CN117723623B - Source analysis method for subdividing secondary organic aerosol by combining contributions of organic matters in inorganic matrix - Google Patents
Source analysis method for subdividing secondary organic aerosol by combining contributions of organic matters in inorganic matrix Download PDFInfo
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- 239000000443 aerosol Substances 0.000 title claims abstract description 53
- 239000011159 matrix material Substances 0.000 title claims abstract description 52
- 238000004458 analytical method Methods 0.000 title claims abstract description 18
- 239000012634 fragment Substances 0.000 claims abstract description 84
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 56
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 56
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000009792 diffusion process Methods 0.000 claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 46
- 239000011593 sulfur Substances 0.000 claims abstract description 46
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 38
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 35
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 32
- 229910001959 inorganic nitrate Inorganic materials 0.000 claims abstract description 24
- 230000008859 change Effects 0.000 claims abstract description 19
- 238000002474 experimental method Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 65
- 150000002500 ions Chemical class 0.000 claims description 58
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920000557 Nafion® Polymers 0.000 claims description 9
- 239000013618 particulate matter Substances 0.000 claims description 6
- 238000002076 thermal analysis method Methods 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 4
- 238000009533 lab test Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052920 inorganic sulfate Inorganic materials 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention discloses a source analysis method for finely dividing secondary organic aerosol by combining the contribution of organic matters in an inorganic matrix, which comprises the following steps of S1, calibrating the ratio of nitrogenous fragments to sulphurous fragments; s2, determining the optimal temperature for distinguishing organic nitrate and inorganic nitrate; s3, determining a concentration matrix of the PMF; s4, determining an error matrix of the PMF. The advantages are that: based on the observation of a thermal diffusion tube-aerosol mass spectrometer system, utilizing the difference of the volatility of inorganic nitrate and organic nitrate to separate the contribution of the organic nitrate from the ammonium nitrate; the contribution of the organic sulfide is separated from the ammonium sulfate by utilizing the difference of the ratio of the sulfur-containing fragments between the inorganic sulfate and the organic sulfide, and the inorganic sulfate and the organic sulfide are combined with an organic matrix, so that the precise analysis of the SOA in the complex atmospheric environment is realized, and the method is suitable for various scenes including external field observation experiments and laboratory researches. The method has important significance for complex environments, especially for quantitative and real-time change research of SOA in the actual atmosphere of complex precursors.
Description
Technical Field
The invention relates to the technical field of environmental science, in particular to a source analysis method for subdividing secondary organic aerosol by combining contributions of organic matters in an inorganic matrix.
Background
Organic Aerosols (OA) are important components of aerosols, accounting for about 20-90% of submicron aerosols worldwide. Depending on the manner of generation, OA can be divided into Primary Organic Aerosols (POA) that are directly discharged into the atmosphere, and Secondary Organic Aerosols (SOA) that are generated after oxidation of gaseous precursors in the atmosphere, which have a very important impact on human health, interactions of aerosols and clouds, and even global climate change. However, the source components of the SOA, the aging process generated and other characteristics are not completely clear, so that a large difference exists between the mode simulation and the observation.
Early studies of SOA have mainly utilized some rough assumptions to estimate SOA, or were limited to some organic acids and polyols. With the development of on-line technology, EC trace/CO trace, OC/EC ratio method and orthogonal matrix model (PMF) based aerosol mass spectrometer method are widely used for the study of SOA. In particular, the use of an aerosol mass spectrometer (e.g., a four-bar aerosol chemical composition monitor Q-ACSM, a time-of-flight aerosol chemical composition monitor ToF-ACSM, a four-bar aerosol mass spectrometer Q-AMS, a high resolution aerosol mass spectrometer HR-AMS) in combination with PMF for source resolving organic aerosols using organic matrices has become a common method for source resolving organic aerosols. In the process of source analysis of an SOA, the SOA is often analyzed into an organic aerosol (MO-OOA) in a high oxidation state and an organic aerosol (LO-OOA) in a low oxidation state. In practice, however, MO-OOA is affected by different precursors and chemical processes and cannot be further distinguished by mass spectrometers such as HR-AMS, Q-ACSM, toF-ACSM, Q-AMS, etc. using PMF methods, where different types of organic components, e.g., organic nitrogen and organic sulfur, etc., may be mixed, resulting in MO-OOA exhibiting different physicochemical characteristics such as volatility at different relative humidities.
