Atmospheric gaseous and particulate organic matter orbital hydrazine mass spectrum rapid analysis method and processing system

Abstract

The invention provides a system for collecting, analyzing and processing organic matter components in atmospheric gaseous and particulate matters. The invention further provides application of the system for collecting, analyzing and processing the organic matter components in the atmospheric gaseous and particulate matter in detection of weak-polarity and / or polar organic matter components in the atmospheric gaseous and particulate matter. The invention further provides an orbital hydrazine mass spectrum rapid analysis method for organic matter components in atmospheric gaseous and granular substances. The invention further provides a method for detecting the organic sulfate components in the atmospheric gaseous and granular substances. According to the gas-gas state and particle state organic matter orbital hydrazine mass spectrum rapid analysis method and the processing system provided by the invention, an instrument is simple in structure, offline is not needed, only one-step pretreatment is needed, pretreatment loss and pollution are avoided, and determination can be carried out after spectrogram intelligent analysis on the instrument; the method is suitable for rapid quantitative analysis and non-targeted screening of organic matters in atmospheric gaseous and granular samples.

Description

Technical Field

[0001] This invention belongs to the technical field of environmental monitoring, and relates to a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. Specifically, it relates to a high-resolution rapid quantitative analysis and non-targeted screening method for organic components in gaseous and particulate matter in ambient air and pollution source gases after ionization at normal pressure by orbital hydrazine mass spectrometry, as well as its sample collection, pretreatment, ionization method and data processing system. Background Technology

[0002] Ambient air and exhaust emissions from pollution sources contain gaseous and particulate matter of different sizes. Among them, highly volatile organic compounds, some moderately volatile and semi-volatile organic compounds exist in the gaseous state, while semi-volatile and non-volatile organic compounds usually exist in the particulate state.

[0003] Traditional methods for analyzing gaseous moderately volatile or semi-volatile organic compounds typically employ adsorbents such as activated carbon, molecular sieves, or Tenax-TA. After collecting a certain volume, the gaseous organic compounds are extracted or desorbed in the laboratory using solvent extraction or thermal desorption methods, followed by gas chromatography-mass spectrometry (GC-MS) analysis. Offline methods for particulate organic compounds are suitable for offline collection using filter membranes, but have low temporal resolution and require pretreatment processes such as solvent extraction and concentration before GC-MS or LC-MS analysis. Polar organic compounds usually require derivatization before analysis, and some require different pretreatments before analysis on liquid chromatography-mass spectrometry (LC-MS).

[0004] Online organic mass spectrometry, widely used in scientific research in recent years, primarily obtains mass spectrometry fragments. The substance category is determined by the ratio of characteristic fragments. However, this method suffers from background interference, and large molecules are easily fragmented, with similar fragments mixed together, making it difficult to infer their molecular composition. Furthermore, the limited molecular weight measurement range, weak signal response of high-boiling-point organics, and difficulty in identifying secondary organic compounds have become limiting factors in atmospheric organic matter analysis. For example, while existing technologies such as patent CN201811376380.3 employ high-resolution mass spectrometry, they are mainly aimed at agricultural product detection and still rely on traditional chromatographic separation methods, failing to meet the needs for rapid detection of atmospheric organic matter.

[0005] Traditional methods for analyzing atmospheric organic matter suffer from the following technical bottlenecks: 1) Complex sample pretreatment, requiring multiple extraction, concentration, and derivatization steps. 2) Long analysis cycles, making rapid response monitoring difficult. 3) Insufficient resolution of conventional mass spectrometry methods, making it difficult to accurately identify organic matter in complex matrices. 4) Limited data processing methods, lacking dedicated analytical algorithms for atmospheric organic matter. Summary of the Invention

[0006] Existing mass spectrometry methods require large amounts of samples and complex pretreatment procedures or equipment for mass spectrometry analysis. The purpose of this invention is to provide a rapid mass spectrometry analysis method and processing system for atmospheric gaseous and particulate organic compounds. This method enables rapid pretreatment, high-quality quantitative analysis, and qualitative screening of weakly polar or nonpolar organic components in atmospheric gaseous and particulate samples, achieving efficient, rapid, and high-precision detection of organic components in the atmosphere.

[0007] To achieve the above and other related objectives, the first aspect of the present invention provides a system for collecting, analyzing and processing organic components in atmospheric gaseous and particulate matter, comprising a shell, an ion transmission tube disposed on the shell, the shell being hollow and the ion transmission tube penetrating through the shell, an ionization source and a sample disk disposed inside the shell, the sample inlet of the sample disk cooperating with the output end of the ionization source, the sample outlet of the sample disk cooperating with the input end of the ion transmission tube, and the output end of the ion transmission tube being connected to an orbital hydrazine mass spectrometer.

[0008] The second aspect of this invention provides the use of an atmospheric gaseous and particulate matter organic component collection, analysis and processing system in the detection of weakly polar and / or polar organic components in atmospheric gaseous and particulate matter.

[0009] The third aspect of this invention provides a rapid orbital hydrazine mass spectrometry analysis method for organic components in atmospheric gaseous and particulate matter, comprising: collecting samples using the aforementioned atmospheric gaseous and particulate matter organic component acquisition and analysis processing system, placing the samples on a sample tray, exciting and ionizing them with an ion source, obtaining ionized target molecules, detecting them by orbital hydrazine mass spectrometry, analyzing the obtained mass spectrum data, and screening based on the precise mass number or ion abundance ratio of the molecular ions to determine the target components in the sample molecules.

[0010] A fourth aspect of this invention provides a method for detecting organic sulfate esters in atmospheric gaseous and particulate matter, comprising the following steps: 1) Samples containing gaseous organic matter and / or particulate organic matter in ambient air or exhaust gas from pollution sources are analyzed using the same steps as the above-mentioned rapid analysis method for organic matter in gaseous and particulate matter in the atmosphere by orbital hydrazine mass spectrometry to obtain ionized sample molecules. 2) The standards for organic sulfate esters, namely glycolate sulfate, lactate sulfate, pinene sulfate, limonene sulfate, and limonene sulfate, are obtained by using the same steps as the rapid analysis method of orbital hydrazine mass spectrometry for organic components in atmospheric gaseous and particulate matter, to obtain ionized standard molecules. 3) The ionized standard molecules obtained in step 2) are measured using the same steps as the rapid analysis method for organic components in gaseous and particulate matter in the atmosphere described above. Based on the precise mass number or ion abundance ratio of the molecular ion of the standard molecules, the mass spectrum and response intensity are extracted from the corresponding spectral library. Then, the ionized sample molecules obtained in step 1) are measured using the same steps as the rapid analysis method for organic components in gaseous and particulate matter in the atmosphere described above. Based on the mass spectrum of the sample molecules, the specific organic sulfate ester components are determined, and the content of organic sulfate ester components in the sample molecules is calculated based on the response intensity of the sample molecules using any one of the external standard method, internal standard method, or standard addition method.

[0011] As described above, the rapid analysis method and processing system for orbital hydrazine mass spectrometry of atmospheric gaseous and particulate organic matter provided by the present invention has the following beneficial effects: (1) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry, which can realize the ionization of gaseous organic matter collected offline on adsorbent and particulate samples enriched on quartz filter membrane by direct ionization technology under open atmospheric pressure environment. Only a small amount of sample and a small amount of solvent are required to achieve direct and rapid analysis.

[0012] (2) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry, which can be widely used for rapid ionization and high-resolution mass spectrometry analysis of gaseous and particulate samples of ambient air and pollution source exhaust gas. It is suitable for the analysis of gaseous and particulate organic matter emitted from ambient air and pollution source exhaust gas such as motor vehicle exhaust, industrial point source, area source, etc., and can perform high-resolution quantitative analysis and screening of unknowns.

[0013] (3) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter orbital hydrazine mass spectrometry, which requires only a small amount of solvent and simple pretreatment. That is, it only requires simple sampling, adding a trace amount of solvent and internal standard and mixing, and can directly achieve room temperature excitation in the sample tray. The solvent system is developed using methanol / water mixed solvent or methanol / acetonitrile / water mixed solvent. The in-situ excitation efficiency is 30% higher than that of traditional Soxhlet extraction followed by ionization (recovery rate >85%). The pretreatment time is shortened from the traditional 4-8 hours to 1-5 minutes, which can achieve efficient and rapid quantitative analysis with high resolution.

[0014] (4) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. It has few steps, no pretreatment loss or pollution, and realizes rapid low-solvent extraction and high-resolution detection of atmospheric gaseous and particulate organic matter. It has a simple structure, is easy to maintain, requires only one pretreatment step, has no transfer loss, and can be used for analysis. It can be used for quantitative analysis of nonpolar, weakly polar and polar organic molecules in atmospheric samples and screening of unknowns.

[0015] (5) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. The instrument has a simple structure, is easy to maintain, requires only one pretreatment step, has no transfer loss, and can be used for analysis immediately. It is suitable for rapid quantitative analysis and non-targeted screening of organic matter in atmospheric gaseous and particulate samples. It effectively improves the efficiency of instrument operation and personnel operation. After assembly, there is no need for traditional extraction and concentration steps, avoiding sample loss and solvent consumption caused by multiple extraction and transfer. Multiple samples can be rapidly analyzed in one processing step. It has high ionization efficiency and high mass-time resolution.

