A high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter

Abstract

This invention provides a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter. Through two sample pretreatment processes, trace extraction, concentration, purification, internal standard quantification, and recovery indicator calibration of target analytes in the gas and liquid phases are performed respectively. This method optimizes PM2.5 analysis. 2.5 Sample pretreatment procedures and instrument analysis parameters enable the analysis of PM. 2.5 This method enables the efficient trace determination of over 600 novel and traditional organic pollutants and their transformation products, with method detection limits reaching pg / m³ for each target analyte. 3 This system is conducive to a broad-spectrum analysis of atmospheric pollution, providing more comprehensive data support for the formulation of more detailed atmospheric environmental control standards and measures. It has the advantages of high throughput, short processing time, low cost, and strong comparability of results.

Description

Technical Field

[0001] This invention relates to the field of high-throughput targeted analysis technology for trace organic pollutants, and particularly to a high-throughput targeted mass spectrometry analysis method for traditional and new organic pollutants and their transformation products in atmospheric fine particulate matter. Background Technology

[0002] Air quality deterioration caused by atmospheric particulate matter (PM) is one of the leading global public health risks, and the physicochemical properties of PM itself (such as particle size and compound composition) are closely related to its potential negative effects. Among these, fine particulate matter, namely PM... 2.5 Given its ability to penetrate the respiratory tract and its high adsorption potential for organic pollutants, PM has become an environmental medium of great concern. 2.5 The attached organic pollutants not only impact the ecological environment but also pose numerous threats to human health. Existing research indicates that some compounds can harm the respiratory, endocrine, nervous, and immune systems, and these risks typically exhibit significant spatiotemporal evolution due to the heterogeneity of organic components. However, current research on PM2.5... 2.5 Analytical methods for organic pollutants (OPCs) in the atmosphere often only screen one or a few types of compounds, resulting in large experimental workloads and low efficiency. This makes it difficult for current research to conduct a comprehensive and systematic assessment of OPCs present in representative regional atmospheres. Even studies that cover several types of OPCs are generally conducted in batches, leading to increased time costs, reduced comparability of results, and high demands for experimental consumables. Furthermore, previous analytical methods are mostly geared towards traditional persistent organic pollutants, and are not suitable for monitoring PM2.5. 2.5 Methods for identifying and addressing the residues of emerging pollutants remain very scarce. On the other hand, unlike persistent organic pollutants (POPs), some emerging pollutants themselves have short environmental half-lives, but their transformation products typically exhibit high environmental persistence, and the resulting eco-health effects are becoming increasingly prominent. Considering the current domestic and international efforts to address PM2.5... 2.5 Research on high-throughput analytical methodologies for new pollutants is still very limited and fragmented, which seriously hinders relevant departments from promptly refining and formulating control standards and measures for new pollutants in the atmosphere. Therefore, it is urgent to characterize the occurrence characteristics and potential public health risks of organic components (especially new pollutants and their transformation products) that are produced in large quantities, used in large quantities, widely distributed, and have potential toxicity in the atmospheric environment. Summary of the Invention

[0003] The purpose of this invention is to provide a solution for fine particulate matter (PM2.5) in the atmosphere. 2.5This high-throughput, broad-spectrum targeted analysis method for traditional and new organic pollutants and their transformation products in atmospheric fine particulate matter utilizes two sets of sample pretreatment and instrumental analysis procedures to achieve trace determination of more than 600 organic pollutants, improving analytical efficiency, saving experimental resources, and ensuring the comparability and reliability of results.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter is used to screen for the types and concentrations of potentially present organic pollutants in atmospheric fine particulate matter, comprising the following steps:

[0006] Step S1: Using a PM-equipped 2.5 The cut-head active atmospheric sampler collects fine particulate matter samples from the atmosphere and uses the fine particulate matter captured by the quartz fiber filter membrane as the PM2.5 to be measured. 2.5 sample;

[0007] Step S2: Process the PM collected in step S1 2.5 The samples are subjected to gas phase pretreatment for the detection of volatile or semi-volatile organic pollutants to form a gas phase analytical solution for gas chromatography-mass spectrometry analysis.

[0008] For the PM 2.5 The samples are pretreated with liquid chromatography for the detection of non-volatile or polar organic pollutants to form a liquid analysis solution for liquid chromatography-mass spectrometry analysis.

[0009] Step S3: Perform quantitative analysis on the gas phase analysis liquid and the liquid phase analysis liquid obtained in step S2, wherein the gas phase analysis liquid is analyzed by gas chromatography-triple quadrupole mass spectrometry, and the liquid phase analysis liquid is analyzed by liquid chromatography-triple quadrupole mass spectrometry.

[0010] Step S4: Based on the analysis results, high-throughput screening is performed on multiple categories of target substances, including traditional organic pollutants, new organic pollutants and their transformation products, according to the retention time of chromatographic peaks (offset less than 0.1 min), chromatographic peak shape (gaussian distribution), relative abundance between multiple reaction monitoring ion pairs (deviation less than 15%), and signal-to-noise ratio (greater than 3.0) on the obtained spectra.

[0011] Preferably, the gas phase pretreatment step includes: treating the PM 2.5 The target analytes in the sample are extracted and concentrated, and internal standards and recovery indicators are added to obtain a gas chromatography-tandem mass spectrometry analysis solution suitable for gas chromatography-tandem mass spectrometry analysis.

[0012] The liquid phase pretreatment step includes: treating PM 2.5The target analytes in the sample are extracted, purified, concentrated, and filtered, and internal standards and recovery indicators are added to obtain a liquid analysis solution suitable for liquid chromatography-tandem mass spectrometry analysis.

[0013] Preferably, the gas phase pretreatment step includes:

[0014] Step S21-1: Crop 1 / 4 of the image to capture PM 2.5 The quartz fiber filter membrane of the sample was placed in a 20 mL glass test tube, and 25 ng of recovery indicator was added to the sample to be tested. The recovery indicator was a gas phase analysis target with 32 isotope labels.

[0015] Step S21-2: Add a mixed solution of n-hexane and dichloromethane in a 1:1 volume ratio to a test tube, so that PM... 2.5 The sample is completely immersed in the solution;

[0016] PM in a 40 kHz ultrasonic bath 2.5 The sample was subjected to ultrasonic extraction for 15 minutes, repeated three times, and the extracts from the three extractions were combined.

[0017] Step S21-3: Concentrate the combined extract to 200-300 μL using nitrogen blowing and transfer it to a 2 mL sample vial with an inner liner.

[0018] Step S21-4: Add 25 ng of internal standard to the concentrated sample. The internal standard is a gas phase analysis target analyte labeled with 11 isotopes.

[0019] Step S21-5: Quantitative analysis of the processed sample is performed using gas chromatography-triple quadrupole mass spectrometry (GC-MS). The target analytes for gas chromatography analysis include organochlorine pesticides, polycyclic aromatic hydrocarbons and their alkylated, halogenated, nitrated, and oxidized derivatives, phthalates, polychlorinated biphenyls (PCBs), traditional brominated flame retardants, alternative brominated flame retardants, declone analogs, halogenated carbazoles, liquid crystal monomers, siloxanes, and substances with high electron collision ionization efficiency and vapor pressures higher than 3.0 × 10⁻⁶ on the GC-MS instrument. -4 Ultraviolet absorbers, synthetic antioxidants and their conversion products at Pa (25 degrees Celsius).

