Method and device for determining adsorption error in collecting particulate matter using quartz membrane

Abstract

The present application relates to a method and device for determining adsorption errors in particulate matter collected by a quartz membrane, the method comprising: performing full two-dimensional gas chromatography and mass spectrometry analysis on a first sample and a second sample respectively, obtaining a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; comparing the elements in the same position in the first matrix and the second matrix one by one; if the elements in the first matrix are smaller than the elements in the corresponding position in the second matrix, then filling the elements in the first matrix into the third matrix according to the corresponding position; if the elements in the first matrix are greater than or equal to the elements in the corresponding position in the second matrix, then filling the elements in the second matrix into the third matrix according to the corresponding position; and calculating the adsorption error based on the third matrix. Through the present application, the problem that the gaseous adsorption error cannot be accurately quantified in the related art, resulting in low quantitative accuracy of particulate organic matter in the sample, is solved.

Description

Technical Field

[0001] The present application belongs to the field of environmental monitoring technology, and in particular, relates to a method and device for determining adsorption errors in particulate matter collected by a quartz membrane. Background Art

[0002] Particulate matter pollution in the atmospheric environment is one of the main challenges of today's environmental problems. Organic compounds are an important component of particulate matter, accounting for about 20% to 70%. They come not only from natural sources such as plant emissions or aerosol release from the ocean, but also from human sources such as traffic exhaust, industrial waste gas, and biomass burning. Therefore, the organic components of particulate matter are diverse, including not only the oxidation products of volatile organic compounds, but also toxic and harmful substances such as polycyclic aromatic hydrocarbons and organic acids. With the process of urbanization and industrialization, the complexity of the organic components contained in the particulate matter in the atmospheric environment has increased dramatically.

[0003] The collection and quantification of particulate organic matter is an important part of understanding the mechanism of air pollution and quantitatively evaluating pollution sources. Due to the chemical stability, high temperature resistance, and low background signal of quartz membrane, it is often used to collect particulate organic matter in environmental samples. Chemical composition analysis reveals information such as the type, concentration, and source of particulate organic matter, providing key data for air pollution prevention and health risk assessment. However, quartz membrane has an adsorption effect on gaseous organic matter during the sample collection process. This adsorption error will cause an overestimation of the organic matter content in the particulate sample.

[0004] Currently, there is still a lack of accurate and effective quantitative solutions for the gaseous adsorption errors in samples collected by quartz membranes, resulting in reduced accuracy in the quantitative determination of particulate organic matter in the samples. Summary of the invention

[0005] The embodiments of the present application provide a method and device for determining adsorption errors in particulate matter collected by a quartz membrane, so as to at least solve the problem in the related art that the gaseous adsorption error cannot be accurately quantified, resulting in low quantification accuracy of particulate organic matter.

[0006] In a first aspect, an embodiment of the present application provides a method for determining adsorption errors in particulate matter collected by a quartz membrane, which is applied to determining adsorption errors occurring during the sampling process of a particulate matter sampling device, wherein the particulate matter sampling device comprises a first channel and a second channel, the first channel comprises a Teflon membrane and a first quartz membrane, and the second channel comprises a second quartz membrane, the method comprising: performing full two-dimensional gas chromatography and mass spectrometry analysis on a first sample collected by the first quartz membrane and a second sample collected by the second quartz membrane, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; wherein the elements in the first matrix are Indicates that the first sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the second matrix Indicates that the second sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the same position in the first matrix and the second matrix are compared one by one; if the element in the first matrix is ​​smaller than the element in the corresponding position in the second matrix, the elements in the first matrix are filled into the third matrix according to the corresponding position; if the element in the first matrix is ​​greater than or equal to the element in the corresponding position in the second matrix, the elements in the second matrix are filled into the third matrix according to the corresponding position; the adsorption error is calculated based on the third matrix.

[0007] In some embodiments, performing full two-dimensional gas chromatography and mass spectrometry analysis on a first sample collected from a first quartz film and a second sample collected from a second quartz film, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample includes: performing full two-dimensional gas chromatography analysis on the first sample and the second sample, respectively, to obtain a one-dimensional gas chromatogram and a two-dimensional gas chromatogram; dividing the one-dimensional gas chromatogram into multiple volatility intervals; performing mass spectrometry analysis on the first sample and the second sample, dividing all detected compounds in the two-dimensional gas chromatogram into multiple compound types; determining the content of substances in each volatility interval and belonging to each compound type in the first sample and the second sample according to the multiple volatility intervals divided on the one-dimensional gas chromatogram and the multiple compound types divided on the two-dimensional gas chromatogram, to obtain the first matrix and the second matrix.

[0008] In some embodiments, dividing the one-dimensional gas chromatogram into a plurality of volatility intervals includes: dividing the one-dimensional gas chromatogram into 30 volatility intervals based on the peak time of each normal alkane.

[0009] In some embodiments, the types of compounds include at least two of the following: straight-chain alkanes, branched-chain alkanes, olefins, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons, oxygen-containing polycyclic aromatic hydrocarbons, alkyl-substituted polycyclic aromatic hydrocarbons, halogenated hydrocarbons, amines, and nitrates.

[0010] In some embodiments, after calculating the adsorption error based on the third matrix, the method further includes: performing error correction on elements in corresponding positions in the second matrix based on each element in the third matrix to obtain a corrected second matrix.

[0011] In some embodiments, before performing full two-dimensional gas chromatography and mass spectrometry analysis on the first sample collected by the first quartz membrane and the second sample collected by the second quartz membrane, respectively, the method further includes: using a particle sampling device to collect particles from the target airflow; wherein, after the target airflow enters the first channel and the second channel of the particle sampling device, the particles in the target airflow are collected by the Teflon membrane in the first channel, the gaseous adsorbates in the target airflow are collected by the first quartz membrane in the first channel, and the particles and gaseous adsorbates in the target airflow are collected by the second quartz membrane in the second channel; the gaseous adsorbates collected by the first quartz membrane, and the particles and gaseous adsorbates collected by the second quartz membrane are pre-treated to obtain the first sample and the second sample.