[0016] (6) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. The processing system is an integrated sampling-analysis coupling system that directly couples the sampling device with the high-resolution mass spectrometry system. Through the designed "sample disk-ionization source-ion transport" three-in-one structure, a "zero-loss" process from sampling to analysis is achieved. Compared with the traditional pretreatment method, which requires offline extraction, concentration, transfer, filtration and other multi-step processes after separate sampling, this processing system shortens the analysis time from 4 to 24 hours in the traditional method to within 5 to 10 minutes. At the same time, it can realize the analysis of online and offline samples.

[0017] (7) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter orbital hydrazine mass spectrometry. The processing system adopts a modular design sample tray, integrates 12 independent sample positions, and supports batch continuous analysis. It has a built-in positioning coding system (A1-C4 identification) to ensure accurate and repeatable analysis positions. It is compatible with two carriers: adsorbent (gaseous sample) and filter membrane (particulate sample), and can realize rapid synchronous analysis of collected atmospheric gaseous and particulate samples, greatly shortening the sample pretreatment time and solving the problem of long process of traditional methods.

[0018] (8) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. The processing system has developed an open-type ion source and a connection method between the sample and the mass spectrometer; optimized the carrier gas composition and discharge parameters to improve the ionization efficiency of semi-volatile organic compounds; realized in-situ ionization of the sample, avoiding sample loss in the traditional ionization process, and improved the response of weakly polar organic compounds. By combining glow discharge with Penning ionization mode, ionization excitation can be performed simultaneously using a "dual-mode ionization source"; the discharge chamber uses special ceramic materials to ensure discharge stability (CV<5%); the adjustable discharge needle design (2-5kV continuously adjustable); and the carrier gas mixing chamber achieves precise control of the He / N2 ratio (±2%).

[0019] (9) This invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. An adaptive adjustment algorithm for ionization parameters is established, automatically optimizing the discharge voltage based on the initial scan signal intensity, and dynamically adjusting the carrier gas ratio based on the mass number distribution. A "low-high" adjustable ionization mode is developed: a low ionization mode (0.5~2.5kV) for easily ionized compounds, and a high ionization mode (2.5~5kV) for difficult-to-ionize substances.

[0020] (10) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry, which has a dedicated internal standard channel in the sample pan and adopts... 13 C isotope-labeled compounds were used as internal standards to achieve real-time signal drift correction (RSD<8%).

[0021] (11) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. It uses a peak identification algorithm based on a deconvolutional neural network (CNN) to identify characteristic target substances that are different from matrix and solvent interference. The high-resolution mass spectrometry can identify unknown substances with an accuracy of >95% and can distinguish adjacent peaks with an overlap of up to 80%. A two-dimensional matching model of retention time and precise mass number is established with a matching accuracy of 0.001 Da and a false positive rate of <3%. An automatic time series analysis function is designed to perform multi-sample comparison and clustering as well as analysis of the time change trend of the same substance.

[0022] (12) The present invention provides a rapid analysis method and processing system for atmospheric gaseous and particulate organic matter by orbital hydrazine mass spectrometry. Based on the type of target substance and the availability of standard samples, it integrates three quantitative methods, including the external standard method (R... 2 >0.99), internal standard method (RSD<10%), standard addition method (recovery rate 85-115%), establish a combination of multidimensional quantitative analysis methods.

[0023] (13) This invention provides a rapid mass spectrometry analysis method and processing system for atmospheric gaseous and particulate organic compounds, improving analytical efficiency and performance. The analysis time for a single sample is ≤10 min, pretreatment time is reduced by more than 90%, and solvent consumption is reduced by more than 95%. The detection limit can reach pg / m³. 3 With a relative standard deviation of <15%, it can simultaneously perform qualitative and quantitative detection of 300+ organic compounds. Suitable for rapid monitoring of trace organic compounds and supports screening for unknown substances. Attached Figure Description

[0024] Figure 1 The diagram shows the overall structure of the system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter according to the present invention.

[0025] Figure 2 The diagram shown is a partial structural diagram of the system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter according to the present invention.

[0026] Figure 3 The diagram shown is a structural diagram of the sample tray in the atmospheric gaseous and particulate matter organic component acquisition, analysis and processing system of the present invention.

[0027] Figure 4 The diagram shows the analysis flowchart of the rapid analysis method for atmospheric gaseous and particulate organic matter using orbital hydrazine mass spectrometry in this invention.

[0028] Figure 5 The diagram shows the sample tray of the system for collecting, analyzing and processing organic components in atmospheric gaseous and particulate matter according to the present invention.

[0029] Figure 6 shows the mass spectrum of the molecular ion composition of organic sulfate components with typical atmospheric source characteristics detected in environmental samples according to the present invention. Figure 6a C3H5O4S - , Figure 6b C4H7O4S - , Figure 6c C6H9O6S - , Figure 6d C8H 17 O4S - , Figure 6e C6H5O4S - , Figure 6f C7H7O4S - , Figure 6g C5H8NO8S - , Figure 6h C8H 13 O7S - , Figure 6i C 10 H 15O7S - , Figure 6j C 10 H 16 NO7S - , Figure 6k C9H 14 NO8S - , Figure 6l C 15 H 25 O5S - , Figure 6m C 18 H 33 O8S - , Figure 6n C 20 H 37 O7S - , Figure 6o C 19 H 37 O8S - , Figure 6p C 10 H 31 O5S - .

[0030] Figure Labels 1 is the ionization source; 2 is the ion transmission tube; 3 is the orbital hydrazine mass spectrometer; 4 is the sample tray; 5 is the shell; 6 is the motor; 61 is the rotating shaft; 7 is the non-perforated tray cover; 8 is the perforated tray cover; 9 is the carrier gas input tube; 10 is the sampling tube; 11 is the sample placement hole; 12 is the opening; 13 is the support. Detailed Implementation

[0031] After extensive research and exploration, the inventors of this invention will now describe the specific technical details of the rapid analysis method and processing system for atmospheric gaseous and particulate organic matter using orbital hydrazine mass spectrometry.

[0032] The first aspect of this invention provides a system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter, such as... Figure 1-3 As shown, it includes a housing, on which an ion transmission tube is provided. The housing is hollow and the ion transmission tube passes through the housing. An ionization source and a sample disk are provided inside the housing. The sample inlet of the sample disk is matched with the output end of the ionization source, and the sample outlet of the sample disk is matched with the input end of the ion transmission tube. The output end of the ion transmission tube is connected to an orbital hydrazine mass spectrometer.

[0033] In the above-described device, the housing is rectangular in shape, and at least one observation window is provided on each of the four side walls of the housing. The housing seals the ionization source and the sample tray within it. The observation windows are used to observe the positions of the ionization nozzle of the ionization source, the sample tray, and the ion transmission tube, facilitating adjustment.

[0034] In one specific embodiment, observation windows are provided on all four side walls of the housing.

[0035] In the aforementioned device, the housing is made of stainless steel or aluminum oxide. This ensures that the housing material will not react with reactive substances in the atmosphere.

[0036] In one specific embodiment, the observation window is made of heat-resistant quartz.

[0037] In the above-mentioned device, the ion transmission tube is a conventional spare tube for the ion source.

[0038] In the above-mentioned device, such as Figure 1 As shown, the output end of the ion transmission tube is connected to the gas inlet of the orbital hydrazine mass spectrometer.

[0039] The aforementioned orbital hydrazine mass spectrometry is a quadrupole-electrostatic orbittrap mass spectrometer (Q Exactive). Q Exactive is a liquid chromatography-mass spectrometry (LC-MS) instrument manufactured by Thermo Fisher Scientific, based on orbitrap technology, featuring an ultra-high resolution mass analyzer. It boasts ultra-high resolution, ultra-high mass precision, ultra-high sensitivity, and quantitative capabilities superior to high-end triple quadrupole spectrometers. The aforementioned orbital hydrazine mass spectrometry is also an open ion trap mass spectrometer.

[0040] After the carrier gas is introduced through the carrier gas input tube, the ion transmission tube is used to transport the thermionic electrons generated by the collision and ionization of particulate organic matter into the orbital hydrazine mass spectrometer for detection.

[0041] In the aforementioned apparatus, the ionization source is an open-type atmospheric pressure desorption ionization source. Specifically, the ionization source is an atmospheric pressure ionization source that directly ionizes at atmospheric pressure.

[0042] In one specific embodiment, the ionization source is selected from one of the following: electrospray ionization source (ESI), microwave-induced plasma desorption / discharge ionization source (MIPDI), direct analysis in real-time (DART) ionization source, and flowing atmospheric pressure ionization source (FAPA).

[0043] The ionization source has a discharge chamber that allows a carrier gas to be introduced, which comes into contact with the discharge needle to form a glow discharge, and the generated excited-state high-energy gas atoms or molecules are ejected from the ion source.