[0020] Preferably, the liquid phase pretreatment step includes:

[0021] Step S22-1: Crop 1 / 4 of the image to capture PM 2.5 The quartz fiber filter membrane of the sample was placed in a 20 mL glass test tube, and 25 ng of recovery indicator was added to the sample to be tested. The recovery indicator was a liquid phase analysis target with 32 isotope labels.

[0022] Step S22-2: Add a mixed solution of methanol and acetonitrile in a 1:1 volume ratio to a test tube, so that PM... 2.5 The sample is completely immersed in the solution;

[0023] PM in a 40 kHz ultrasonic bath 2.5 The sample was subjected to ultrasonic extraction for 15 minutes, repeated three times, and the extracts from the three extractions were combined.

[0024] Step S22-3: Concentrate the combined extract to 1 mL using nitrogen blowing;

[0025] Step S22-4: The concentrated sample is purified by passing it through an 18-alkylsilane bonded silica solid-phase extraction column. The solid-phase extraction column is pre-activated with 6 mL of methanol before loading the sample, and the target analyte for liquid phase analysis is eluted with 6 mL of methanol.

[0026] Step S22-5: Concentrate the eluent to 200-300 μL using nitrogen blowing;

[0027] Step S22-6: Filter the concentrated sample through a polytetrafluoroethylene filter membrane with a pore size of 0.2 μm, and centrifuge at 3500 r / min for 5 min to remove insoluble particles to prevent clogging of the liquid chromatography injection needle;

[0028] Step S22-7: Transfer the filtrate to a 2mL sample vial with an inner liner. Before injection, add 25ng of internal standard to the sample. The internal standard is a liquid chromatography target analyte labeled with 13 isotopes.

[0029] Step S22-8: Quantitative analysis of the processed sample is performed using liquid chromatography-triple quadrupole mass spectrometry (LC-MS / MS). The target analytes for LC-MS / MS include aniline promoters, bisphenol A analogs, phthalate substitutes, organophosphates and their conversion products, phthalate conversion products, biodegradable plastic modifiers, and substances with high electrospray ionization efficiency and vapor pressure below 8.5 × 10⁻⁶ on the LC-MS / MS instrument. -1 Ultraviolet absorbers, synthetic antioxidants and their conversion products at Pa (25 degrees Celsius).

[0030] This invention also provides a system for high-throughput targeted analysis of multiple organic pollutants in atmospheric fine particulate matter, including a sampling module, a gas phase pretreatment module, a liquid phase pretreatment module, a first analysis module, a second analysis module, and a data processing module;

[0031] The sampling module, equipped with PM 2.5 The cut-head active sampler uses a quartz fiber filter membrane to capture atmospheric PM2.5. 2.5 sample;

[0032] The gas phase pretreatment module is used for PM2.5. 2.5 The target analytes for gas phase analysis in the sample were subjected to ultrasonic extraction, merging, and concentration in the first solvent.

[0033] The liquid phase pretreatment module is used for PM 2.5 The target analytes in the liquid phase analysis of the sample were subjected to ultrasonic extraction with a second solvent, purification by solid phase extraction, and concentration filtration.

[0034] The first analysis module is used to perform gas chromatography-triple quadrupole mass spectrometry (GC-MS) analysis on the gas phase extract.

[0035] The second analytical module is used for multi-reaction monitoring analysis of the liquid extract using liquid chromatography-triple quadrupole mass spectrometry.

[0036] The data processing module is used to perform quantitative calculations on the analysis results and to achieve high-throughput screening of multiple categories of traditional and new organic pollutants and their transformation products.

[0037] Preferably, the gas phase pretreatment module includes an addition unit for adding isotopically labeled recovery indicators and internal standards, an extraction unit for ultrasonic extraction with a mixed solvent of n-hexane and dichloromethane, and a concentration unit for concentrating the extract to a small volume.

[0038] The liquid phase pretreatment module includes an addition unit for adding isotopically labeled recovery indicators and internal standards, an extraction unit for ultrasonic extraction using a methanol and acetonitrile mixed solvent, and a unit for C... 18 The purification unit for solid-phase extraction purification, the filtration unit for centrifugal filtration, and the concentration unit for concentrating the extract and filtrate to a small volume.

[0039] Preferably, the first analysis module and the second analysis module each have a multi-reaction monitoring mode control unit, which is used to select the corresponding ion pair according to different target substances to achieve highly selective and highly sensitive quantitative analysis.

[0040] Preferably, the data processing module is used to integrate gas phase analysis data and liquid phase analysis data, perform quality control verification on pollutant concentration, recovery rate, method detection limit and matrix effect, and output screening results of traditional and new organic pollutants and their transformation products.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] 1. This invention achieves PM2.5 analysis through two sets of pretreatment and analysis processes: gas phase and liquid phase. 2.5 Comprehensive detection of traditional pollutants, new pollutants and their transformation products in samples, covering more than 600 target compounds.

[0043] 2. This invention integrates and optimizes the pretreatment process for multiple types of pollutants, enabling simultaneous treatment of the same PM2.5. 2.5 Parallel analysis of samples significantly improves detection throughput and saves experimental resources, achieving high efficiency and broad-spectrum screening.

[0044] 3. This invention enables high-throughput targeted analysis of pollutants with different physicochemical properties. Based on the isotope-labeled internal standard method, it achieves trace-level quantitative determination, ensuring the accuracy and reliability of the data.

[0045] 4. This invention effectively reduces the impact of differences in experimental reagents, changes in operators and instrument status on results through standardized pretreatment procedures and internal standard / substitute standard calibration and quantification strategies, ensuring the comparability of data from different batches of samples.

[0046] 5. This invention can simultaneously obtain information on parent pollutants and their degradation products, providing a scientific basis for atmospheric pollution behavior research, pollution source analysis, health risk assessment, and prevention and control strategies.

[0047] In summary, this invention not only establishes targeted analysis methods for traditional organic pollutants, including OCPs (26 types), PAHs (34 types), APAHs (40 types), NPAHs (24 types), OPAHs (13 types), XPAHs (27 types), PAEs (26 types), PCBs (37 types), and LBFRs (58 types), but also measures emerging pollutants that are of widespread interest to environmental scientists, including AALs (18 types), SAOs (43 types), ABFRs (18 types), BPAAs (15 types), DECs (12 types), PAEAs (44 types), PHCZs (15 types), OPEs (37 types), UVAs (35 types), LCMs (61 types), SXs (12 types), and BPMAs (11 types). Furthermore, since the aforementioned organic compounds undergo (non-)biotransformation in the environment to form metabolites, in order to gain a more comprehensive understanding of their atmospheric degradation process and improve detection accuracy and environmental significance, we also simultaneously measured the transformation derivatives (TPs) of some target analytes (especially the degradation products of SAOs, OPEs, and PAEs, totaling 48). A list of over 600 targeted analytical compounds and information on the isotopically labeled target substances used (as substitutes or internal standards, totaling 88) are shown in Tables 1 and 2.