[0012] In some embodiments, before the target airflow enters the first channel and the second channel, the cutter in the particle sampling device performs particle size screening on the target airflow.

[0013] In a second aspect, an embodiment of the present application provides a device for determining an adsorption error in particulate matter collected by a quartz membrane, which is used to determine an adsorption error occurring during a sampling process of a particulate matter sampling device, wherein the particulate matter sampling device includes a first channel and a second channel, the first channel includes a Teflon membrane and a first quartz membrane, the second channel includes a second quartz membrane, and the device for determining an adsorption error in particulate matter collected by a quartz membrane includes: an analysis module for performing full two-dimensional gas chromatography and mass spectrometry analysis on a first sample collected by the first quartz membrane and a second sample collected by the second quartz membrane, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; wherein the elements in the first matrix Indicates that the first sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the second matrix Indicates that the second sample is in the volatility range And belongs to the compound type a comparison module for comparing the elements at the same position in the first matrix and the second matrix one by one; a filling module for filling the elements in the first matrix into the third matrix according to the corresponding position if the elements in the first matrix are smaller than the elements at the corresponding position in the second matrix; and filling the elements in the second matrix into the third matrix according to the corresponding position if the elements in the first matrix are greater than or equal to the elements at the corresponding position in the second matrix; and a calculation module for calculating the adsorption error based on the third matrix.

[0014] In a third aspect, an embodiment of the present application provides a terminal device, including a memory, a processor, and a computer program stored in the memory and executable on the processor. When the processor executes the computer program, the method for determining the adsorption error in particulate matter collected by a quartz membrane according to any one of the first aspects above is implemented.

[0015] In a fourth aspect, an embodiment of the present application provides a computer program product, including a computer program. When the computer program is executed, the method for determining adsorption errors in particulate matter collected by a quartz membrane described in any one of the first aspects above is executed.

[0016] Compared with the related art, the method, device, terminal device and computer program product for determining the adsorption error in the quartz film collected particulate matter provided in the embodiment of the present application respectively perform full two-dimensional gas chromatography and mass spectrometry analysis on the samples collected by the quartz film in each sampling channel of the particulate matter sampling device, and obtain a first matrix and a second matrix; and compare the elements in the same position in the first matrix and the second matrix one by one, and obtain a third matrix based on the size relationship between the elements in the first matrix and the elements in the corresponding position in the second matrix; finally, calculate the adsorption error based on the third matrix; in this way, the volatilization of organic matter in the sample and the influence of the instrument analysis error of individual intervals can be effectively eliminated, and a matrixed fine adsorption error result can be obtained, which can improve the accuracy of quantifying the gaseous adsorption error and help to correct the sample content later. Through this application, the problem that the gaseous adsorption error cannot be accurately quantified in the related art, resulting in low quantitative accuracy of the particulate organic matter in the sample, is solved, and the technical effect of improving the accuracy of quantifying the gaseous adsorption error in the quantitative process of the particulate organic matter in the sample is achieved.

[0017] Details of one or more embodiments of the present application are set forth in the following drawings and description to make other features, objects, and advantages of the present application more readily apparent. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1 is a structural schematic diagram of a particle sampling device according to an embodiment of the present application;

[0020] Figure 2 is a schematic structural diagram of a first membrane series sampler according to an embodiment of the present application;

[0021] Figure 3 is a flow chart of a method for determining adsorption error in collecting particulate matter using a quartz membrane according to an embodiment of the present application;

[0022] Figure 4 is a schematic diagram of a one-dimensional gas chromatogram according to an embodiment of the present application;

[0023] Figure 5 is a schematic diagram of a two-dimensional gas chromatogram according to an embodiment of the present application;

[0024] Figure 6 It is a structural schematic diagram of a device for determining adsorption errors in collecting particulate matter using a quartz membrane according to an embodiment of the present application;

[0025] Figure 7 It is a structural diagram of a terminal device according to an embodiment of the present application. DETAILED DESCRIPTION

[0026] In the following description, specific details such as specific system structures, technologies, etc. are provided for the purpose of illustration rather than limitation, so as to provide a thorough understanding of the embodiments of the present application. However, it should be clear to those skilled in the art that the present application may also be implemented in other embodiments without these specific details. In other cases, detailed descriptions of well-known systems, devices, circuits, and methods are omitted to prevent unnecessary details from obstructing the description of the present application.

[0027] It should be understood that when used in the present specification and the appended claims, the term "comprising" indicates the presence of described features, wholes, steps, operations, elements and / or components, but does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or combinations thereof.

[0028] It should also be understood that the term “and / or” used in the specification and appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes these combinations.

[0029] As used in the specification and appended claims of this application, the term "if" can be interpreted as "when" or "uponce" or "in response to determining" or "in response to detecting", depending on the context. Similarly, the phrase "if it is determined" or "if [described condition or event] is detected" can be interpreted as meaning "uponce it is determined" or "in response to determining" or "uponce [described condition or event] is detected" or "in response to detecting [described condition or event]", depending on the context.

[0030] In addition, in the description of the present application specification and the appended claims, the terms "first", "second", "third", etc. are only used to distinguish the descriptions and cannot be understood as indicating or implying relative importance.