[0044] In the above-mentioned device, such as Figure 1 , 2 As shown, the input terminal of the ionization source is connected to a carrier gas input pipe.

[0045] In one specific implementation, such as Figure 1 As shown, the carrier gas input pipe passes through the housing and the output end of the carrier gas input pipe is connected to the input end of the ionization source.

[0046] In one specific embodiment, the carrier gas input pipe is made of carbon black or copper.

[0047] In one specific embodiment, the carrier gas introduced into the carrier gas inlet pipe is an inert gas, preferably helium (He) or nitrogen (N2). The purity of the helium (He) or nitrogen (N2) is not less than 99.999%.

[0048] In the above-mentioned device, such as Figure 1-3 As shown in Figure 5, the sample disk includes a disk body, and a motor is provided outside the disk body. The center of the disk body is detachably sleeved on the rotating shaft of the motor so that the disk body can move circumferentially around the rotating shaft of the motor under the drive of the motor. The disk body is provided with at least one downwardly recessed sample placement hole, which is matched with the output end of the ionization source and the input end of the ion transmission tube, respectively.

[0049] In one specific implementation, such as Figure 1-3 As shown, the disk is circular.

[0050] In one specific embodiment, the motor is a conventionally provided shaft motor. It is used to cause the disc to move circumferentially around the motor's shaft under the motor's drive. Specifically, the disc is detachably snapped onto the motor's shaft, and under the drive of the shaft motor, it rotates around the shaft at a certain speed within the housing, thus achieving continuous sample injection.

[0051] In one specific embodiment, the rotation speed of the disk is adjustable and can be adjusted according to the response intensity of the excited molecular ions in the mass spectrometer. After the analysis of one set of sample disks is completed, another set of samples can be inserted to continue the analysis.

[0052] In one specific implementation, such as Figure 3 As shown, the number of sample placement holes is 12-24, preferably 12 or 24. These sample placement holes are used to place samples to prevent solvent splashing during sample ionization. By integrating 12 or 24 independent sample positions, batch continuous analysis is supported, enabling continuous analysis of multiple samples or daily variation data.

[0053] In one specific embodiment, the disc body is marked with letter identifiers, and the sample placement holes are marked with number identifiers. The combination of letter and number identifiers on the disc body and sample placement holes forms a built-in positioning coding system, such as A1-C4, indicating the positions of different sample discs and different sample placement holes on the same sample disc. For example, A1 and A2 represent the positions of sample placement holes 1 and 2 on sample disc A, and A1 and B1 represent the positions of sample placement holes 1 on sample disc A and sample disc B, ensuring accurate and repeatable analysis positions.

[0054] In one specific embodiment, when the sample is a gaseous organic component in ambient air or exhaust gas from a pollution source, an adsorbent is placed in the sample placement hole; when the sample is a particulate organic component in ambient air or exhaust gas from a pollution source, a filter membrane is placed in the sample placement hole.

[0055] In a further embodiment, the adsorbent is an XAD adsorbent or a Tenax-TA adsorbent. For example, the XAD adsorbent is DuPont or Merck Supelco's Amberlite XAD-2 adsorbent, containing poly(styrene-divinylbenzene) adsorbent resin or Amber Lite XAD-4 polymer. The Tenax-TA adsorbent is Merck Supelco's 2,6-diphenyl-p-phenyl ether-based adsorbent, containing 2,6-p-phenyl diphenyl ether or poly2,6-diphenyl-p-phenyl ether, with a particle size of 60-80 mesh (0.18-0.25 mm).

[0056] In a further embodiment, the filter membrane is a quartz fiber filter membrane.

[0057] In one specific embodiment, the fact that the sample placement hole is matched with the output end of the ionization source and the input end of the ion transmission tube means that the sample placement hole is directly opposite the output end of the ionization source and the input end of the ion transmission tube, respectively.

[0058] In one specific implementation, such as Figure 3 , 5 As shown, the sample tray also includes a tray cover, which includes a non-perforated tray cover and a perforated tray cover. The tray cover completely covers the tray body, and the perforated tray cover has an opening that matches the position of the sample placement hole.

[0059] In a further embodiment, such as Figure 5 As shown, the disk cover is detachably connected to a bracket to detachably fix the disk cover above the disk body. The user can freely replace the non-perforated disk cover and the perforated disk cover. The non-perforated disk cover is used to seal the disk body for dust prevention, while the perforated disk cover is used for sampling. During sample injection, it seals the sample that is not to be excited by the ion source while opening the sample to be excited by the ion source.

[0060] In a further embodiment, the disc cover is detachably connected to a bracket, and the disc cover is sleeved on the support rod of the bracket.

[0061] In a further embodiment, the disc body and disc cover are made of quartz or polytetrafluoroethylene (PTFE), which is corrosion-resistant and prevents adsorption.

[0062] In a further embodiment, such as Figure 3 , 5 As shown, the aperture of the opening is not smaller than the aperture of the sample placement hole. The opening is the location where the sample is excited by the ion source, that is, the sample undergoes an excitation ionization reaction at this location.

[0063] In a further embodiment, the matching of the position of the opening and the sample placement hole means that each sample placement hole is moved to a position below the opening and is connected to the opening, and the sample placement hole is directly opposite the output end of the ionization source and the input end of the ion transport tube through the connected opening.

[0064] In one specific implementation, such as Figure 1-3 As shown in Figure 5, a sampling tube is also matched on the disc body. The sampling tube penetrates the shell and the output end of the sampling tube is matched with the position of the disc body. A sampling pump is provided at the input end of the sampling tube.

[0065] In a further embodiment, the sampling tube is selected from at least one of quartz or passivated copper tube.

[0066] In a further embodiment, the sampling pump is a conventionally used vacuum pump. By adjusting the sampling flow rate and the rotary table speed, the volume collected at each sample location can be controlled by the sampling speed and residence time.

[0067] In a further embodiment, the position of the output end of the sampling tube matching the position of the disk body means that the output end of the sampling tube is directly opposite the position of the disk body, which facilitates the input of samples onto the disk body.

[0068] In a further embodiment, when collecting gaseous organic matter components from ambient air or exhaust gas from pollution sources, the sampling tube input end is provided with a first filter membrane for filtering particulate organic matter, and the disk is filled with an adsorbent for adsorbing gaseous organic matter components; when collecting particulate organic matter components from ambient air or exhaust gas from pollution sources, the disk is provided with a second filter membrane for adsorbing particulate organic matter components.

[0069] In the optimal implementation, the adsorbent is an XAD adsorbent or a Tenax-TA adsorbent.

[0070] In the optimized embodiment, the first filter membrane is a Teflon filter membrane or a stainless steel fine mesh. It is used to filter particulate organic matter and block the adsorbent.

[0071] In the optimized embodiment, the second filter membrane is a quartz fiber filter membrane. It is used to filter particulate organic matter and block the adsorbent.

[0072] In the above-mentioned device, the system further includes a controller, which is communicatively connected to the ionization source and the orbital hydrazine mass spectrometer, respectively, and is used to send an excitation ionization command to the ionization source to drive the ionization source to perform excitation ionization, and to send a detection command to the orbital hydrazine mass spectrometer to drive the orbital hydrazine mass spectrometer to perform component detection.

[0073] In one specific embodiment, the controller is also communicatively connected to the motor and the sampling pump, and is used to send start or stop rotation commands to the motor to drive the disk to rotate or stop rotation via the rotating shaft. It also sends start or stop sampling commands to the sampling pump to drive the sampling pump to sample or stop sampling via the sampling tube. This allows the sample disk to rotate according to a set time under the drive of the motor, thereby achieving the purpose of switching samples.

[0074] In one specific embodiment, the controller is a conventionally used controller. As those skilled in the art will understand, the controller's calculation, comparison, judgment, and instruction output processes can all be implemented using existing integrated circuit modules, programmable logic devices, other hardware, or by installing corresponding software modules. The controller is externally powered.

[0075] The second aspect of this invention provides the use of an atmospheric gaseous and particulate matter organic component collection, analysis and processing system in the detection of weakly polar and / or polar organic components in atmospheric gaseous and particulate matter.

[0076] The third aspect of this invention provides a rapid orbital hydrazine mass spectrometry analysis method for organic components in atmospheric gaseous and particulate matter, comprising: collecting samples using the aforementioned atmospheric gaseous and particulate matter organic component acquisition, analysis, and processing system; placing the samples on a sample tray; exciting and ionizing them with an ion source; obtaining ionized target molecules; detecting them using orbital hydrazine mass spectrometry; analyzing the obtained mass spectrum data; and screening based on the precise mass number or ion abundance ratio of the molecular ions to determine the target components in the sample molecules. For detailed detection procedures, see [details omitted]. Figure 4 .