[0048] Based on the physicochemical properties of the target organic pollutants (such as volatility, thermal stability, molecular polarity, key functional groups, and solubility in common organic solvents), this invention enables trace determination of all more than 600 targeted mass spectrometry screening compounds through two sets of sample pretreatment and instrumental analysis procedures.

[0049] This invention can achieve PM through two pretreatment processes. 2.5 The comprehensive coverage of over 600 organic pollutants in the sample significantly improves efficiency and saves resources, while effectively avoiding reduced comparability of results due to differences in experimental reagents, operators, and the condition of experimental instruments. Attached Figure Description

[0050] Figure 1 Polycyclic aromatic hydrocarbons (PAHs), alkylated polycyclic aromatic hydrocarbons (APAHs), nitropolycyclic aromatic hydrocarbons (NPAHs), oxidized polycyclic aromatic hydrocarbons (OPAHs), and halogenated polycyclic aromatic hydrocarbons (XPAHs) were found in Beijing PM. 2.5 The overall concentration distribution level in the sample;

[0051] Figure 2 The recovery rate distribution of gas phase analysis target compounds under different solvent extraction conditions is provided in a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter, which is an embodiment of the present invention. HEX, DCM, and ACE represent n-hexane, dichloromethane, and acetone, respectively, and the prefix SS represents the recovery rate after correction with a substitute standard.

[0052] Figure 3 This diagram illustrates the recovery rates of target compounds in a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter under different solvent extraction conditions, provided as an embodiment of the present invention. ACE, MeOH, and ACN represent acetone, methanol, and acetonitrile, respectively. The prefix SS indicates the recovery rate after correction for a standard substitute.

[0053] Figure 4 This invention provides an embodiment of a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter, showing the recovery rate distribution of liquid phase analysis target compounds under different solid phase extraction column purification conditions. Among these, Envi-Carb and ODS-C... 18 PSA stands for graphitized carbon black, octadecylsilane-bonded silica gel, and [other components]. N -Propylethylenediamine solid phase extraction column, the prefix SS indicates the recovery rate after correction for substituted standards.

[0054] Figure 5 The flowchart illustrates a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter, provided as an embodiment of the present invention. Detailed Implementation

[0055] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0056] like Figure 5As shown in this embodiment, a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter is provided, comprising the following steps:

[0057] Step S1: Use the device equipped with PM 2.5 Samples were collected using a high-flow-rate active atmospheric sampler (TE-5070-BLX, Tisch Environmental, Ohio, USA), with each sample collected at a depth of 1.0–1.3 m. 3 The sampling head is equipped with a quartz fiber filter (QM-A grade QFF; size: 203mm × 254mm; Whatman, Buckinghamshire, UK) and a flow rate of / minute for 24 hours to capture PM2.5 in the atmosphere. 2.5 Samples. Before sampling, the quartz fiber filter membrane was baked in a muffle furnace at 450°C for six hours to remove organic impurities and was weighed. Additionally, during sampling, the air temperature and pressure difference before and after sample collection were recorded to calculate the gas flow rate. After sampling, the sample was weighed, wrapped in aluminum foil, and frozen at -20°C until analysis. A blank sample collection method involved placing a blank quartz fiber filter membrane in a non-operating sampler and recovering it after 24 hours.

[0058] Step S2: Process the PM collected in step S1 2.5 The gas phase analysis target analytes in the sample are labeled with recovery indicators, extracted and concentrated, and internal standards are added for instrument quantification to obtain a gas phase analysis solution suitable for gas chromatography-tandem mass spectrometry analysis.

[0059] The liquid phase pretreatment step includes: processing the captured PM2.5 2.5 The target analytes in the sample are labeled with recovery indicators, extracted, purified and concentrated, and internal standards are added for instrument quantification to obtain a liquid analysis solution suitable for liquid chromatography-tandem mass spectrometry analysis.

[0060] Specifically, the steps include the following:

[0061] Step S21: Pretreatment steps for gas phase analysis target analytes:

[0062] Step S21-1: Crop 1 / 4 of the image to capture PM 2.5 The quartz fiber filter membrane of the sample was placed in a 20 mL glass test tube, and 25 ng of recovery indicator was added to the sample to be tested. The recovery indicator was a gas phase analysis target with 32 isotope labels.

[0063] Step S21-2: Add a mixed solution of n-hexane and dichloromethane in a 1:1 volume ratio to a test tube, so that PM... 2.5 The sample is completely immersed in the solution;

[0064] PM in a 40 kHz ultrasonic bath 2.5 The sample was subjected to ultrasonic extraction for 15 minutes, repeated three times, and the extracts from the three extractions were combined.

[0065] Step S21-3: Concentrate the combined extract to 200-300 μL using nitrogen blowing and transfer it to a 2 mL sample vial with an inner liner.

[0066] Step S21-4: Add 25 ng of internal standard to the concentrated sample. The internal standard is a gas phase analysis target analyte labeled with 11 isotopes.

[0067] Step S21-5: Quantitative analysis of the processed sample is performed using gas chromatography-triple quadrupole mass spectrometry (GC-MS). The target analytes for gas chromatography analysis include organochlorine pesticides, polycyclic aromatic hydrocarbons and their alkylated, halogenated, nitrated, and oxidized derivatives, phthalates, polychlorinated biphenyls (PCBs), traditional brominated flame retardants, alternative brominated flame retardants, declone analogs, halogenated carbazoles, liquid crystal monomers, siloxanes, and substances with high electron collision ionization efficiency and vapor pressures higher than 3.0 × 10⁻⁶ on the GC-MS instrument. -4 Ultraviolet absorbers, synthetic antioxidants and their conversion products at Pa (25 degrees Celsius).

[0068] Step S22: Pretreatment steps for target analytes in liquid chromatography:

[0069] Step S22-1: Crop 1 / 4 of the image to capture PM 2.5 The quartz fiber filter membrane of the sample was placed in a 20 mL glass test tube, and 25 ng of recovery indicator was added to the sample to be tested. The recovery indicator was a liquid phase analysis target with 32 isotope labels.

[0070] Step S22-2: Add a mixed solution of methanol and acetonitrile in a 1:1 volume ratio to a test tube, so that PM... 2.5 The sample is completely immersed in the solution;

[0071] PM in a 40 kHz ultrasonic bath 2.5 The sample was subjected to ultrasonic extraction for 15 minutes, repeated three times, and the extracts from the three extractions were combined.

[0072] Step S22-3: Concentrate the combined extract to 1 mL using nitrogen blowing;

[0073] Step S22-4: The concentrated sample is purified by passing it through an 18-alkylsilane bonded silica solid-phase extraction column. The solid-phase extraction column is pre-activated with 6 mL of methanol before loading the sample, and the target analyte for liquid phase analysis is eluted with 6 mL of methanol.

[0074] Step S22-5: Concentrate the eluent to 200-300 μL using nitrogen blowing;

[0075] Step S22-6: Filter the concentrated sample through a polytetrafluoroethylene filter membrane with a pore size of 0.2 μm, and centrifuge at 3500 r / min for 5 min to remove insoluble particles to prevent clogging of the liquid chromatography injection needle;

[0076] Step S22-7: Transfer the filtrate to a 2 mL injection bottle with an inner liner. Before injection, add 25 ng of internal standard to the sample. The internal standard is a liquid phase analysis target labeled with 13 isotopes.