[0031] References to "one embodiment" or "some embodiments" etc. described in the specification of this application mean that one or more embodiments of the present application include specific features, structures or characteristics described in conjunction with the embodiment. Therefore, the statements "in one embodiment", "in some embodiments", "in some other embodiments", "in some other embodiments", etc. that appear in different places in this specification do not necessarily refer to the same embodiment, but mean "one or more but not all embodiments", unless otherwise specifically emphasized in other ways. The terms "including", "comprising", "having" and their variations all mean "including but not limited to", unless otherwise specifically emphasized in other ways.

[0032] Particle pollution in the atmosphere is one of the main challenges of today's environmental problems. Particles have negative impacts on human health and ecosystems, especially fine particles (PM 2.5). It can penetrate deep into the respiratory tract and cause a series of health problems such as respiratory diseases and cardiovascular diseases. At the same time, particles can change the surface radiation balance by scattering and absorbing sunlight, causing global climate change.

[0033] Organic compounds are an important component of particulate matter, accounting for about 20% to 70%. They come not only from natural sources such as plant emissions or aerosol release from the ocean, but also from human sources such as traffic exhaust, industrial waste gas, and biomass burning. Therefore, the organic components of particulate matter are diverse, including not only the oxidation products of volatile organic compounds, but also toxic and harmful substances such as polycyclic aromatic hydrocarbons and organic acids. With the process of urbanization and industrialization, the complexity of the organic components contained in particulate matter in the atmospheric environment has increased dramatically.

[0034] The collection and quantification of particulate organic matter is an important part of understanding the mechanism of air pollution and quantitatively evaluating pollution sources. Due to the chemical stability, high temperature resistance, and low background signal of quartz membrane, it is often used to collect particulate organic matter in environmental samples. Chemical composition analysis reveals information such as the type, concentration, and source of particulate organic matter, providing key data for air pollution prevention and health risk assessment. However, quartz membrane has an adsorption effect on gaseous organic matter during the sample collection process. This adsorption error will cause an overestimation of the organic matter content in the particulate sample.

[0035] Currently, there is still a lack of accurate and effective quantitative solutions for the gaseous adsorption errors in samples collected by quartz membranes, resulting in reduced accuracy in the quantitative determination of particulate organic matter in the samples.

[0036] In view of this, the embodiment of the present application provides a method for determining the adsorption error in particulate matter collected by a quartz membrane, by performing full two-dimensional gas chromatography and mass spectrometry analysis on the samples collected by the quartz membrane in each sampling channel of the particulate matter sampling device, respectively, to obtain a first matrix and a second matrix; and the elements in the same position in the first matrix and the second matrix are compared one by one, and a third matrix is ​​obtained based on the size relationship between the elements in the first matrix and the elements in the corresponding positions in the second matrix; finally, the adsorption error is calculated based on the third matrix; in this way, the volatilization of organic matter present in the sample and the influence of the instrument analysis error of individual intervals can be effectively eliminated, and a matrixed fine adsorption error result can be obtained, which can improve the accuracy of quantifying the gaseous adsorption error and help to correct the sample content later. Through this application, the problem that the gaseous adsorption error cannot be accurately quantified in the related art, resulting in low quantitative accuracy of the particulate organic matter in the sample, is solved, and the technical effect of improving the accuracy of quantifying the gaseous adsorption error in the quantitative process of the particulate organic matter in the sample is achieved.

[0037] The method for determining the adsorption error in the quartz film collected particles provided in the embodiment of the present application can be applied to determine the adsorption error (also called gas adsorption error) that occurs during the sampling process of the particle sampling device. Figure 1 For an explanation of the particle sampling device provided in one embodiment of the present application, see Figure 1 , Figure 1 is a schematic diagram of the structure of a particle sampling device according to an embodiment of the present application. Figure 1 As shown, the particle sampling device includes: a cutter 10 , a first channel 11 , a second channel 12 , a first mass flow controller 13 , a second mass flow controller 14 , a three-way solenoid valve 15 , a diaphragm vacuum pump 16 and a controller 17 .

[0038] In this embodiment, the cutter 10 may include an aerodynamic equivalent particle size cutting head, the first channel 11 may include a first membrane series sampler, and the second channel 12 may include a second membrane series sampler.

[0039] The specific structure of the first membrane series sampler can be found in Figure 2 , Figure 2 is a schematic diagram of the structure of a first membrane series sampler according to an embodiment of the present application, such as Figure 2 As shown, the first membrane series sampler includes: a sampler air inlet 20, a sealing cover 21 above the sampler, an upper part 22 of the first group of membrane supports, a lower part 23 of the first group of membrane supports, a membrane support connecting platform 24, an upper part 25 of the second group of membrane supports, a lower part 26 of the second group of membrane supports, a sealing cover 27 below the sampler, and a sampler air outlet 28.

[0040] In this embodiment, the specific structures of the first membrane series sampler and the second membrane series sampler are similar, and the difference between the two is that the adsorption membranes they contain are different. Specifically, the first membrane series sampler includes a front Teflon membrane and a rear first quartz membrane, wherein the Teflon membrane is arranged between the upper part 22 of the first group of membrane holders and the lower part 23 of the first group of membrane holders in the first membrane series sampler, and the first quartz membrane is arranged between the upper part of the second group of membrane holders and the lower part of the second group of membrane holders in the first membrane series sampler. The membrane holder connection platform 24 is short, which can eliminate the gas-solid equilibrium change caused by the excessive series pipeline. The second membrane series sampler only includes a front second quartz membrane, wherein the second quartz membrane is arranged between the upper part of the first group of membrane holders and the lower part of the first group of membrane holders in the second membrane series sampler.