[0077] In the above methods, sample collection includes any of the following: A) When the sample is gaseous organic matter in ambient air or exhaust gas from a pollution source collected online, an adsorbent is placed in the sample placement hole on the sample plate, and a perforated plate cover is placed on the plate. The plate is driven by a motor to move, and the sample is input into the plate of the sample plate through a sampling tube via a sampling pump. The sample flows into the sample placement hole connected to the opening and is adsorbed by the adsorbent to collect gaseous organic matter. B) When the sample is particulate organic matter in ambient air or exhaust gas from a pollution source collected online, a filter membrane is placed in the sample placement hole on the sample tray, and a perforated tray cover is placed on the tray body. The tray body is driven by a motor to move, and the sample is input into the tray body of the sample tray through the sampling tube via a sampling pump. The sample flows into the sample placement hole connected to the opening and is intercepted by the filter membrane to collect particulate organic matter. C) When the sample is gaseous or particulate organic matter from ambient air or exhaust gas from a pollution source collected offline, an adsorbent or filter membrane is placed in the sample placement hole on the sample tray. After covering the tray with a non-porous cover, the tray is removed from the shell and ultrasonically extracted and mixed. The non-porous cover is then removed, the tray is placed back into the shell, and a perforated cover is placed on the tray. The tray is then driven by a motor to move, and the sample is fed into the tray through a sampling tube by a sampling pump. The sample flows into the sample placement hole connected to the opening and is adsorbed by the adsorbent to collect gaseous organic matter or retained by the filter membrane to collect particulate organic matter.

[0078] In A) or C), the adsorbent is an XAD adsorbent or a Tenax-TA adsorbent.

[0079] In A), the sampling flow rate of the sample input to the disk is 50-200 mL / min. This can be determined based on the degree of sample contamination.

[0080] In A) or C), before the sample flows into the sample placement hole that communicates with the opening, it is first filtered by a first filter membrane to remove particulate organic matter.

[0081] In one specific embodiment, the first filter membrane is a Teflon filter membrane or a stainless steel fine mesh. It is used to filter particulate organic matter and block the adsorbent.

[0082] In B) or C), the filter membrane is a second filter membrane.

[0083] In one specific embodiment, the second filter membrane is a quartz fiber filter membrane.

[0084] In section B), the sampling flow rate of the sample input to the disk is 50-500 mL / min. Depending on the atmospheric pollution level, a sampling tube with a flow rate ranging from low to high can be used.

[0085] In C), the sampling flow rate of the sample input to the disk is 50-500 mL / min for gaseous organic components and 100-2000 mL / min for particulate organic components.

[0086] In A), B), or C), a solvent is added to the sample placement hole, and the amount of solvent added is sufficient to cover the sample.

[0087] In one specific embodiment, the ratio of the mass (g) of the adsorbent or filter membrane added to the volume (μL) of the solvent added is 1:50 to 1:200. Depending on the sample to be analyzed, the adsorbent or filter membrane can be placed in the membrane, and the sample-to-solvent ratio can be adjusted based on the signal response. The volumetric concentration can then be calculated based on the sample volume and the amount of solvent added.

[0088] In one specific embodiment, the amount of sample placed in the sample placement hole does not exceed 2 / 3 of the hole's volume to prevent sample overflow during excitation.

[0089] In one specific embodiment, the solvent is selected from a methanol / water mixed solvent or a methanol / acetonitrile / water mixed solvent.

[0090] In a further embodiment, in the methanol / water mixed solvent, the volume ratio (v / v) of methanol to water is 1:1 to 5:1, preferably 1:1; in the methanol / acetonitrile / water mixed solvent, the volume ratio (v / v) of methanol, acetonitrile, and water is 1:0.5:0.5 to 1:1.5:1.5, preferably 1:1:1. The proportion of polar solvents can be appropriately increased according to the polarity of the target substance.

[0091] In a further embodiment, the solvent is a methanol / water mixture.

[0092] Add a quantitative amount of high-purity organic solvent, such as methanol, acetonitrile, deionized water, or a mixture thereof, to the sample placement hole of the sample tray. Different solvents can be added according to the polarity of the target substance. Cover the sample tray and use low-temperature sonication to fully dissolve and mix the target substance, ensuring that the solution contacted by the ion source for excitation is uniformly mixed.

[0093] In step C), the sample can also be directly placed into a sample placement hole that communicates with the opening. That is, the sampling pump is turned off, and a sample of a certain mass or area is placed in the sample.

[0094] In C), the ultrasonic extraction conditions are: extraction temperature of 25±2℃, preferably 25℃; extraction time of 5±1min, preferably 5min; and extraction power of 100±10W, preferably 100W.

[0095] In the above methods, such as Figure 4 As shown, the excitation ionization includes: discharging after inputting carrier gas into the ionization source, obtaining excited-state ions, electrons or gas molecules, colliding with organic components in the collected sample, ionizing them, and obtaining ionized sample molecules.

[0096] In one specific embodiment, the carrier gas is selected from at least one of helium (He) or nitrogen (N2). The purity of the stable gas is at least 99.99%, i.e., it is a high-purity carrier gas.

[0097] In a further embodiment, the carrier gas is a mixture of helium and nitrogen, wherein the volume ratio of helium to nitrogen is 4:1, with an error of less than ±2%.

[0098] In one specific embodiment, the discharge voltage is 2-5 kV, preferably 2.0-3.8 kV, and more preferably 2.5-3.5 kV. The discharge occurs in the discharge chamber of the ionization source when the carrier gas contacts the corona discharge needle to form a glow discharge, generating excited-state gas molecules or atoms, such as excited-state metastable helium atoms or excited-state metastable nitrogen molecules, into the sample dish from the ionization source nozzle. This desorbs and ionizes the analyte, causing proton and charge transfer, and exciting the target organic compound into molecular ions. The discharge needle is adjustable; typically, a discharge voltage of 2.5 kV is used for fragile compounds, and a discharge voltage of 3.5 kV is used for poorly ionized substances.

[0099] In a further embodiment, during the excitation of the discharge, the excited-state ions, electrons, or gas molecules are selected from at least one of excited-state metastable helium atoms (He*, 19.8 eV) and excited-state metastable nitrogen molecules (N2*, 8.5~11.5 eV). The higher energy states of the aforementioned excited-state ions, electrons, or gas molecules are greater than 11.5 eV. Most organic compounds have an ionization energy of around 10 eV. Using the aforementioned reactive gases allows for the ionization of organic molecules without generating excessive fragment ions, i.e., high-energy gas atoms or molecules.

[0100] In one specific embodiment, the discharge stability CV is less than 5%.

[0101] In one specific embodiment, the ionization source in the excited ionization can be selected as either a positive ion mode or a negative ion mode. Hot electrons are generated through Penning ionization, achieving proton transfer and charge transfer.

[0102] In one specific embodiment, the distance between the tip of the ionization source probe and the sample placement hole where the sample to be tested is placed is 1~10 cm; the angle between the ionization source probe and the input surface of the sample disk where the sample to be tested is placed is 30°~90°; the distance between the tip of the ionization source probe and the mass analyzer inlet of the orbital hydrazine mass spectrometer is 1~10 cm; and the angle between the ionization source probe and the mass analyzer inlet of the orbital hydrazine mass spectrometer is 30°~180°. The above-mentioned distances and angles are systematically adjusted based on the sample concentration and the intensity of the mass spectrometry response signal, i.e., manually adjusted based on the intensity of the mass spectrometry response signal during previous tests.

[0103] In the above method, the ionized target molecule is input into the orbital hydrazine mass spectrometer via an ion transmission tube.

[0104] The atmospheric gaseous and particulate samples collected on the sample plate are desorbed and ionized by an open ionization source. The ionized target molecules are then introduced into the ion transmission tube by the pressure difference caused by the vacuum at the ion transmission tube of the orbital hydrazine mass spectrometer, and then input into the orbital hydrazine mass spectrometer for mass spectrometry scanning (first-stage full scan or second-stage scan) and detection.

[0105] In one specific embodiment, the carrier gas input to the ionization target molecule in the ion transmission tube is the same as the carrier gas input to the ionization source.

[0106] In one specific embodiment, the pressure difference between the ionized sample molecules and the input ion transmission tube is 1~2 mbar (0.1~0.2 kPa).

[0107] In the above method, the measurement conditions for the orbital hydrazine mass spectrometry include: the intensity of the mass spectrometry response signal is 10E. 6 ~10E 9 The time resolution is 1–10 s; the carrier gas flow rate is 0.2–2.5 L / min; a DC voltage of 100–300 V is applied to the electrodes; the plasma is argon or helium plasma; the plasma is generated by atmospheric pressure antiglow discharge, and the total power of the discharge is maintained below 4 W; under operating conditions of 2–20 mA, the argon plasma gas temperature is 40–100 °C, and the helium plasma gas temperature is 20–80 °C; the Orbitrap mass resolution is ≥70,000, preferably 140,000 at m / z 200. Ionization conditions are optimized by adjusting the current and gas flow rate. The distance and excitation angle between the ionization source, the ion transmission tube, and the sample disk can be adjusted according to the signal response intensity of standard and actual samples to meet the requirements of mass spectrometry analysis sensitivity and detection range. After the organic matter in the sample is excited by the ionization source, the obtained [M+H] can be used... + and [MH] - Molecular weight confirmation was performed.

