent gas chromatography-mass spectrometer under Negative Chemical Ionization (NCI) and selecting a SIM mode to complete; the separation was performed using a DB-XLB column (30 m.times.250 μm i.d.. times.0.25 μm) with a column flow rate of 1 mL/min. The pressure of the ion source is 2.5X 10^-3Pa, adopting non-split flow sample injection, wherein the sample injection amount is 1 mu L, the temperatures of a sample injection port and an ion source are respectively 290 ℃ and 200 ℃, and the interface temperature is 280 ℃; GC temperature program: the initial temperature is 110 ℃ and kept for 1min, the temperature is raised to 180 ℃ at 8 ℃/min and kept for 1min, then the temperature is raised to 240 ℃ at 2 ℃/min and kept for 5min, then the temperature is raised to 280 ℃ at 2 ℃/min and kept for 15min, and finally the temperature is raised to 300 ℃ at 10 ℃/min and kept for 15 min;

the analysis of the high-brominated PBDEs and DBDPE of the 8-10 brominated monomers is completed by selecting an SIM mode under Negative Chemical Ionization (NCI) by adopting an Shimadzu gas chromatography-mass spectrometer; performing separation using a DB-5HT chromatography column (15m × 0.25mm i.d. × 0.10 μm) at a column flow rate of 1 mL/min; GC temperature program: the initial temperature is 110 ℃ and kept for 5min, the temperature is raised to 200 ℃ at 20 ℃/min and kept for 4.5min, and then the temperature is raised to 310 ℃ at 20 ℃/min and kept for 20 min.

9. The method of claim 6, wherein the method comprises the steps of:

and the analysis of the CPs is completed by adopting an Agilent gas chromatography-mass spectrometer and selecting an SIM mode under electron capture negative chemical ionization (ENCI). The separation was performed using a DB-5HT chromatography column (15 m.times.250 μm i.d.. times.0.1 μm) at a column flow rate of 1.5 mL/min. The non-split flow sample injection is adopted, the sample injection amount is 1 mu L, the sample injection port and the ion source temperature are respectively 250 ℃ and 200 ℃, and the interface temperature is 280 ℃. GC temperature program: the initial temperature is 80 ℃ and kept for 3min, the temperature is increased to 160 ℃ at 25 ℃/min and kept for 6min, and then the temperature is increased to 300 ℃ at 20 ℃/min and kept for 15 min.

10. The method of claim 6, wherein the method comprises the steps of:

the analysis of HBCDs and TBBPA is completed by adopting an Agilent liquid chromatography-mass spectrometer and selecting a multi-reaction monitoring mode (MRM) under an ESI negative ion mode; using XDB-C₁₈The column (50 mm. times.4.6 mm i.d.. times.1.8 mm) was used for separation at a column flow rate of 0.3mL/min, a column temperature of 35 ℃ and a sample volume of 10. mu.L. The mobile phase A is methanol water solution with volume ratio of 1: 9, the mobile phase B is acetonitrile, and the elution gradient is 0min 70% A and 30% B, 5min 10% A and 90% B, and 10min 70% A and 30% B.