[0041] The working process of the particle sampling device may include: before the target airflow enters the first channel 11 and the second channel 12, the cutter 10 in the particle sampling device screens the target airflow for particle size; the particle sampling device is used to collect particles from the target airflow; wherein, after the target airflow enters the first channel 11 and the second channel 12 of the particle sampling device, the Teflon membrane in the first channel 11 collects the particles in the target airflow, the first quartz membrane in the first channel 11 collects the gaseous adsorbents (also called gaseous organic matter) in the target airflow, and the second quartz membrane in the second channel 12 collects the particles and gaseous adsorbents in the target airflow; the gaseous adsorbents collected by the first quartz membrane, and the particles and gaseous adsorbents collected by the second quartz membrane are pre-treated to obtain a first sample and a second sample.

[0042] Specifically, the target airflow enters the aerodynamic equivalent particle size cutting head for particle size screening, which can generally screen fine particulate matter (PM 2.5); then, the target airflow is divided into two paths, entering the first channel 11 on the left and the second channel 12 on the right respectively. The first channel 11 includes a front Teflon membrane and a rear first quartz membrane. The front Teflon membrane collects particulate matter in the target airflow entering the first channel 11, and the rear first quartz membrane (also called adsorption membrane) collects gaseous adsorbates in the target airflow entering the first channel 11, thereby eliminating adsorption errors; the second channel 12 only includes the front second quartz membrane, and the second quartz membrane (also called sample membrane) collects particulate matter and gaseous adsorbates in the target airflow entering the second channel 12. Therefore, the particulate matter and gaseous adsorbates collected by the second quartz membrane are actual samples containing adsorption errors.

[0043] During the operation of the particle sampling device, after the adsorption film is placed at the corresponding position, the first mass flow controller 13 and the second mass flow controller 14 can be used to set the same sampling flow rate, and the diaphragm vacuum pump 16 can be turned on to start sample collection. In actual sampling, the particle sampling device can be placed in a constant temperature and humidity sampling box. After the sampling is completed, the first quartz film and the second quartz film can be taken out and balanced at a specific temperature and humidity for 24 hours to obtain the first sample and the second sample, and then the first sample and the second sample are quantified and the adsorption error is determined.

[0044] The following will be combined Figure 3 The method for determining the adsorption error in the quartz film collected particles provided by an embodiment of the present application is described, see Figure 3 , Figure 3 is a flow chart of a method for determining adsorption error in collecting particulate matter using a quartz membrane according to an embodiment of the present application. Figure 3 As shown, the method includes:

[0045] Step S101, performing full two-dimensional gas chromatography and mass spectrometry analysis on the first sample collected from the first quartz film and the second sample collected from the second quartz film, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; wherein the elements in the first matrix are Indicates that the first sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the second matrix Indicates that the second sample is in the volatility range And belongs to the compound type The content of the substance.

[0046] In this embodiment, the first matrix can be expressed as:

[0047]

[0048] The second matrix can be expressed as:

[0049]

[0050] As shown above, the rows of the first matrix and the second matrix can represent volatility intervals, and the columns of the first matrix and the second matrix can represent compound types. Specifically, the volatility intervals can include 30 volatility intervals divided on a one-dimensional gas chromatogram based on the peak time of each normal alkane; the compound types can include 17 types - straight-chain alkanes, branched alkanes, olefins, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons, oxygen-containing polycyclic aromatic hydrocarbons, alkyl-substituted polycyclic aromatic hydrocarbons, halogenated hydrocarbons, amines, and nitrates.

[0051] At this time, the dimensions of the first matrix and the second matrix are 30*17=510. Assuming that the position (1,1) corresponding to the element a1 in the first matrix and A1 in the second matrix represents volatility interval 1 and the compound type is straight-chain alkane, then a1 represents the content of the substance in volatility interval 1 and belonging to straight-chain alkane in the first sample; and A1 represents the content of the substance in volatility interval 1 and belonging to straight-chain alkane in the second sample.

[0052] In this embodiment, based on the constructed two-dimensional matrix, the contents of various organic matter contained in the first sample and the second sample can be calculated respectively. The organic matter in the complex sample can be accurately classified and quantitatively analyzed by full two-dimensional gas chromatography and mass spectrometry analysis, which can improve the accuracy of particulate matter quantification and provide accurate data input for the subsequent adsorption error determination step.

[0053] The specific process of obtaining the first matrix and the second matrix may include the following steps:

[0054] Step 1: Perform full two-dimensional gas chromatography analysis on the first sample and the second sample respectively to obtain a one-dimensional gas chromatogram and a two-dimensional gas chromatogram.

[0055] Step 2: divide the one-dimensional gas chromatogram into multiple volatility intervals.

[0056] In this embodiment, dividing the one-dimensional gas chromatogram into a plurality of volatility intervals includes dividing the one-dimensional gas chromatogram into 30 volatility intervals based on the peak time of each normal alkane.

[0057] Specifically, the saturated vapor pressure of normal alkanes decreases as the carbon number increases. Generally, normal alkanes with smaller carbon numbers have higher saturated vapor pressures, while normal alkanes with larger carbon numbers have lower vapor pressures. For normal alkanes with different carbon numbers, the difference between the saturated vapor pressures is regular. The saturated vapor pressure is closely related to factors such as temperature and carbon number, and can be estimated using an empirical formula. In general, the concentration of saturated vapor pressure decreases approximately linearly with the increase of carbon number.

[0058] The saturated vapor pressure concentration interval is 0.44 (log10 C * intervals), to determine the range of each volatility interval. Figure 4 , Figure 4 This is a schematic diagram of a one-dimensional gas chromatogram according to an embodiment of the present application. As shown in the figure, 30 volatility intervals can be divided on the x-axis of the one-dimensional gas chromatogram - one-dimensional retention time. By setting the starting point of the first volatility interval (such as the saturated vapor pressure value of the lowest volatile normal alkane), and then calculating the boundaries of the remaining 29 intervals according to the rule that each interval is 0.44, each calculated volatility interval corresponds to the peak time of the gas chromatogram; wherein, the one-dimensional retention time refers to the time required for the solute to pass through the chromatographic column, that is, the time from the start of injection to the appearance of the apex of the chromatographic peak of the component. It is determined by the thermodynamic factors in the chromatographic process and is an important basis for qualitative analysis; the signal intensity is the signal intensity value of the response signal generated when the effluent of the chromatographic column passes through the detector.