[0108] In one specific embodiment, the determination conditions for the orbital hydrazine mass spectrometry further include: the ion source is an ESI source or other open atmospheric pressure desorption ionization source, preferably one of microwave induced plasma desorption / discharge ionization (MIPDI), direct analysis in real-time (DART), or flowing atmospheric pressure afterglow (FAPA); the detection mode of the ESI source is positive ion electrospray ionization mode ESI. + Or negative ion electrospray ionization mode ESI -The spray voltage is 2.0~4.0 kV; the ion source temperature is 310~330℃; the sheath gas flow rate is 30~40 units, preferably 35 units; the auxiliary gas flow rate is 5~15 units, preferably 10 units; the purge gas flow rate is 0 units; the scanning mode is full-spectrum MS or secondary mass spectrometry ddMS. 2 In full-spectrum scanning, the scanning range is 50~2000 amu (m / z); in secondary mass spectrometry scanning, the voltage is selected from any one or more combinations of 20 eV, 40 eV, or 60 eV.

[0109] During the above-mentioned orbital hydrazine mass spectrometry detection, once the atmospheric sample flow rate is stabilized, continuous analysis of the sample can be maintained. The mass spectrometry conditions can be selected and determined using standard samples, and the standard curve and sample analysis are performed under the same conditions.

[0110] The above-mentioned full-spectrum MS scan can obtain mass spectra of all components within a set mass range in a single scan. The above-mentioned secondary mass spectrometry scan (dd MS) 2 You can select sample molecular ions for specific scanning, or select the 100 molecular ions with the highest signal response intensity for secondary scanning.

[0111] In one specific embodiment, during the orbital hydrazine mass spectrometry determination, a mass calibration solution is used to calibrate the mass axis in both positive and negative scan modes of the mass spectrometer. The mass calibration solution is a commercially available, commonly used mass calibration solution, specifically Thermo Scientific Pierce FlexMix calibration solution such as A39239 Pierce. TM FlexMix TM Calibration solution (a mixture of 16 high-purity, ionizable components, with a mass range of m / z: 50~3000).

[0112] In a preferred embodiment, the m / z mass range of the calibration solution is 74~1922. This ensures that the accuracy error of the mass of each substance after calibration is within 2 ppm.

[0113] In the above methods, such as Figure 5 As shown, when analyzing the mass spectrometry data, the mass spectrometry data is matched with data in the spectral library for similarity. If the similarity is ≥0.75, the target analyte in the sample is determined. A similarity of ≥0.75 is sufficient to classify a compound as a target compound.

[0114] In one specific implementation, the spectral library can refer to online spectral libraries like mzCloud, commercial spectral libraries, or self-built spectral libraries. Alternatively, it can be selected based on the deviation between the precise mass of a compound and its theoretical value, with the deviation between the precise mass of the target analyte and the theoretical value being within 5 to 20 ppm, depending on the research needs. After accumulating 200 spectra based on manually labeled characteristic pollutants in the atmosphere or pollution sources, relevant factors for pollution testing are input. The spectra, spectral analysis results, and relevant factors are then imported into machine learning software for identification. After deep learning, pollution characteristics of new samples are identified. Through cluster analysis, the analysis of sample characteristic substances, pollution characteristics, or pollution processes is achieved.

[0115] Among them, a self-built atmospheric organic matter characteristic database can refer to the detection data of published literature and includes the precise mass numbers of no less than 300+ characteristic atmospheric organic matter; the spectral library contains multi-dimensional data such as molecular ion peaks, isotope peaks, characteristic fragments and secondary mass spectra, and combines molecular ion peaks and fragment characteristics to confirm the structure and establish a fragment intensity ratio reference standard library.

[0116] In one specific implementation, such as Figure 5 As shown, the mass spectrometry data is analyzed using the conventional analysis process for mass spectrometry data in orbital hydrazine mass spectrometry. This involves using an averaging algorithm for system background subtraction and a peak identification algorithm based on a deconvolutional neural network (CNN) to identify characteristic target analytes distinct from matrix and solvent interference. High-resolution mass spectrometry achieves an accuracy of >95% for identifying unknowns and can distinguish adjacent peaks with an overlap of up to 80%. A two-dimensional matching model is established for the precise mass numbers of molecular ion peaks, isotope peaks, and characteristic fragments, as well as for secondary mass spectra. Based on the precise mass numbers of molecular ion peaks, isotope peaks, and characteristic fragments, two-dimensional screening of target molecules and their similar compounds is performed. Secondary structure confirmation can be performed when necessary, with a matching accuracy of 0.001 Da and a false positive rate of <3%. An automatic time series analysis function is designed to perform trend analysis. A machine learning-based spectral analysis method is established to achieve simultaneous non-targeted screening and quantitative analysis.

[0117] In a preferred embodiment, the workstation is equipped with Tracer Finder, Orbitool, or MZmine software. Mass spectra are viewed, molecular formulas are confirmed, substances are screened, and qualitative screening and integration of large datasets of target compounds in the sample are performed using the workstation or software. Specifically, based on the precise mass numbers obtained from mass spectrometry, mass spectra are viewed, molecular formulas are confirmed, and substances are screened using instrument-compatible software such as Tracer Finder, or qualitative screening and integration of compounds and long-term sequence spectral processing are performed online using other software such as Orbitool.

[0118] In the above method, the screening is non-targeted screening. During screening, the author can use Orbitool software (based on previously applied software copyrights or published papers) to extract massive amounts of data from long-term sequences. Offline sample extraction can be performed using the software included with the instrument or commercially available MZmine for non-targeted molecular ion extraction and screening.

[0119] In the above method, after sample testing, the sample tray is removed from the shell and cleaned. The cleaning can be conventional ultrasonic cleaning, with the same conditions as ultrasonic extraction. After analysis, each sample tray needs to be thoroughly ultrasonicated at least three times with deionized water and a high-purity organic solvent until the target analyte response intensity in the next blank sample is below the method detection limit. The organic solvent mentioned above is the same solvent used for sample collection.

[0120] In one specific embodiment, the ultrasonic cleaning can be performed after sample testing and before the next analysis to check and clean the nozzle, clean the disc body and disc cover, and, after a long period of time (such as after 3 months of continuous analysis), clean or replace the ion transmission tube. Repeating the above steps allows for continued continuous analysis of samples.

[0121] In the above method, each sample group should have a blank solvent position, a parallel sample position, and an internal standard sample position set on the sample placement hole of the sample tray.

[0122] A fourth aspect of this invention provides a method for detecting organic sulfate esters in atmospheric gaseous and particulate matter, comprising the following steps: 1) Samples containing gaseous organic matter and / or particulate organic matter in ambient air or exhaust gas from pollution sources are analyzed using the same steps as the above-mentioned rapid analysis method for organic matter in gaseous and particulate matter in the atmosphere by orbital hydrazine mass spectrometry to obtain ionized sample molecules. 2) The standards for organic sulfate esters, namely glycolate sulfate, lactate sulfate, pinene sulfate, limonene sulfate, and limonene sulfate, are obtained by using the same steps as the rapid analysis method of orbital hydrazine mass spectrometry for organic components in atmospheric gaseous and particulate matter, to obtain ionized standard molecules. 3) The ionized standard molecules obtained in step 2) are measured using the same steps as the rapid analysis method for organic components in gaseous and particulate matter in the atmosphere described above. Based on the precise mass number or ion abundance ratio of the molecular ion of the standard molecules, the mass spectrum and response intensity are extracted from the corresponding spectral library. Then, the ionized sample molecules obtained in step 1) are measured using the same steps as the rapid analysis method for organic components in gaseous and particulate matter in the atmosphere described above. Based on the mass spectrum of the sample molecules, the specific organic sulfate ester components are determined, and the content of organic sulfate ester components in the sample molecules is calculated based on the response intensity of the sample molecules using any one of the external standard method, internal standard method, or standard addition method.

[0123] In step 1), the particulate organic components include at least one of carbon, hydrogen, oxygen, and nitrogen.

[0124] In step 2), the concentration of the organic sulfate components—glycolic acid sulfate, lactic acid sulfate, pinene sulfate, limonene sulfate, and limonone sulfate—is 10-1000 mg / L.

[0125] In step 3), when the standard molecule is used to detect organic sulfate ester components, the precise mass number or ion abundance ratio of the molecular ion is calculated by detecting the m / z peak of the target analyte, peak matching, peak integration, and molecular formula.

[0126] In step 3), the spectral library can be a self-built spectral library, an online spectral library such as mzCloud, or a commercial spectral library, to accurately identify target quantitative ions and achieve rapid interpretation of mass spectra.

[0127] In step 3), the external standard method, internal standard method, or standard addition method are all conventional methods in the field of instrument detection for calculating the content of target components in sample molecules.