[0077] Step S22-8: Quantitative analysis of the processed sample is performed using liquid chromatography-triple quadrupole mass spectrometry (LC-MS / MS). The target analytes for LC-MS / MS include aniline promoters, bisphenol A analogs, phthalate substitutes, organophosphates and their conversion products, phthalate conversion products, biodegradable plastic modifiers, and substances with high electrospray ionization efficiency and vapor pressure below 8.5 × 10⁻⁶ on the LC-MS / MS instrument. -1 Ultraviolet absorbers, synthetic antioxidants and their conversion products at Pa (25 degrees Celsius).

[0078] Step S3: Perform quantitative analysis on the gas phase analysis liquid and the liquid phase analysis liquid obtained in step S2, wherein the gas phase analysis liquid is analyzed by gas chromatography-triple quadrupole mass spectrometry and the liquid phase analysis liquid is analyzed by liquid chromatography-triple quadrupole mass spectrometry.

[0079] Furthermore, in this embodiment, the parameters of the gas chromatography-triple quadrupole mass spectrometry system are as follows:

[0080] (1) Instruments: Gas chromatography-triple quadrupole mass spectrometry (GCMS-TQ8040 NX; Shimadzu, Kyoto, Japan).

[0081] (2) Ion source temperature: 230℃; AUX end temperature: 300℃; Inlet temperature: 260℃.

[0082] (3) Ionization mode: Electron collision ionization (EI); Ion acquisition mode: Multiple reaction monitoring (MRM); The MRM ion pairs corresponding to each target are shown in Table 1.

[0083] Table 1. Basic information of each analytical target, the acquired multiple reaction monitoring (MRM) ion pairs, and the corresponding isotopically labeled internal and surrogate standards used in quantitative analysis on a gas chromatography-triple quadrupole mass spectrometer.

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] (4) Chromatographic column: Rxi-5Sil MS column (length: 30m, inner diameter: 0.25mm ID, film thickness: 0.25μm; Shimadzu, Kyoto, Japan).

[0097] (5) The initial temperature of the column oven is set to 40℃ and held for 1 minute. Then, the temperature is increased to 150℃ at 20℃ / minute and held for 1 minute. Then, the temperature is increased to 300℃ at 10℃ / minute and held for 8 minutes. Finally, the temperature is increased to 320℃ at 10℃ / minute and held for 15 minutes.

[0098] Furthermore, in this embodiment, the parameters of the liquid chromatography-triple quadrupole mass spectrometry system are as follows:

[0099] (1) Instrument: Ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry (LCMS-8060 NX; Shimadzu, Kyoto, Japan).

[0100] (2) Mobile phase A: 0.1% acetic acid + 2mM ammonium acetate; Mobile phase B: acetonitrile.

[0101] (3) Mobile phase flow rate: 0.4 mL / min.

[0102] (4) Column temperature: 40℃.

[0103] (5) Ionization mode: Based on the ionization characteristics of the target analyte, select ionization modes of different polarities, i.e., positive or negative electrospray ionization (ESI). + / ESI –Ion acquisition mode: Multiple reaction monitoring (MRM); MRM ion pairs corresponding to each target are shown in Table 2.

[0104] Table 2. Basic information of each analyte, acquired multiple reaction monitoring (MRM) ion pairs, and corresponding isotopically labeled internal and surrogate standards used in quantitative analysis using liquid chromatography-triple quadrupole mass spectrometry. + With ESI – These represent positive and negative electrospray ionization modes, respectively.

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] (6) Atomizing gas flow rate: 3L / min; heating gas flow rate: 10L / min; interface temperature: 300℃; desolventizing temperature: 525℃; desolventizing tube temperature: 250℃; heating block temperature: 400℃; drying gas flow rate: 10L / min.

[0114] (7) Chromatographic column: Acquity BEH C 18 Column (Length: 50 mm, Inner Diameter: 2.1 mm, Packing Thickness: 1.7 μm; Waters, Massachusetts, USA).

[0115] (8) Mobile phase procedure: Initially, B% is 10% and is maintained for 0.5 minutes. Then, it is increased to 98% within 14 minutes and maintained for 8 minutes. Finally, B% is restored to the initial state of 10%, and the system is equilibrated for 2.5 minutes.

[0116] Step S4: Based on the analysis results, high-throughput screening is performed on multiple categories of target substances, including traditional organic pollutants, new organic pollutants and their transformation products, according to the retention time of chromatographic peaks (offset less than 0.1 min), chromatographic peak shape (gaussian distribution), relative abundance between multiple reaction monitoring ion pairs (deviation less than 15%), and signal-to-noise ratio (greater than 3.0) on the obtained spectra.

[0117] Specifically as follows:

[0118] To ensure the quality of analytical data, systematic quality control measures were followed. For each batch of 8-10 samples, a process blank and a matrix-spiked sample were prepared simultaneously to evaluate the recovery rate of the target contaminant (absolute recovery rate: the ratio of the detected concentration to the labeled concentration; corrected recovery rate: the absolute recovery rate after correction for the standard recovery rate, with an acceptable range of 70-130%), matrix effect (the ratio of the peak signal of the target analyte in the sample extract to that in the organic solvent; close to 100% indicates a low matrix effect, while significantly higher or lower than 100% indicates that the co-eluting matrix can cause instrument signal gain or suppression, respectively), and method detection limit (the target analyte detectable in the blank: the product of the standard deviation of the concentration in the blank parallel sample and the 99% confidence interval of the t-test; the target analyte without residue in the blank: the product of the standard deviation of the concentration in the trace labeled parallel sample and the 99% confidence interval of the t-test). To detect potential contamination introduced during the testing process, blank samples were collected periodically and analyzed simultaneously.

[0119] In addition, this embodiment also provides a screening system based on a high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter, including a sampling module, a gas phase pretreatment module, a liquid phase pretreatment module, a first analysis module, a second analysis module, and a data processing module.

[0120] The sampling module, equipped with PM 2.5 The cut-head active sampler uses a quartz fiber filter membrane to capture atmospheric PM2.5. 2.5 sample;

[0121] The gas phase pretreatment module is used for PM2.5. 2.5 The target analytes in the gas phase analysis of the sample were subjected to ultrasonic extraction, merging, and concentration in the first solvent.

[0122] The gas phase pretreatment module includes an addition unit for adding isotopically labeled recovery indicators and internal standards, an extraction unit for ultrasonic extraction with a mixed solvent of n-hexane and dichloromethane, and a concentration unit for concentrating the extract to a small volume. The liquid phase pretreatment module is used for PM... 2.5 The target analytes in the sample were subjected to ultrasonic extraction with a second solvent, purification by solid-phase extraction, and concentration filtration.

[0123] The liquid phase pretreatment module includes an addition unit for adding isotopically labeled recovery indicators and internal standards, an extraction unit for ultrasonic extraction using a methanol and acetonitrile mixed solvent, and a unit for C... 18The system includes a purification unit for solid-phase extraction, a filtration unit for centrifugal filtration, and a concentration unit for concentrating the extract and filtrate to a small volume. The first analytical module performs gas chromatography-triple quadrupole mass spectrometry (GC-MS) analysis on the gas-phase extract; the second analytical module performs liquid chromatography-triple quadrupole mass spectrometry (LC-MS) analysis on the liquid-phase extract.