[0059] Step 3: Perform mass spectrometry analysis on the first sample and the second sample to classify all detected compounds in the two-dimensional gas chromatogram into multiple compound types.

[0060] In this embodiment, based on the mass spectral characteristics of each compound, constraints can be set according to the top five ion peaks, characteristic ion peak intensities and ratios to perform mass spectral condition screening, and all detected compounds in the two-dimensional gas chromatogram can be divided into multiple compound types.

[0061] In this embodiment, the types of compounds include at least two of the following: straight-chain alkanes, branched-chain alkanes, olefins, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons, oxygen-containing polycyclic aromatic hydrocarbons, alkyl-substituted polycyclic aromatic hydrocarbons, halogenated hydrocarbons, amines, and nitrates.

[0062] See also Figure 5 , Figure 5 is a schematic diagram of a two-dimensional gas chromatogram according to an embodiment of the present application, such as Figure 5 As shown, all detected compounds in the two-dimensional gas chromatogram can be divided into straight-chain alkanes, branched alkanes, alkenes, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons (PAH), oxygenated PAH, alkyl-substituted PAH, a total of 14 types of compounds; among them, in the two-dimensional gas chromatogram, in addition to the one-dimensional retention time (i.e., the x-axis), it also includes the two-dimensional retention time (y-axis). In the two-dimensional gas chromatogram, each compound peaks according to polarity. The greater the polarity, the greater the two-dimensional retention time.

[0063] It should be noted that the types of compounds to be classified can be set according to actual needs. For example, all detected compounds in the two-dimensional gas chromatogram can be classified into straight-chain alkanes, branched alkanes, olefins, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons, oxygen-containing polycyclic aromatic hydrocarbons, alkyl-substituted polycyclic aromatic hydrocarbons, halogenated hydrocarbons, amines, and nitrates, totaling 17 types of compounds.

[0064] Step 4: According to the multiple volatility intervals divided on the one-dimensional gas chromatogram and the multiple compound types divided on the two-dimensional gas chromatogram, the content of substances in the first sample and the second sample that are in each volatility interval and belong to each compound type is determined to obtain a first matrix and a second matrix.

[0065] It should be noted that although the method for determining the adsorption error in particulate matter collected by a quartz membrane provided in the embodiment of the present application uses a full two-dimensional gas chromatography analysis to obtain the first matrix and the second matrix, thereby improving the accuracy of the subsequent quantification of the adsorption error, in other embodiments, it is also possible to divide the volatility intervals and compound types by only combining the one-dimensional gas chromatogram to obtain the first matrix and the second matrix with lower dimensions or resolution, or it is also possible to use other chemical analysis methods to obtain the first matrix and the second matrix, and then calculate and correct the adsorption error.

[0066] Step S102: compare the elements at the same position in the first matrix and the second matrix one by one.

[0067] Step S103, if the elements in the first matrix are smaller than the elements in the corresponding positions in the second matrix, the elements in the first matrix are filled into the third matrix according to the corresponding positions; if the elements in the first matrix are greater than or equal to the elements in the corresponding positions in the second matrix, the elements in the second matrix are filled into the third matrix according to the corresponding positions.

[0068] In this embodiment, the elements at the same position in the first matrix and the second matrix may be compared one by one to determine the content of the gaseous adsorbent contained in the second sample.

[0069] Specifically, in this embodiment, the first matrix can be expressed as:

[0070]

[0071] The second matrix can be expressed as:

[0072]

[0073] Assuming that the position (1, 1) corresponding to the element a1 in the first matrix and A1 in the second matrix represents volatility interval 1 and the compound type is straight-chain alkane, if a1 is less than A1, it can be considered that the difference between A1 and a1 is the content of particulate organic matter in the second sample with volatility interval 1 and the compound type is straight-chain alkane, that is, a1 is the content of gaseous adsorbent in the second sample with volatility interval 1 and the compound type is straight-chain alkane, and a1 can be filled into the third matrix. If a1 is greater than or equal to A1, it can be considered that the excess content of the first quartz film may come from instrument analysis errors, volatilization of semi-volatile components in the particle sample of the front Teflon film, etc., which all lead to an overestimation of the content of organic matter contained in the first sample collected by the first quartz film. Since instrument analysis errors cannot be avoided, in order to remove the errors caused by the volatilization of components in the particle sample in the front Teflon film, A1 can be used as the content of gaseous adsorbent in the second sample with volatility interval 1 and the compound type is straight-chain alkane.

[0074] Through the above steps, after all elements in the first matrix and the second matrix are compared, a third matrix can be obtained. The third matrix can represent the content of organic matter of different compound types in different volatility ranges in the gaseous adsorbent contained in the second sample. Based on the third matrix, the adsorption error generated by the particulate matter collection device during the sampling process can be calculated.

[0075] Step S104: calculating the adsorption error based on the third matrix.

[0076] In this embodiment, after calculating the adsorption error based on the third matrix, the method further includes: performing error correction on elements in corresponding positions in the second matrix based on each element in the third matrix to obtain a corrected second matrix.

[0077] The third matrix can be used to correct the errors of the elements of the second matrix one by one to obtain a corrected second matrix, and based on the corrected second matrix, the contents of various components contained in the particulate matter in the target airflow can be determined.