[0128] Taking the external standard method as an example, the process includes: transferring a series of standards of different volumes of organic sulfate esters to prepare a series of standard solutions with different concentration gradients; performing the same steps as the rapid analysis method for organic components in gaseous and particulate matter in the atmosphere using orbital hydrazine mass spectrometry; obtaining the linear relationship between the concentration of each organic sulfate ester component in the standard solution and the mass spectrum peak area; plotting the corresponding standard working curve with the mass spectrum peak area corresponding to its concentration; and calculating the regression equation of the standard working curve. Then, the gaseous organic components and / or particulate organic components in ambient air or exhaust gas from pollution sources are measured using the same steps as the rapid analysis method for organic components in gaseous and particulate matter in the atmosphere using orbital hydrazine mass spectrometry. Substituting the obtained mass spectrum peak areas of the target components in the sample molecules into the regression equation of the standard working curve yields the concentration of the corresponding target components in the sample molecules.

[0129] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

[0130] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0131] Example 1 (1) Collection like Figure 1-3 As shown in Figure 5, 2g of XAD adsorbent is placed on the sample tray, and a perforated cover is placed on the tray. The sampling pump is turned on, and the sampling flow rate and the rotary table speed are adjusted. The volume collected at each sample location can be controlled by the sampling speed and residence time. Gaseous samples are filtered for particulate matter by a Teflon filter membrane before being collected by the XAD-2 adsorbent in the sample tray.

[0132] Ambient air samples are introduced into the sample tray at a flow rate of 100 mL / min via a sampling pump and a sampling tube. The sample is placed in the sample placement hole on the tray body, which is connected to the opening. The sampling airflow is introduced into the tray body through the sampling tube. The surface of the input end of the sampling tube is covered with a stainless steel fine mesh to block the adsorbent. The tray body is moved by a motor. After collection, the lid is kept closed before the sample is excited and ionized.

[0133] Add 200 μL of methanol:water mixed solvent (methanol to water volume ratio of 1:1) one by one. It is necessary to test in advance to ensure that the total volume of sample and solvent after adding mixed solvent is not greater than 2 / 3 of the volume of each sample position in the sample tray, so as to avoid adsorbent or sample splashing during sampling and excitation ionization.

[0134] (2) Excitation ionization The ionization source switch is turned on, and a mixture of helium and nitrogen (volume ratio of helium to nitrogen 4:1) is introduced into the ionization source via the carrier gas input tube as the carrier gas for excitation. The purity of the helium and nitrogen input is 99.99%. The carrier gas enters the discharge chamber and contacts the 3.5kV discharge needle to form a glow discharge, producing high-energy gaseous helium atoms (He*, 19.8 eV) and nitrogen molecules (N2*, 8.5~11.5 eV). The obtained excited-state ions, electrons, and gas atoms collide with organic components in the collected sample, causing ionization and obtaining ionized target molecules. The distance between the tip of the ionization source probe and the sample placement hole is 5 cm; the angle between the ionization source probe and the input surface of the sample disk is 60°; the distance between the tip of the ionization source probe and the mass analyzer inlet of the orbital hydrazine mass spectrometer is 5 cm; and the angle between the ionization source probe and the mass analyzer inlet of the orbital hydrazine mass spectrometer is 120°. The ion source for excitation ionization can be selected in negative ion mode.

[0135] (3) Detection The ionized target molecules are introduced into the ion transmission tube by the pressure difference caused by the vacuum at the ion transmission tube of the orbital hydrazine mass spectrometer, and then input into the orbital hydrazine mass spectrometer for detection. The obtained mass spectrum data is analyzed to determine the target components in the sample molecules.

[0136] The pressure difference between the ionized target molecules and the input ion transport tube is 1 mbar. The carrier gas is a mixture of high-purity helium and nitrogen (helium to nitrogen volume ratio of 4:1). The measurement conditions for the orbital hydrazine mass spectrometry are: the intensity of the mass spectrometry response signal is 10E. 7 The time resolution was 4 s; a carrier gas was introduced into the discharge chamber at a flow rate of 1.0 L / min, and a DC voltage of 300 V was applied to the electrodes. The argon plasma was generated by atmospheric pressure antiglow discharge, and the total power of the discharge was kept below 4 W. The ionization conditions were optimized by adjusting the current and gas flow rate; the temperature of the argon plasma gas was 60 °C under the working condition of 10 mA; the Orbitrap mass resolution was set to 70,000~140,000 at m / z 200.

[0137] In addition, the ion source is an ESI source, and the detection mode of the ESI source is negative ion electrospray ionization mode ESI. - The spray voltage was 3.0 kV; the ion source temperature was 320 °C; the sheath gas flow rate was 35 units; the auxiliary gas flow rate was 10 units; the purge gas flow rate was 0 units; the scanning mode was full-spectrum MS; and the scanning range was 90~700 amu in full-spectrum MS.

[0138] During orbital hydrazine mass spectrometry measurements, a mass calibration solution was used to calibrate the mass axis in both positive and negative scanning modes. The calibration solution was Thermo Scientific Pierce FlexMix calibration solution, such as A39239 Pierce™ FlexMix™ calibration solution. The m / z mass range of the calibration solution was 74–1922.

[0139] When analyzing mass spectrometry data, the mass spectrometry data is matched with data in the spectral library for similarity. A similarity score of 0.80 ensures that the deviation between the precise mass number of the target analyte and the theoretical value is within 10 ppm, thus identifying the target analyte component in the sample. The spectral library used in the orbital hydrazine mass spectrometry search is mzCloud. The analysis of mass spectrometry data follows the standard analysis process for orbital hydrazine mass spectrometry data, employing an averaging algorithm for system background subtraction and a deconvolutional neural network (CNN) peak identification algorithm to identify characteristic target analytes distinct from matrix and solvent interference. High-resolution mass spectrometry achieves an accuracy of >95% for identifying unknown substances and can distinguish adjacent peaks with an overlap of up to 80%. A two-dimensional matching model is established for the precise mass numbers of molecular ion peaks, isotope peak ratios, and characteristic fragment ion peaks. Based on the precise mass numbers and isotope peak ratios, two-dimensional screening of target molecules is performed with a matching accuracy of 0.001 Da and a false positive rate of <3%. An automatic time series analysis function is designed to perform trend analysis. A machine learning-based spectral analysis method was established to simultaneously perform non-targeted screening and quantitative analysis, thereby obtaining the sample detection results. The aforementioned ionization source and orbital hydrazine mass spectrometry were all under the control of the controller.

[0140] Example 2 (1) Collection like Figure 1-3 As shown in Figure 5, place a 1.5cm sample on the sample tray. 2 A quartz fiber filter membrane and 100 μL of a methanol:water:acetonitrile mixed solvent (volume ratio 1:1:1) are used to cover the sample pan with a perforated cover. The sampling pump is turned on and the sampling flow rate and the rotation speed of the pan are adjusted. The sampling gas flow is introduced into the pan through the sampling tube. The pollutant source exhaust gas sample is input into the sample placement hole on the sample pan at a flow rate of 50 mL / min through the sampling pump and the sampling tube. The pan is driven by a motor to move, and the particulate organic components are collected by the filter membrane.

[0141] (2) Excitation ionization The ionization source switch is turned on, and a mixture of helium and nitrogen (volume ratio of helium to nitrogen 4:1) is introduced into the ionization source via the carrier gas input tube as the carrier gas for excitation. The purity of the helium and nitrogen input is 99.99%. The carrier gas enters the discharge chamber and contacts the 2.5kV discharge needle to form a glow discharge, producing high-energy gaseous helium atoms (He*, 19.8 eV) and nitrogen molecules (N2*, 8.5~11.5 eV). The obtained excited-state ions, electrons, and gas atoms collide with organic components in the collected sample, causing ionization and obtaining ionized target molecules. The distance between the tip of the ionization source probe and the sample placement hole is 7 cm; the angle between the ionization source probe and the input surface of the sample disk is 45°; the distance between the tip of the ionization source probe and the mass analyzer inlet of the orbital hydrazine mass spectrometer is 8 cm; and the angle between the ionization source probe and the mass analyzer inlet of the orbital hydrazine mass spectrometer is 150°. The ion source for excitation ionization can be selected in positive ion mode.

[0142] (3) Detection The ionized target molecules are introduced into the ion transmission tube by the pressure difference caused by the vacuum at the ion transmission tube of the orbital hydrazine mass spectrometer, and then input into the orbital hydrazine mass spectrometer for detection. The obtained mass spectrum data is analyzed to determine the target components in the sample molecules.

[0143] The pressure difference of the ionized target molecules input into the ion transmission tube is 1.5 mbar. The carrier gas is a mixture of high-purity helium and nitrogen (volume ratio of helium to nitrogen is 4:1). The measurement conditions for the orbital hydrazine mass spectrometry are: the intensity of the mass spectrometry response signal is 10E. 8 The time resolution is 5 s; the carrier gas flow rate is 2.0 L / min; a DC voltage of 100 V is applied to the electrodes; the helium plasma will be generated by atmospheric pressure antiglow discharge; the total power of the discharge is maintained below 4 W; the ionization conditions are optimized by adjusting the current and gas flow rate; the temperature of the helium plasma gas is 50 °C under the working condition of 15 mA; the Orbitrap mass resolution is 70000~140000 at m / z 200.