[0124] The first and second analysis modules each have a multi-reaction monitoring mode control unit, which is used to select the corresponding ion pairs according to different target substances to achieve highly selective and highly sensitive quantitative analysis.

[0125] The data processing module is used to perform quantitative calculations on the analysis results and to achieve high-throughput screening of multiple categories of traditional and new organic pollutants and their transformation products.

[0126] The data processing module is used to integrate gas phase analysis data and liquid phase analysis data, perform quality control verification on pollutant concentration, recovery rate, method detection limit and matrix effect, and output the screening results of traditional and new organic pollutants and their transformation products.

[0127] Furthermore, the high-purity chemical standards involved in this embodiment were purchased from Anpu (Shanghai, China), AccuStandard (Connecticut, USA), TCI (Shanghai, China), TRC (Ontario, Canada), Cambridge Isotope (Massachusetts, USA), Wellington (Ontario, Canada), CNW (Shanghai, China), Chiron (Trondheim, Norway), CATO (Guangzhou, China), Dr. Ehrenstorfer (Augsburg, Germany), and CDNIsotopes (Quebec, Canada).

[0128] This embodiment is simple to operate and optimizes PM. 2.5 The sample pretreatment process and instrument analysis parameters enable efficient trace determination of over 600 novel and traditional organic pollutants and their transformation products in atmospheric particulate matter, with method detection limits for each target analyte reaching pg / m³. 3 This method, at the higher level, facilitates a broad-spectrum analysis of atmospheric pollution, providing more comprehensive data support for formulating more detailed atmospheric environmental control standards and measures. Existing methods suffer from high time costs, resource waste, and reduced comparability of results due to differences in experimental reagents, operators, and instrument conditions. In contrast, this invention offers advantages such as high throughput, short processing time, low cost, and strong comparability of results, making it suitable for widespread application.

[0129] The following details the specific parameters.

[0130] Example 1: Shanghai PM 2.5 Determination of traditional and new organic pollutants in samples

[0131] 1. Reagents and Materials

[0132] A total of 654 target analytes were analyzed, which can be divided into more than twenty categories based on their molecular structure or application purpose. These include OCPs, PAHs, APAHs, XPAHs, NPAHs, OPAHs, PAEs, PCBs, LBFRs, AALs, SAOs, ABFRs, BPAAs, DECs, PAEAs, PHCZs, OPEs, UVAs, LCMs, SXs, BPMAs, and some of the transformation products (TPs) of the above compounds. In addition, 64 isotopically labeled target analytes were used as substitute standards (32 for gas chromatography and 32 for liquid chromatography), and 24 isotopically labeled target analytes were used as internal standards (11 for gas chromatography and 13 for liquid chromatography). Detailed information on the target analytes, substitute standards, and internal standards is shown in Tables 1 and 2.

[0133] 2. Sample Collection

[0134] PM2.5 concentration in Minhang District, Shanghai, between October 2023 and May 2025 2.5 Samples were captured using a high-flow-rate active atmospheric sampler (TE-5070-BLX, Tisch Environmental, Ohio, USA), with each sample taken at a flow rate of 1.0–1.3 m. 3 Collect samples at a flow rate of / min for 24 hours, and record the differential pressure at the start and end of sampling. After sampling, wrap the filter membrane with aluminum foil and store it in a -20°C freezer before analysis. For field blank collection, place a blank filter membrane in a non-operating sampler and recover the membrane after 24 hours.

[0135] 3. Sample pretreatment and instrumental analysis

[0136] 3.1 Target analytes for gas phase analysis

[0137] The pre-weighed material is used to capture PM. 2.5 A quarter of the sample filter membrane was cut and placed in a 20 mL glass tube. 25 ng of a substitute standard was added, followed by the addition of a hexane:dichloromethane (1:1, volume ratio) mixture to completely submerge the filter membrane. The mixture was sonicated in a water bath for 15 min, and then the extract was transferred. This process was repeated three times. The combined extracts were concentrated to 200–300 μL by nitrogen blowing and transferred to a 2 mL vial lined with an inner tube. The vial was then refrigerated. 25 ng of an internal standard was added before instrumental analysis for compound quantification.

[0138] The analytical instrument used was a gas chromatography-triple quadrupole mass spectrometer (GCMS-TQ8040 NX; Shimadzu, Kyoto, Japan). The gas chromatograph was equipped with an Rxi-5Sil MS column (length: 30.0 m, inner diameter: 0.25 mm ID, film thickness: 0.25 μm; Shimadzu, Kyoto, Japan). The column oven temperature was initially set at 40 °C for 1 minute, then increased to 150 °C for 1 minute, then increased to 300 °C for 8 minutes, and then increased to 320 °C for 15 minutes. The ion source and interface temperatures were 230 °C and 300 °C, respectively; the solvent delay time was 3 min. Target ion acquisition was achieved using multiple reaction monitoring (MRM) in electron collision ionization (EI) mode.

[0139] 3.2 Target analytes for liquid chromatography analysis

[0140] The pre-weighed material is used to capture PM. 2.5 A quarter of the sample filter membrane was cut and placed in a 20 mL glass test tube. 25 ng of a standard was added, followed by the addition of a 1:1 (v / v) mixture of methanol and acetonitrile to completely submerge the filter membrane. The mixture was sonicated in a water bath for 15 min, and then the extract was transferred. This process was repeated three times. The combined extract was concentrated to 1 mL by nitrogen blowing and then transferred to a solid-phase extraction column (ODS C) activated with 6 mL of methanol. 18 The target compound was eluted in a packing material and eluted with 6 mL of methanol. The eluent was then purged with nitrogen to 200–300 μL and transferred to a centrifugal filter membrane (PTFE filter element; 0.2 μm pore size) for filtration. The filtrate was then transferred to a 2 mL vial with an inner liner and stored frozen. 25 ng of internal standard was added before instrumental analysis for compound quantification.

[0141] The analytical instrument used was an ultra-high performance liquid chromatography-triple quadrupole mass spectrometer (LCMS-8060 NX; Shimadzu, Kyoto, Japan). Different ionization modes (ESI) were selected based on the molecular weight and polarity characteristics of the target analytes. + / ESI - AcquityBEH C 18A column (length: 50 mm, inner diameter: 2.1 mm, packing thickness: 1.7 μm; Waters, Milford, MA) was used to separate the analytes. The mobile phase was 0.1% acetic acid + 2 mm ammonium acetate (A) and acetonitrile (B), with a constant flow rate of 0.4 mL / min. Initially, B% was 10% and held for 0.5 min, then increased to 98% over 14 min and held for 8 min, before returning to the initial mobile phase ratio. The mass spectrometer end interface temperature, desolvation temperature, and heating block temperature were 300ºC, 525ºC, and 400ºC, respectively. The nebulizer and heating gas / drying gas flow rates were set to 3 L / min, 10 L / min, and 10 L / min, respectively. Target ion acquisition was performed using multiple reaction monitoring (MRM) mode.