[0078] Specifically, the elements in the second matrix can be subtracted from the elements in the corresponding positions in the third matrix, and after completing the error correction of all positions, the corrected second matrix can be obtained. In this way, the errors caused by the different positive and negative error sensitivities of organic matter in different volatile ranges can be eliminated, thereby improving the accuracy of quantifying gaseous adsorption errors in the quantitative process of particulate organic matter in the sample, and improving the accuracy of quantifying various components contained in the particulate matter.

[0079] In the front Teflon membrane, the error caused by the volatilization of organic matter of different volatility ranges and different compound types will greatly affect the estimation of the content of gaseous adsorbents. The method for determining the adsorption error in particulate matter collected by a quartz membrane provided in the embodiment of the present application can effectively determine the content of organic matter of different volatility ranges and different compound types in the gaseous adsorbents contained in the sample collected by the quartz membrane, thereby improving the accuracy of quantifying the gaseous adsorption error and facilitating the subsequent correction of the sample content.

[0080] In the test of light gasoline vehicle exhaust samples, it was found that when only a quartz membrane was used to collect particulate matter and the adsorption error of the particulate matter was estimated, the adsorption error was as high as 80%; however, when the adsorption error was calculated according to the adsorption error determination method provided in the embodiment of the present application, the log 10 C * For substances with a value less than 7, the adsorption error is only 10 to 20%, and the overall adsorption error is only 30%. In this way, the volatilization of organic matter on particles and the influence of instrument analysis errors in individual intervals can be largely eliminated, and the accuracy of quantitative gas adsorption errors can be improved in the quantitative process of particulate organic matter in samples, and the accuracy of quantitative analysis of various compounds contained in particulate organic matter can be improved.

[0081] Through the above steps S101 to S104, the samples collected by the quartz membrane in each sampling channel of the particulate matter sampling device are subjected to full two-dimensional gas chromatography and mass spectrometry analysis respectively to obtain a first matrix and a second matrix; and the elements in the same position in the first matrix and the second matrix are compared one by one, and a third matrix is ​​obtained based on the size relationship between the elements in the first matrix and the elements in the corresponding positions in the second matrix; finally, the adsorption error is calculated based on the third matrix; in this way, the volatilization of organic matter on the particulate matter and the influence of the instrument analysis error of individual intervals can be effectively eliminated, and a matrixed and fine adsorption error result can be obtained, which can improve the accuracy of quantifying the gaseous adsorption error and help to correct the sample content later. Through this application, the problem that the gaseous adsorption error cannot be accurately quantified in the related art, resulting in low accuracy in quantifying the particulate organic matter in the sample, is solved, and the technical effect of improving the accuracy of quantifying the gaseous adsorption error in the process of quantifying the particulate organic matter in the sample is achieved.

[0082] Corresponding to the method for determining the adsorption error in the quartz film collecting particles described in the above embodiment, Figure 6 A schematic structural diagram of a device for determining adsorption errors in particulate matter collected by a quartz membrane according to an embodiment of the present application is shown. For ease of explanation, only the parts related to the embodiment of the present application are shown.

[0083] See also Figure 6 The device 6 for determining the adsorption error in particulate matter collected by the quartz membrane is used to determine the adsorption error that occurs during the sampling process of the particulate matter sampling device, wherein the particulate matter sampling device includes a first channel 11 and a second channel 12, the first channel 11 includes a Teflon membrane and a first quartz membrane, and the second channel 12 includes a second quartz membrane. The device 6 for determining the adsorption error in particulate matter collected by the quartz membrane includes: an analysis module 60, which is used to perform full two-dimensional gas chromatography and mass spectrometry analysis on the first sample collected by the first quartz membrane and the second sample collected by the second quartz membrane, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; wherein the elements in the first matrix are Indicates that the first sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the second matrix Indicates that the second sample is in the volatility range And belongs to the compound type The content of the substance; a comparison module 61, used to compare the elements in the same position in the first matrix and the second matrix one by one; a filling module 62, used to fill the elements in the first matrix into the third matrix according to the corresponding position if the elements in the first matrix are smaller than the elements in the corresponding position in the second matrix; if the elements in the first matrix are greater than or equal to the elements in the corresponding position in the second matrix, then fill the elements in the second matrix into the third matrix according to the corresponding position; a calculation module 63, used to calculate the adsorption error based on the third matrix.

[0084] In one embodiment, the analysis module 60 is also used to perform full two-dimensional gas chromatography analysis on the first sample and the second sample, respectively, to obtain a one-dimensional gas chromatogram and a two-dimensional gas chromatogram; divide the one-dimensional gas chromatogram into multiple volatility intervals; perform mass spectrometry analysis on the first sample and the second sample, and divide all detected compounds in the two-dimensional gas chromatogram into multiple compound types; determine the content of substances in each volatility interval and belonging to each compound type in the first sample and the second sample according to the multiple volatility intervals divided on the one-dimensional gas chromatogram and the multiple compound types divided on the two-dimensional gas chromatogram, and obtain a first matrix and a second matrix.

[0085] In one embodiment, the analysis module 60 is further configured to divide the one-dimensional gas chromatogram into 30 volatility intervals based on the peak time of each normal alkane.

[0086] In one embodiment, the compound types include at least two of the following: straight-chain alkanes, branched-chain alkanes, olefins, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons, oxygen-containing polycyclic aromatic hydrocarbons, alkyl-substituted polycyclic aromatic hydrocarbons, halogenated hydrocarbons, amines, and nitrates.

[0087] In one embodiment, the device 6 for determining adsorption errors in particles collected by quartz membrane further includes a correction module for performing error correction on elements at corresponding positions in the second matrix based on elements in the third matrix to obtain a corrected second matrix.