[0144] In addition, the ion source is an ESI source, and the detection mode of the ESI source is positive ion electrospray ionization mode (ESI). + The spray voltage was 3.0 kV; the ion source temperature was 320 °C; the sheath gas flow rate was 35 units; the auxiliary gas flow rate was 10 units; the purge gas flow rate was 0 units; the scanning mode was full-spectrum MS; and the scanning range was 90~700 amu in full-spectrum MS.

[0145] During the mass spectrometry determination of orbital hydrazine, a mass calibration solution was used to calibrate the mass axis in both positive and negative scan modes. The mass calibration solution was Thermo Scientific Pierce FlexMix calibration solution, such as Pierce A39239. TM FlexMix TM Calibration solution. The m / z mass range of the mass calibration solution is 74~1922.

[0146] When analyzing mass spectrometry data, the mass spectrometry data is matched with data in the spectral library for similarity. A similarity score of 0.75 ensures that the deviation between the precise mass number of the target analyte and the theoretical value is within 5 ppm, thus identifying the target analyte component in the sample. The spectral library used in the orbital hydrazine mass spectrometry search is mzCloud. The analysis of mass spectrometry data follows the standard analysis process for orbital hydrazine mass spectrometry data, employing an averaging algorithm for system background subtraction and a deconvolutional neural network (CNN) peak identification algorithm to identify characteristic target analytes distinct from matrix and solvent interference. High-resolution mass spectrometry achieves an accuracy of >95% for identifying unknown substances and can distinguish adjacent peaks with an overlap of up to 75%. A two-dimensional matching model is established for the precise mass numbers of molecular ion peaks, isotope peak ratios, and characteristic fragment ion peaks. Based on the precise mass numbers and isotope peak ratios, two-dimensional screening of target molecules is performed with a matching accuracy of 0.001 Da and a false positive rate of <3%. An automatic time series analysis function is designed to perform trend analysis. A machine learning-based spectral analysis method was established to simultaneously perform non-targeted screening and quantitative analysis, thereby obtaining the sample detection results. The aforementioned ionization source and orbital hydrazine mass spectrometry were all under the control of the controller.

[0147] Example 3 (1) Collection Offline processing was performed by placing 2g of XAD adsorbent and 200μL of a methanol:water mixture (1:1 volume ratio) on the sample tray. A non-porous cover was placed on the tray, and the tray was removed from the shell for ultrasonic extraction. The extraction conditions were: extraction temperature 25℃; extraction time 5 min; extraction power 100W. The non-porous cover was removed, the tray was returned to the shell, and a perforated cover was placed on top. The tray was then moved by a motor, and the sample was pumped into the sample tray via a sampling tube. The sample flowed into the sample placement holes connected to the perforations and was adsorbed by the adsorbent to collect gaseous organic components. The sampling flow rate was 100mL / min.

[0148] (2) Excitation ionization The excitation ionization process is the same as step 2 in Example 1.

[0149] (3) Detection The detection process is the same as step 3 in Example 1.

[0150] (4) Comparative discussion Comparing the detection process of Example 3 with that of Example 1, it can be found that the pretreatment time of Example 1 is greatly shortened to 1-5 minutes, realizing online processing, no transfer loss, and can be analyzed on the instrument. Thus, the analysis time is shortened to within 5-10 minutes, the pretreatment time is shortened by more than 90%, and the solvent consumption is reduced by more than 95%.

[0151] Example 4 The same steps as in Example 1 were used to obtain ionized sample molecules from the pollutant source exhaust gas sample.

[0152] Standards for organic sulfate components—glycolic acid sulfate, lactic acid sulfate, pinene sulfate, limonene sulfate, and limonene sulfate—were analyzed using standard curves plotted at concentration gradients of 10, 50, 100, 500, and 1000 mg / L. The same procedures as in Example 1 were followed to obtain a series of ionized standard molecules.

[0153] The standard molecules to be ionized are measured using the same steps as in Example 1. Based on the precise mass number or ion abundance ratio of the molecular ion of the standard molecules, the mass spectrum and response intensity are extracted from the corresponding spectral library. Then, the sample molecules to be ionized are measured using the same steps as in Example 1. Based on the mass spectrum of the sample molecules, the specific organic sulfate ester components are determined, and the content of organic sulfate ester components in the sample molecules is calculated using the external standard method based on the response intensity of the sample molecules.

[0154] Specifically, a series of standard samples of organic sulfate esters with different volumes were transferred to prepare a series of standard solutions with different concentration gradients. The same steps as in Example 1 were used for determination to obtain the linear relationship between the concentration of each organic sulfate ester component in the standard solution and the mass spectrometry peak area. The corresponding concentrations of the mass spectrometry peak areas were then mapped to corresponding standard working curves, and the regression equations for the standard working curves were calculated. Next, gaseous organic components and / or particulate organic components in ambient air or polluted exhaust gas were determined using the same steps as in Example 1. The mass spectrometry peak areas of the target components in the obtained sample molecules were substituted into the regression equations of the standard working curves to obtain the concentrations of the corresponding target components in the sample molecules.

[0155] The target components in the sample molecules: The detection results of five organic sulfate esters are shown in Table 1, which effectively enables accurate qualitative and quantitative analysis of these five organic sulfate esters. Furthermore, based on the principle of similar linearity and retention time in Table 1, precise molecular weight information of molecular ions from different precursor classifications in the pollution source exhaust gas samples can be obtained. This allows for semi-quantitative or qualitative screening of 33 organic sulfate esters in the pollution source exhaust gas samples. The specific classifications of different precursors and their molecular composition and precise molecular weights in the pollution source exhaust gas samples are shown in Table 2.

[0156] In summary, this invention provides a rapid method and processing system for the orbital mass spectrometry analysis of gaseous and particulate organic compounds. The instrument has a simple structure, requires no offline operation, and only one pretreatment step, resulting in no pretreatment loss or contamination. Measurements can be performed directly on the instrument after intelligent spectral analysis. This method is suitable for rapid quantitative analysis and non-targeted screening of organic compounds in atmospheric gaseous and particulate samples. Therefore, this invention effectively overcomes the various shortcomings of existing technologies and has high industrial application value. This method can also be referenced for the detection of cyclohexane residues using headspace gas chromatography.

[0157] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter, characterized in that, The device includes a housing with an ion transmission tube mounted on it. The housing is hollow, and the ion transmission tube penetrates through the housing. An ionization source and a sample disk are located inside the housing. The sample inlet of the sample disk is matched with the output end of the ionization source, and the sample outlet of the sample disk is matched with the input end of the ion transmission tube. The output end of the ion transmission tube is connected to an orbital hydrazine mass spectrometer.

2. The system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter according to claim 1, characterized in that, Includes one or more of the following conditions: A1) The shell is rectangular in shape and has at least one observation window on each of its four side walls; A2) The output end of the ion transmission tube is connected to the gas inlet of the orbital hydrazine mass spectrometer; A3) The input end of the ionization source is connected to a carrier gas input pipe; A4) The sample disk includes a disk body, and a motor is provided outside the disk body. The center of the disk body is detachably sleeved on the rotating shaft of the motor so that the disk body can move circumferentially around the rotating shaft of the motor under the drive of the motor. The disk body is provided with at least one downwardly recessed sample placement hole, and the sample placement hole is matched with the output end of the ionization source and the input end of the ion transmission tube, respectively. A5) The ionization source is an open-type atmospheric pressure desorption ionization source.

3. The system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter according to claim 2, characterized in that, Includes one or more of the following conditions: B1) In item A1), observation windows are provided on all four side walls of the housing; B2) In item A3), the carrier gas input pipe penetrates the housing and the output end of the carrier gas input pipe is connected to the input end of the ionization source; B3) In item A4), the number of sample placement holes is 12-24; B4) In item A4), the disk body is marked with letter identifiers, and the sample placement hole is marked with number identifiers; B5) In item A4), the sample tray further includes a tray cover, the tray cover includes a non-perforated tray cover and a perforated tray cover, the tray cover completely covers the tray body, the perforated tray cover has an opening, the opening is matched with the position of the sample placement hole; B6) In item A4), the disk body is also matched with a sampling tube, the sampling tube penetrates the shell and the output end of the sampling tube is matched with the position of the disk body, and the input end of the sampling tube is equipped with a sampling pump; B7) In item A5), the ionization source is selected from one of the following: electrospray ionization source, microwave induced plasma desorption / discharge ion source, real-time direct analysis ion source, and flowing atmospheric pressure ionization source.

4. The system for collecting, analyzing, and processing organic components in atmospheric gaseous and particulate matter according to claim 3, characterized in that, Includes one or more of the following conditions: C1) In item B5), the disc cover is detachably connected to a bracket so that the disc cover is detachably fixed above the disc body; C2) In item B5), the diameter of the opening is not less than the diameter of the sample placement hole; C3) In item B6), when collecting gaseous organic matter components from ambient air or exhaust gas from pollution sources, the sampling tube input end is provided with a first filter membrane for filtering particulate organic matter and the disk is filled with adsorbent for adsorbing gaseous organic matter components; when collecting particulate organic matter components from ambient air or exhaust gas from pollution sources, the disk is provided with a second filter membrane for adsorbing particulate organic matter components. Preferably, the first filter membrane is a Teflon filter membrane or a stainless steel fine mesh; and / or, the second filter membrane is a quartz fiber filter membrane.