[0142] 4. Quality Assurance and Quality Control

[0143] To ensure the reliability of experimental data, a process blank and a matrix-spiked sample were analyzed simultaneously for each batch of 8-10 samples. This was done to track potential contamination introduced during the experimental process and to assess the extraction and purification efficiency of the analytical steps, thereby calculating the detection limit of the method used. The recoveries of over 96% of the target analytes, after correction with substituted standards, were between 70% and 130%. The matrix effects for gas chromatography and liquid chromatography ranged from 77-129% and 71-119%, respectively, with method detection limits ranging from 0.16 to 3.98 pg / m³. 3 and 0.01 – 6.51 pg / m 3 level.

[0144] 5. Results Analysis

[0145] As shown in Table 3, the PM2.5 concentration in Shanghai's atmosphere... 2.5 The sample contained all the analytical target types covered by this patent, especially PAHs, APAHs, and OPEs, with over 30 homologues detected. Furthermore, the residual levels of SAOs, UVAs, PAEs, and their alternatives (i.e., PAEAs) were also quite significant. These substances are primarily derived from industrial and transportation emissions, highlighting the environmental impact caused by the increased intensity of human activities resulting from Shanghai's urbanization process. Meanwhile, compared to traditional pollutants (such as OCPs, PCBs, and LBFRs), emerging pollutants and their transformation products have a greater impact on PM2.5 levels. 2.5 The more frequent detection in the samples indicates that new pollutants have accumulated significantly in urban environmental media in recent years and have caused secondary pollution as atmospheric transformation processes occur.

[0146] Table 3. Traditional and new organic pollutants and their transformation products detected in Shanghai atmospheric PM2.5 using the sample pretreatment and instrumental analysis methods described in this patent.

[0147] Analysis target substance types Detected homologues ABFRs BEHTEBP, EHTBB, PBBZ, PBT, TBBZ, TBP DECs Anti-DCC-CO LBFRs BB-7, BB-29, BB-30, BB-101, BDE-15, BDE-47, BDE-77, BDE-99, BDE-100, BDE-154 LCMs 5CT, DPeBB, EBMB, ECTB, PPB OCPs DDE, Endrin PAHs NAP, THNAP, ACY, ACE, BP, FLUO, ANTH, PHEN, DBT, FLAN, PYRN, BaFlu, BcFlu, CCP, BaA, BcPhen, TPH, CHRY, BbF, BjF, BkF, BaP, BeP, PER, BghiP, I123P, DacA, DahA, COR, DaeF, DaeP, DahP, DaiP, DalP APAHs 1-MNAP, 2-MNAP, 2-ENAP, 1,2-MNAP, 1,3-MNAP, 2,7-MNAP, 2,6-MNAP, 1,4,5-MNAP, 2,3,5-MNAP, 1,4,6,7-MNAP, 1-MFLUO, 2-MFLUO, 9-MFLUO, 9,9-MFLUO, 1-MANTH, 2-MANTH, 2,3-MANTH, 1-MPHEN, 2-MPHEN, 3-MPHEN, 4-MPHEN, 9-MPHEN, 1,8-MPHEN, 3,6-MPHEN, 1,2,6-MPHEN, RET, 2-MDBT, 4-MDBT, 4,6-MDBT, 2-MFLAN, 3-MFLAN, 1-MBaA, 7,12-MBaA, 1-MCHRY, 6-MCHRY, 5-MCHRY, 7-MBaP NPAHs 1-M-4-NNAP, 5-NACE, 2-NBP, 3-NBP, 2-NFLUO, 3-NBF, 9-NANTH, 1-NPYRN, 4-NPYRN, 6-NCHRY, 7-NBaA OPAHs 1-IND, 1-NALD, 1,4-NQ, 1,8-NANH, 5,12-NACQ, 9-FLU, 1,2-ACNQ, 2-BPCA, 9,10-ANQ, 2-MANQ, BaFLUO, BANTone, BANTdione XPAHs CN-10, CN-73, CN-75, 1-ClANTH, 2-ClANTH, 9-ClPHEN, 3-ClFLAN, 1-ClPYRN,1368-ClPYRN, 1-BrPYRN, 6-ClBaP, 6-BrBaP PAEs DEP, DAlP, DiPrP, DnPrP, DiBP, DnBP, BMEP, DAMP, DiPeP, DEEP, BBP, DHxP,DEHP, DiOP, DnHeP, BBEP, DnOP, DnNP, DiDP, DnDP PCBs CB-15, CB-28, CB-37, CB-52, CB-104, CB-153, CB-155, CB-194, CB-206, CB-208, CB-209 PHCZs CZ, 1368-CCZ, 1368-BCZ SAOs 24-DBP, 26-DBP, BHT, DTBSBP, AO-246, AO-232, DTPD, PBNA, PANA, BDPA,DBDPA, DODPA, diAMS, DChA, AO-4703, AO-2246, AO-1081, AO-425, AO-2544, AO-15,B BBOT, AO-1076, AO-1024, AO-245, AO-1098, AO-1010 SAOTPs <![CDATA[BHT-Q, BHT-quinol, 4-NO2-DPA, 2-NO2-DPA , 4,4'-NO2-DPA, IPPD-Q, 6PPD-Q,BHT-CHO, BHT-OH, BHT-COOH, TDTBPP]]> SXs D6, D7, D8, D9, L3, L4, L5, L6, L7, L8 UVAs 3-BC, 4-MBC, IMC, EHS, HMS, 3-OH-BP, 4-HB, 4-DHB, BP-3, BP-2, BP-4, BP-12,UV-P, UV-326, UV-329, UV-328, UV-234, UV-360, SA-PA, OBA, OBA, PBMC Tinuvin622, AVO, OCT, EHT AALs BG, DPG, DTG, TPG, 2-Me-BTH, 2-MeS-BTH, 2-NH-BTH, MBTS, NCBA, Nocceler 64 BPAAs BPA, BPAF, BPB, BPE, BPM, BPP, BPS, BPZ BPMAs ATCEMM, BDMENP, DiPA, ECA, ERAcid, ERAMide, HDIE, ODBD, SYAD OPEs TCEP, TCIPP, TDCIPP, TEP, TIPRP, TPRP, TNBP, TBOEP, TEHP, TPHP, CDP, EHDPHP, TMTP, TOTP, TPTP, 2IPPDPP, 4IPPDPP, 4tBPDPP, IDDPP, T35DMPP, B2IPPP, 24DIPPDPP, B4IPPPP, B4tBPPP, B2tBPPP, T2IPPP, T3IPPP, B24DIPPP, T4tBPP, RDP, BPA - BDPP OPETPs BCEP, BCIPP, BDCIPP, DNBP, BBOEP, BEHP, BBOEHEP, 3 - OH - TNBP, DPHP PAEAs DMA, DnBA, DiBA, DHeNoA, DEHA, TCTM, TiNTM, TiDTM, MO, GMO, TEC, ATEC, TBC, ATBC, BTHC, DMAZ, DEHAZ, DMS, DBS, DEHS, DEGDB, DPGDB, DBM, DEHM, IPMS, DESU, TOCTT, DINCH, CTBTP PAETPs mMP, mEP, miPrP, miBP, mBP, mHxP, mBzP, mEHP, mCPP, mEOHP, mEHHP, mECPP, mCMHP

[0148] Example 2: Beijing PM 2.5 Quantitative analysis of polycyclic aromatic hydrocarbons and their derivatives in samples

[0149] 1. Reagents and Materials

[0150] The targeted screening analytes cover five classes of polycyclic aromatic hydrocarbons and their derivatives, including PAHs, APAHs, XPAHs, NPAHs, and OPAHs, totaling 138 homologues. Detailed information on the target analytes, corresponding substitutes, and internal standards is shown in Table 1.