[0088] In one embodiment, the device 6 for determining the adsorption error in particulate matter collected by the quartz membrane further includes a collection module for collecting particulate matter from the target airflow using the particulate matter sampling device; wherein, after the target airflow enters the first channel 11 and the second channel 12 of the particulate matter sampling device, the particulate matter in the target airflow is collected by the Teflon membrane in the first channel 11, the gaseous adsorbates in the target airflow are collected by the first quartz membrane in the first channel 11, and the particulate matter and gaseous adsorbates in the target airflow are collected by the second quartz membrane in the second channel 12; the gaseous adsorbates collected by the first quartz membrane, and the particulate matter and gaseous adsorbates collected by the second quartz membrane are pre-processed to obtain a first sample and a second sample.

[0089] In one embodiment, before the target airflow enters the first channel 11 and the second channel 12 , the cutter 10 in the particle sampling device performs particle size screening on the target airflow.

[0090] It should be noted that the information interaction, execution process, etc. between the above-mentioned devices / units are based on the same concept as the method embodiment of the present application. Their specific functions and technical effects can be found in the method embodiment part and will not be repeated here.

[0091] The technicians in the relevant field can clearly understand that for the convenience and simplicity of description, only the division of the above-mentioned functional units and modules is used as an example for illustration. In practical applications, the above-mentioned function allocation can be completed by different functional units and modules as needed, that is, the internal structure of the device can be divided into different functional units or modules to complete all or part of the functions described above. The functional units and modules in the embodiment can be integrated in a processing unit, or each unit can exist physically separately, or two or more units can be integrated in one unit. The above-mentioned integrated unit can be implemented in the form of hardware or in the form of software functional units. In addition, the specific names of the functional units and modules are only for the convenience of distinguishing each other, and are not used to limit the scope of protection of this application. The specific working process of the units and modules in the above-mentioned system can refer to the corresponding process in the aforementioned method embodiment, which will not be repeated here.

[0092] Figure 7 is a schematic diagram of the structure of a terminal device according to an embodiment of the present application. Figure 7 As shown, the terminal device 7 includes: at least one processor 70 ( Figure 7 (only one is shown in the figure) a processor, a memory 71, and a computer program 72 stored in the memory 71 and executable on at least one processor 70. When the processor 70 executes the computer program 72, the steps in any of the above-mentioned embodiments of the method for determining the adsorption error in particulate matter collected by a quartz membrane are implemented.

[0093] The terminal device 7 may be a computing device such as a desktop computer, a notebook, a PDA, or a cloud server. The terminal device 7 may include, but is not limited to, a processor 70 and a memory 71. It is understood by those skilled in the art that Figure 7 It is only an example of the terminal device 7 and does not constitute a limitation on the terminal device 7. It may include more or fewer components than shown in the figure, or a combination of certain components, or different components. For example, it may also include input and output devices, network access devices, etc.

[0094] The processor 70 may be a central processing unit (CPU), or other general-purpose processors, digital signal processors (DSP), application-specific integrated circuits (ASIC), field-programmable gate arrays (FPGA) or other programmable logic devices, discrete gate or transistor logic devices, discrete hardware components, etc. A general-purpose processor may be a microprocessor or any conventional processor, etc.

[0095] In some embodiments, the memory 71 may be an internal storage unit of the terminal device 7, such as a hard disk or memory of the terminal device 7. In other embodiments, the memory 71 may also be an external storage device of the terminal device 7, such as a plug-in hard disk, a smart media card (SMC), a secure digital (SD) card, a flash card, etc. equipped on the terminal device 7. In other embodiments, the memory 71 may also include both an internal storage unit and an external storage device of the terminal device 7. The memory 71 is used to store an operating system, an application program, a boot loader (BootLoader), data, and other programs, such as program codes of a computer program 72. The memory 71 may also be used to temporarily store data that has been output or is to be output.

[0096] The embodiment of the present application further provides a computer-readable storage medium storing a computer program, which, when executed by a processor, can implement the steps in the above-mentioned embodiments of the method for determining adsorption errors in particulate matter collected by a quartz membrane.

[0097] The embodiment of the present application provides a computer program product. When the computer program product is executed on a mobile terminal, the mobile terminal can implement the steps in the above-mentioned embodiments of the method for determining adsorption errors in particulate matter collected by a quartz film.

[0098] The present application implements all or part of the processes in the above-mentioned embodiment method, which can be completed by instructing the relevant hardware through a computer program, and the computer program can be stored in a computer-readable storage medium. When the computer program is executed by the processor, the steps of each of the above-mentioned method embodiments can be implemented. Among them, the computer program includes computer program code, and the computer program code can be in source code form, object code form, executable file or some intermediate form. The computer-readable medium may at least include: any entity or device that can carry the computer program code to the camera device / terminal device, recording medium, computer memory, read-only memory (ROM, Read-Only Memory), random access memory (RAM, Random Access Memory), electrical carrier signal, telecommunication signal and software distribution medium. For example, a USB flash drive, a mobile hard disk, a disk or an optical disk.

[0099] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described or recorded in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0100] Those of ordinary skill in the art will appreciate that the units and algorithm steps of each example described in conjunction with the embodiments disclosed herein can be implemented in electronic hardware, or a combination of computer software and electronic hardware. Whether these functions are performed in hardware or software depends on the specific application and design constraints of the technical solution. Professional and technical personnel can use different methods to implement the described functions for each specific application, but such implementation should not be considered to be beyond the scope of this application.

[0101] In the embodiments provided in the present application, it should be understood that the disclosed devices / network equipment and methods can be implemented in other ways. For example, the device / network equipment embodiments described above are only schematic. For example, the division of modules or units is only a logical function division. There may be other division methods in actual implementation, such as multiple units or components can be combined or integrated into another system, or some features can be ignored or not executed. Another point is that the mutual coupling or direct coupling or communication connection shown or discussed can be through some interfaces, indirect coupling or communication connection of devices or units, which can be electrical, mechanical or other forms.