5. The use of the atmospheric gaseous and particulate matter organic component acquisition, analysis and processing system according to any one of claims 1-4 in the detection of weakly polar and / or polar organic components in atmospheric gaseous and particulate matter.

6. A rapid orbital hydrazine mass spectrometry method for the analysis of organic components in atmospheric gaseous and particulate matter, comprising: After the sample is collected using the atmospheric gaseous and particulate matter organic component acquisition and analysis processing system according to any one of claims 1-4, it is placed on a sample tray and excited and ionized by an ion source. The ionized target molecules are obtained and detected by orbital hydrazine mass spectrometry. The obtained mass spectrum data is analyzed, and the target components in the sample molecules are determined by screening based on the precise mass number or ion abundance ratio of the molecular ions.

7. The rapid orbital hydrazine mass spectrometry analysis method for organic components in atmospheric gaseous and particulate matter according to claim 6, characterized in that, Includes one or more of the following conditions: D1) Collect samples, selected from any of the following: A) When the sample is gaseous organic matter in ambient air or exhaust gas from a pollution source collected online, an adsorbent is placed in the sample placement hole on the sample plate, and a perforated plate cover is placed on the plate. The plate is driven by a motor to move, and the sample is input into the plate of the sample plate through a sampling tube via a sampling pump. The sample flows into the sample placement hole connected to the opening and is adsorbed by the adsorbent to collect gaseous organic matter. B) When the sample is particulate organic matter in ambient air or exhaust gas from a pollution source collected online, a filter membrane is placed in the sample placement hole on the sample tray, and a perforated tray cover is placed on the tray body. The tray body is driven by a motor to move, and the sample is input into the tray body of the sample tray through the sampling tube via a sampling pump. The sample flows into the sample placement hole connected to the opening and is intercepted by the filter membrane to collect particulate organic matter. C) When the sample is gaseous or particulate organic matter from ambient air or exhaust gas from a pollution source collected offline, an adsorbent or filter membrane is placed in the sample placement hole on the sample plate. After covering the plate with a non-porous plate cover, the plate is removed from the shell and ultrasonically extracted and mixed. The non-porous plate cover is then removed, the plate is placed back into the shell, and a perforated plate cover is placed on the plate. The plate is then driven to move by a motor. The sample is then pumped into the plate of the sample plate through a sampling tube by a sampling pump. The sample flows into the sample placement hole connected to the opening and is adsorbed by the adsorbent to collect gaseous organic matter or retained by the filter membrane to collect particulate organic matter. D2) The excitation ionization includes: after the carrier gas is input into the ionization source, the excited state ions, electrons or gas molecules obtained collide with the organic components in the collected sample and ionize to obtain ionized sample molecules. D3) The ionized target molecules are input into the orbital hydrazine mass spectrometer via an ion transmission tube; D4) The measurement conditions for the orbital hydrazine mass spectrometry include: the intensity of the mass spectrometry response signal is 10E. 6 ~10E 9 The time resolution is 1–10 s; the carrier gas flow rate is 0.2–2.5 L / min; a DC voltage of 100–300 V is applied to the electrodes; the plasma is argon or helium plasma; the plasma is generated by atmospheric pressure antiglow discharge, and the total power of the discharge is maintained below 4 W; under operating conditions of 2–20 mA, the temperature of the argon plasma gas is 40–100 °C, and the temperature of the helium plasma gas is 20–80 °C; the Orbitrap mass resolution is ≥70000, preferably 140000 at m / z 200; D5) When analyzing the mass spectrometry data, the mass spectrometry data is matched with the data in the spectral library. If the similarity is ≥0.75, the target analyte in the sample is determined. D6) After testing the sample, remove the sample tray from the shell and clean it.

8. The rapid orbital hydrazine mass spectrometry analysis method for organic components in atmospheric gaseous and particulate matter according to claim 7, characterized in that, Includes one or more of the following conditions: E1) In item D1) A) or C), the adsorbent is XAD adsorbent or Tenax-TA adsorbent; E2) In section A) of D1), the sampling flow rate of the sample input to the disk is 50-200 mL / min; E3) In A) or C) of item D1), before the sample flows into the sample placement hole that communicates with the opening, it is first filtered by the first filter membrane to remove particulate organic matter. E4) In option B) or C) of item D1), the filter membrane is a second filter membrane; E5) In section B) of item D1), the sampling flow rate of the sample input to the disk is 50-500 mL / min; E6) In section C) of item D1), the sampling flow rate of the sample input to the disk is 50-500 mL / min for gaseous organic components and 100-2000 mL / min for particulate organic components. E7) In item D1), A), B), or C), a solvent is added to the sample placement hole, and the amount of solvent added is sufficient to cover the sample. E8) In section B of item D1), the filter membrane is a quartz fiber filter membrane; E9) In item D2), the carrier gas is selected from at least one of helium (He) or nitrogen (N2); In item D2), the discharge voltage is 2-5kV; (E10) In item D2), E11) the distance between the tip of the ionization source probe and the sample placement hole for placing the sample to be tested is 1–10 cm; the angle between the ionization source probe and the input surface of the sample disk for placing the sample to be tested is 30°–90°; the distance between the tip of the ionization source probe and the inlet of the mass analyzer for the orbital hydrazine mass spectrometer is 1–10 cm; and the angle between the ionization source probe and the inlet of the mass analyzer for the orbital hydrazine mass spectrometer is 30°–180°. In item E12)D3), the carrier gas input to the ionization target molecule in the ion transmission tube is the same as the carrier gas input to the ionization source. E13) In item D3), the pressure difference of the ionized sample molecules input to the ion transmission tube is 1-2 mbar; E14) In item D4), during the orbital hydrazine mass spectrometry determination, the mass axis is calibrated in the positive and negative scanning modes of the mass spectrometer using a mass calibration solution, and the mass calibration solution is Thermo Scientific Pierce FlexMix calibration solution.

9. The rapid orbital hydrazine mass spectrometry analysis method for organic components in atmospheric gaseous and particulate matter according to claim 8, characterized in that, Includes one or more of the following conditions: F1) In item E3), the first filter membrane is a Teflon filter membrane or a stainless steel fine mesh. In item F2) E4), the second filter membrane is a quartz fiber filter membrane; F3) In item E7), the ratio of the mass g of the adsorbent or filter membrane added to the volume μL of the solvent added is 1:50 to 1:200; In item F4) of E7), the amount of sample placed in the sample placement hole shall not exceed 2 / 3 of the volume of the placement hole; In item F5) of E7), the solvent is selected from either a methanol / water mixture or a methanol / acetonitrile / water mixture. Preferably, in the methanol / water mixed solvent, the volume ratio (v / v) of methanol to water is 1:1 to 5:1; in the methanol / acetonitrile / water mixed solvent, the volume ratio (v / v) of methanol, acetonitrile, and water is 1:0.5:0.5 to 1:1.5:1.

5. In item F6) of E9), the carrier gas is a mixture of helium and nitrogen, and the volume ratio of helium to nitrogen is 4:1 with an error of less than ±2%. In item F7) of E10), when the discharge is excited, the excited-state ions, electrons or gas molecules are selected from at least one of excited-state metastable helium atoms and excited-state metastable nitrogen molecules; In item F8) E14), the m / z mass range of the mass calibration solution is 74 to 1922.

10. A method for detecting organic sulfate components in gaseous and particulate matter in the atmosphere, comprising the following steps: 1) Samples containing gaseous organic components and / or particulate organic components in ambient air or exhaust gas from pollution sources are subjected to the same steps as the rapid analysis method for organic components in atmospheric gaseous and particulate matter by orbital hydrazine mass spectrometry according to any one of claims 6-9 to obtain ionized sample molecules. 2) The standards of organic sulfate esters, namely glycolate sulfate, lactate sulfate, pinene sulfate, limonene sulfate, and limonene sulfate, are obtained by using the same steps as the rapid analysis method of organic components in atmospheric gaseous and particulate matter by orbital hydrazine mass spectrometry according to any one of claims 6-9, to obtain ionized standard molecules. 3) The ionized standard molecules obtained in step 2) are measured using the same steps as the rapid analysis method for organic components in atmospheric gaseous and particulate matter by orbital hydrazine mass spectrometry according to any one of claims 6-9. Based on the precise mass number or ion abundance ratio of the molecular ion of the standard molecules, the mass spectrum and response intensity are extracted from the corresponding spectral library. Then, the ionized sample molecules obtained in step 1) are measured using the same steps as the rapid analysis method for organic components in atmospheric gaseous and particulate matter by orbital hydrazine mass spectrometry according to any one of claims 6-9. Based on the mass spectrum of the sample molecules, the specific organic sulfate ester components are determined, and the content of organic sulfate ester components in the sample molecules is calculated based on the response intensity of the sample molecules by any one of the external standard method, internal standard method, or standard addition method.

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