[0151] 2. Sample Collection

[0152] The sampling site was located in Haidian District, Beijing. From January 2024 to January 2025, atmospheric PM2.5 was collected using the same sampling procedure as in Example 1. 2.5 sample.

[0153] 3. Sample pretreatment and instrumental analysis

[0154] The sample extraction steps and gas chromatography-triple quadrupole mass spectrometry parameters are the same as those in Example 1 for gas chromatography analysis of target analytes (including PAHs and their derivatives).

[0155] 4. Quality Assurance and Quality Control

[0156] The quality control standards and experimental procedures were the same as in Example 1. The recoveries of all target analytes, after correction for substitutes, ranged from 72% to 118%, with matrix effects ranging from 77% to 127%, and the method detection limits were between 0.19 pg / m³. 3 Up to 3.67 pg / m 3 between.

[0157] 5. Results Analysis

[0158] Figure 1 Five types of target objects were showcased in Beijing PM 2.5 The concentrations in the sample (denoted by "∑"), with median concentrations of ∑PAHs and ∑OPAHs reaching 4200 and 1920 pg / m³, respectively. 3 It is higher than ∑APAHs (median: 933 pg / m³). 3 ) and ∑NPAHs (225pg / m 3 The residual level of ∑XPAHs was on the order of magnitude greater than that of 29.3 pg / m³. 3 The relative lowest concentration was observed. Homologues constituted a significant proportion of the composition, with median concentrations exceeding 150 pg / m³. 3The compounds include four OPAHs (1,8-NANH, 1,2-ACNQ, BANTone, BANTdione), 11 PAHs (BbF, BjF, BghiP, BeP, BaP, CHRY, BkF, I123P, COR, DaeP, FLAN) and one APAH (7-MBaP).

[0159] Comparative Example 1: Comparison of Extraction Efficiency with Different Organic Solvents

[0160] The recovery rates of target substances using the extraction solvent selected in the sample pretreatment process were compared with those of commonly used extraction solvents.

[0161] The extraction solvents used in this comparative example were: a 1:1 mixture of n-hexane and dichloromethane (volume ratio) for gas chromatography analysis of the target analytes; and a 1:1 mixture of methanol and acetonitrile (volume ratio) for liquid chromatography analysis of the target analytes.

[0162] Other commonly used extraction solvents for gas phase analysis target analytes include n-hexane, dichloromethane, dichloromethane:acetone mixed solution (1:1, volume ratio), and acetone; other commonly used extraction solvents for liquid phase analysis target analytes include acetone, acetone:methanol mixed solution (1:1, volume ratio), methanol, and acetonitrile.

[0163] Using the solvents mentioned above, PM labeled with the target substances covered by this patent (see Tables 1 and 2) was extracted by water bath ultrasonication. 2.5 For the filtered membrane samples, the ultrasonication process was repeated three times, and the extracts were combined. The concentrated extract was then transferred to a vial and quantitatively analyzed using a gas chromatography-liquid chromatography-mass spectrometry (GCMS-TQ8040 NX and LCMS-8060 NX; Shimadzu, Kyoto, Japan). The extraction efficiencies of different extraction solvents were compared to select the optimal extraction reagent.

[0164] Gas phase analysis results of target analyte recovery with different extraction solvents are as follows: Figure ② As shown, the hexane:dichloromethane mixed solution (1:1, volume ratio) used in this comparative example had the best extraction effect; at the same time, if the recovery rate of the target analytes is corrected with a suitable substituted standard (see Table 1), the recovery rate of approximately 97% of the target analytes after substituted standard correction can be between 70% and 130%.

[0165] In the selection of liquid phase extraction solvents, the methanol:acetonitrile mixed solution (1:1, volume ratio) and pure methanol used in this comparative example showed the highest extraction efficiency; however, considering that the nitrogen blowing time required for pure methanol was too long, we chose the methanol-acetonitrile mixture; Figure 3 As shown, the target substance recovery rate of 95% can be between 70% and 130% after being corrected for with appropriate substitutes (see Table 2).

[0166] In summary, under the premise of unified operating standards, the extraction solvent selected in this comparative example has a higher extraction efficiency for more than 600 target organic pollutants than other commonly used organic solvents.

[0167] Comparative Example 2: Comparison of Results from Different Solid Phase Extraction Column Packing Materials

[0168] Since solid-phase extraction columns, namely silica gel columns, Florisil columns, and amino-bonded silica gel columns, are commonly used for gas phase analysis, the packing material contains the target compounds covered by this patent, resulting in excessively high process blank residue. Therefore, solid-phase extraction columns are not used for purification during the gas phase analysis sample pretreatment process.

[0169] The solid-phase extraction column used for the target analyte in this comparative example was: ODS C. 18 Solid phase extraction column.

[0170] Other commonly used solid-phase extraction columns for liquid chromatography analysis target analytes include: N-propylethylenediamine (PSA) solid-phase extraction column and graphitized carbon black (Envi-Carb) solid-phase extraction column.

[0171] The methanol solutions containing the target analytes for liquid chromatography were purified by passing them through the pre-activated methanol solid-phase extraction columns described above. After sample loading, elution was performed with methanol, and the eluent was concentrated before analysis using liquid chromatography-mass spectrometry (LCMS-8060 NX; Shimadzu, Kyoto, Japan). The recoveries of the target analytes on each solid-phase extraction column are shown below. Figure 4 It should be noted that there may be an error in the tag where "图2" is translated as "Figure ②" in the provided translation. It should probably be "Figure 2". You may want to double - check and correct it if necessary. As shown, the ODS C selected in this comparative example 18 The column performed significantly better than the other two solid-phase extraction columns. Furthermore, after correction with appropriate standard substitutes, the recoveries of approximately 97% of the target analytes remained between 70% and 130%. Therefore, under the premise of uniform operating standards, the solid-phase extraction column selected in this comparative example is superior to other commonly used solid-phase extraction packing materials.

[0172] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," and "counterclockwise," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0173] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0174] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter, used for quantitative analysis of PM2.