[0102] The units described as separate components may or may not be physically separated, and the components shown as units may or may not be physical units, that is, they may be located in one place or distributed on multiple network units. Some or all of the units may be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0103] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application, and should all be included in the protection scope of the present application.

Claims

1. A method for determining adsorption error in the collection of particulate matter by a quartz membrane, which is applied to determine the adsorption error occurring during the sampling process of a particulate matter sampling device, wherein: The particle sampling device comprises a first channel and a second channel, the first channel comprises a Teflon membrane and a first quartz membrane, the second channel comprises a second quartz membrane, and the method comprises: The first sample collected from the first quartz film and the second sample collected from the second quartz film are respectively subjected to full two-dimensional gas chromatography and mass spectrometry analysis to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; wherein the elements in the first matrix Indicates that the first sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the second matrix Indicates that the second sample is in the volatility range And belongs to the compound type the content of the substance; Compare the elements at the same position in the first matrix and the second matrix one by one; If the elements in the first matrix are smaller than the elements in the corresponding positions in the second matrix, the elements in the first matrix are filled into the third matrix according to the corresponding positions; if the elements in the first matrix are greater than or equal to the elements in the corresponding positions in the second matrix, the elements in the second matrix are filled into the third matrix according to the corresponding positions; A suction error is calculated based on the third matrix.

2. The method according to claim 1, characterized in that Performing full two-dimensional gas chromatography and mass spectrometry analysis on the first sample collected from the first quartz film and the second sample collected from the second quartz film, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample, including: Performing full two-dimensional gas chromatography analysis on the first sample and the second sample respectively to obtain a one-dimensional gas chromatogram and a two-dimensional gas chromatogram; dividing a plurality of volatility intervals on the one-dimensional gas chromatogram; Performing mass spectrometry analysis on the first sample and the second sample, and dividing all compounds detected in the two-dimensional gas chromatogram into multiple compound types; According to the multiple volatility intervals divided on the one-dimensional gas chromatogram and the multiple compound types divided on the two-dimensional gas chromatogram, the content of substances in the first sample and the second sample that are in each volatility interval and belong to each compound type is determined to obtain the first matrix and the second matrix.

3. The method according to claim 2, characterized in that Dividing the one-dimensional gas chromatogram into a plurality of volatility intervals comprises: Based on the peak time of each normal alkane, 30 volatility intervals are divided on the one-dimensional gas chromatogram.

4. The method according to any one of claims 1 to 3, characterized in that The compound types include at least two of the following: straight-chain alkanes, branched-chain alkanes, olefins, alcohol ethers, aldehydes, ketones, acids, monocyclic aromatic hydrocarbons, phthalates, hopanes, steranes, polycyclic aromatic hydrocarbons, oxygen-containing polycyclic aromatic hydrocarbons, alkyl-substituted polycyclic aromatic hydrocarbons, halogenated hydrocarbons, amines, and nitrates.

5. The method according to any one of claims 1 to 3, characterized in that After calculating the adsorption error based on the third matrix, the method further includes: Based on each element in the third matrix, error correction is performed on the elements in the corresponding position in the second matrix to obtain the corrected second matrix.

6. The method according to any one of claims 1 to 3, characterized in that Before respectively performing comprehensive two-dimensional gas chromatography and mass spectrometry analysis on the first sample collected from the first quartz film and the second sample collected from the second quartz film, the method further includes: The particle sampling device is used to collect particles from a target airflow; wherein, after the target airflow enters the first channel and the second channel of the particle sampling device, the Teflon membrane in the first channel collects particles in the target airflow, the first quartz membrane in the first channel collects gaseous adsorbates in the target airflow, and the second quartz membrane in the second channel collects the particles and the gaseous adsorbates in the target airflow; The gaseous adsorbate collected by the first quartz film, and the particulate matter and the gaseous adsorbate collected by the second quartz film are pre-processed to obtain the first sample and the second sample.

7. The method according to claim 6, characterized in that Before the target airflow enters the first channel and the second channel, the cutter in the particle sampling device performs particle size screening on the target airflow.

8. A device for determining adsorption errors in the collection of particles by a quartz membrane, used to determine adsorption errors that occur during the sampling process of a particle sampling device, wherein: The particle sampling device comprises a first channel and a second channel, the first channel comprises a Teflon membrane and a first quartz membrane, the second channel comprises a second quartz membrane, and is characterized in that the adsorption error determination device in the particle collected by the quartz membrane comprises: An analysis module is used to perform full two-dimensional gas chromatography and mass spectrometry analysis on the first sample collected by the first quartz film and the second sample collected by the second quartz film, respectively, to obtain a first matrix corresponding to the first sample and a second matrix corresponding to the second sample; wherein the elements in the first matrix Indicates that the first sample is in the volatility range And belongs to the compound type The content of the substance; the elements in the second matrix Indicates that the second sample is in the volatility range And belongs to the compound type the content of the substance; A comparison module, used for comparing elements at the same position in the first matrix and the second matrix one by one; A filling module, configured to fill the elements in the first matrix into the third matrix according to the corresponding positions if the elements in the first matrix are smaller than the elements in the second matrix at the corresponding positions; and fill the elements in the second matrix into the third matrix according to the corresponding positions if the elements in the first matrix are greater than or equal to the elements in the second matrix at the corresponding positions; A calculation module is used to calculate the adsorption error based on the third matrix.

9. A terminal device, comprising a memory, a processor, and a computer program stored in the memory and executable on the processor, characterized in that: When the processor executes the computer program, the method for determining adsorption errors in collecting particulate matter with a quartz membrane as described in any one of claims 1 to 7 is implemented.

10. A computer program product, characterized in that The invention comprises a computer program, and when the computer program is executed, the method for determining adsorption error in collecting particulate matter with a quartz membrane as claimed in any one of claims 1 to 7 is executed.

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