5. 2.5 The types and concentrations of potentially present organic pollutants in the sample, characterized in that, Includes the following steps: Step S1: Using a PM-equipped 2.5 The cut-head active atmospheric sampler collects fine particulate matter samples from the atmosphere and uses the fine particulate matter captured by the quartz fiber filter membrane as the PM2.5 to be measured. 2.5 sample; Step S2: Process the PM collected in step S1 2.5 The sample is pretreated by gas chromatography to form a gas phase analysis solution for gas chromatography-mass spectrometry analysis; The gas phase pretreatment step includes: Step S21-1: Crop 1 / 4 of the image to capture PM 2.5 The quartz fiber filter membrane of the sample was placed in a 20 mL glass test tube, and 25 ng of recovery indicator was added to the sample to be tested. The recovery indicator was a gas phase analysis target with 32 isotope labels. Step S21-2: Add a mixed solution of n-hexane and dichloromethane in a 1:1 volume ratio to a test tube, so that PM... 2.5 The sample is completely immersed in the solution; PM in a 40 kHz ultrasonic bath 2.5 The sample was subjected to ultrasonic extraction for 15 minutes, repeated three times, and the extracts from the three extractions were combined. Step S21-3: Concentrate the combined extract to 200-300 μL using nitrogen blowing and transfer it to a 2 mL sample vial with an inner liner. Step S21-4: Add 25 ng of internal standard to the concentrated sample. The internal standard is a gas phase analysis target analyte labeled with 11 isotopes. Step S21-5: Quantitative analysis of the processed sample is performed using gas chromatography-triple quadrupole mass spectrometry (GC-MS). The target analytes for gas chromatography analysis include organochlorine pesticides, polycyclic aromatic hydrocarbons and their alkylated, halogenated, nitrated, and oxidized derivatives, phthalates, polychlorinated biphenyls (PCBs), traditional brominated flame retardants, alternative brominated flame retardants, declone analogs, halogenated carbazoles, liquid crystal monomers, siloxanes, and substances with high electron collision ionization efficiency and vapor pressures higher than 3.0 × 10⁻⁶ on the GC-MS instrument. -4 Pa's ultraviolet absorbers, synthetic antioxidants and their conversion products; For the PM 2.5 The sample is pretreated with liquid chromatography to form a liquid analysis solution for liquid chromatography-mass spectrometry analysis; The liquid phase pretreatment step includes: Step S22-1: Crop 1 / 4 of the image to capture PM 2.5 The quartz fiber filter membrane of the sample was placed in a 20 mL glass test tube, and 25 ng of recovery indicator was added to the sample to be tested. The recovery indicator was a liquid phase analysis target with 32 isotope labels. Step S22-2: Add a mixed solution of methanol and acetonitrile in a 1:1 volume ratio to a test tube, so that PM... 2.5 The sample is completely immersed in the solution; PM in a 40 kHz ultrasonic bath 2.5 The sample was subjected to ultrasonic extraction for 15 minutes, repeated three times, and the extracts from the three extractions were combined. Step S22-3: Concentrate the combined extract to 1 mL using nitrogen blowing; Step S22-4: The concentrated sample is purified by passing it through an 18-alkylsilane bonded silica solid-phase extraction column. The solid-phase extraction column is pre-activated with 6 mL of methanol before loading the sample, and the target analyte for liquid phase analysis is eluted with 6 mL of methanol. Step S22-5: Concentrate the eluent to 200-300 μL using nitrogen blowing; Step S22-6: Filter the concentrated sample through a polytetrafluoroethylene filter membrane with a pore size of 0.2 μm, and centrifuge at 3500 r / min for 5 min to remove insoluble particles to prevent clogging of the liquid chromatography injection needle; Step S22-7: Transfer the filtrate to a 2mL sample vial with an inner liner. Before injection, add 25ng of internal standard to the sample. The internal standard is a liquid chromatography target analyte labeled with 13 isotopes. Step S22-8: Quantitative analysis of the processed sample is performed using liquid chromatography-triple quadrupole mass spectrometry (LC-MS / MS). The target analytes for LC-MS / MS include aniline promoters, bisphenol A analogs, phthalate substitutes, organophosphates and their conversion products, phthalate conversion products, biodegradable plastic modifiers, and substances with high electrospray ionization efficiency and vapor pressure below 8.5 × 10⁻⁶ on the LC-MS / MS instrument. -1 Pa's ultraviolet absorbers, synthetic antioxidants and their conversion products; Step S3: Perform mass spectrometry quantification on the gas phase analysis liquid and the liquid phase analysis liquid obtained in step S2, wherein the gas phase analysis liquid is analyzed by gas chromatography-triple quadrupole mass spectrometry, and the liquid phase analysis liquid is analyzed by liquid chromatography-triple quadrupole mass spectrometry. Step S4: Based on the analysis results, high-throughput screening is performed on multiple categories of target substances, including traditional organic pollutants, new organic pollutants and their transformation products, according to the retention time of chromatographic peaks, chromatographic peak shape, relative abundance between multiple reaction monitoring ion pairs, and signal-to-noise ratio on the obtained spectra.

2. A screening system based on the high-throughput targeted analysis method for multiple organic pollutants in atmospheric fine particulate matter as described in claim 1, characterized in that, It includes a sampling module, a gas phase pretreatment module, a liquid phase pretreatment module, a first analysis module, a second analysis module, and a data processing module; The sampling module, equipped with PM 2.5 The cut-head active sampler uses a quartz fiber filter membrane to capture atmospheric PM2.

5. 2.5 sample; The gas phase pretreatment module is used for PM2.

5. 2.5 The target analytes for gas phase analysis in the sample were subjected to ultrasonic extraction, merging, and concentration in the first solvent. The liquid phase pretreatment module is used for PM 2.5 The target analytes in the liquid phase analysis of the sample were subjected to ultrasonic extraction with a second solvent, purification by solid phase extraction, and concentration filtration. The first analysis module is used to perform gas chromatography-triple quadrupole mass spectrometry (GC-MS) analysis on the gas phase extract. The second analytical module is used for multi-reaction monitoring analysis of the liquid extract using liquid chromatography-triple quadrupole mass spectrometry. The data processing module is used to perform quantitative calculations on the analysis results and to achieve high-throughput screening of multiple categories of traditional and new organic pollutants and their transformation products.

3. The screening system for a high-throughput targeted analysis method of multiple organic pollutants in atmospheric fine particulate matter according to claim 2, characterized in that, The gas phase pretreatment module includes an addition unit for adding isotopically labeled recovery indicators and internal standards, an extraction unit for ultrasonic extraction of a mixed solvent of n-hexane and dichloromethane, and a concentration unit for concentrating the extract to a small volume. The liquid phase pretreatment module includes an addition unit for adding isotopically labeled recovery indicators and internal standards, an extraction unit for ultrasonic extraction using a methanol and acetonitrile mixed solvent, and a unit for C... 18 The purification unit for solid-phase extraction purification, the filtration unit for centrifugal filtration, and the concentration unit for concentrating the extract and filtrate to a small volume.

4. The screening system for a high-throughput targeted analysis method of multiple organic pollutants in atmospheric fine particulate matter according to claim 2, characterized in that, The first and second analysis modules each have a multi-reaction monitoring mode control unit, which is used to select the corresponding ion pairs according to different target substances to achieve highly selective and highly sensitive quantitative analysis.

5. The screening system for a high-throughput targeted analysis method of multiple organic pollutants in atmospheric fine particulate matter according to claim 2, characterized in that, The data processing module is used to integrate gas phase analysis data and liquid phase analysis data, perform quality control verification on pollutant concentration, recovery rate, method detection limit and matrix effect, and output screening results of traditional and new organic pollutants and their transformation products.

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