Indeed, there have been a number of studies showing that fragments associated with inorganic substances in aerosol mass spectrometry still contain information on organic substances. For example, fragments NO + and NO 2 + of nitrate, there may be a signal of organic nitrate; the presence of organic sulfur signals in sulfate fragment SO +,SO2 +,SO3 +,HSO3 +. Thus, using PMF resolution using only an organic matrix has certain drawbacks in distinguishing the sources of SOAs.
Disclosure of Invention
The present invention aims to provide a source analysis method for subdividing secondary organic aerosols by combining contributions of organic matters in an inorganic matrix, so as to solve the aforementioned problems in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A source analysis method for subdividing secondary organic aerosol by combining contributions of organic matters in an inorganic matrix comprises the following steps,
S1, calibrating the ratio of the nitrogenous chips to the sulfur-containing chips:
respectively generating nitrate particles and sulfate particles from pure ammonium nitrate and pure ammonium sulfate solutions with different concentrations by utilizing an aerosol generator, measuring the dried nitrate particles and sulfate particles by utilizing an HR-AMS, and obtaining the ratio of nitrogen-containing fragment ions and the ratio of sulfur-containing fragment ions of the pure ammonium nitrate and the pure ammonium sulfate under different concentrations by analyzing mass spectrogram data;
S2, determining the optimal temperature for distinguishing organic nitrate and inorganic nitrate:
Calibrating the loss efficiency of the thermal diffusion tube by using a TD-HR-AMS system, obtaining a thermal analysis chart of pure ammonium nitrate, obtaining a change chart of the mass residual fraction of the ammonium nitrate along with the temperature, and determining the volatilization temperature of the pure ammonium nitrate based on the change chart; the method comprises the steps of (1) determining the optimal temperature for distinguishing organic nitrate from inorganic nitrate by analyzing two paths of particle chemical components and an organic aerosol mass spectrogram through a TD-HR-AMS system;
S3, determining a concentration matrix of PMF:
Determining a concentration matrix of PMF based on the conventional organic matrix, the mass concentration of nitrogen-containing fragments remaining after the thermal diffusion pipeline is heated to an optimal temperature, and the concentration of sulfur-containing fragments;
S4, determining an error matrix of the PMF:
The error matrix of the PMF is determined based on the error matrix of the conventional organic matrix, the standard error of the mass concentration of the nitrogen-containing chips remaining after the thermal diffusion line is heated to the optimal temperature, and the standard error of the concentration of the sulfur-containing chips.
Preferably, in the step S1, a pure ammonium nitrate and ammonium sulfate solution with a certain concentration is prepared, the concentration of the solution is not more than 5mM, nitrate particles and sulfate particles are respectively generated by the prepared solution through an aerosol generator, the nitrate particles and the sulfate particles are dried through a drying system, 250-300nm nitrate particles are screened out from the dried nitrate particles based on a differential particle electromigration device, then the nitrate particles and the sulfate particles are measured through an HR-AMS, and the ratio of nitrogen-containing fragment ions to the ratio of sulfur-containing fragment ions under the pure ammonium nitrate and the pure ammonium sulfate is obtained through analyzing mass spectrogram data; and obtaining the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions under the pure ammonium nitrate and the pure ammonium sulfate with different concentrations by adjusting the concentrations of the pure ammonium nitrate and the pure ammonium sulfate solution.
Preferably, the nitrate-generated nitrogen-containing fragment ions include NO + andSulfate-generated sulfur-containing fragment ions include SO +,/>
Preferably, for the external field observation, the calibration of the ratio of the nitrogen-containing fragment ions in the pure nitrate and the ratio of the sulfur-containing fragment ions in the pure ammonium sulfate comprises three times, namely before observation, during observation and after observation, respectively, so as to evaluate the stability of the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions during the operation of the instrument; in laboratory experiments, the ratio of the nitrogen-containing fragment ions in the pure nitrate and the ratio of the sulfur-containing fragment ions in the pure ammonium sulfate are calibrated twice, namely after the instrument is stabilized before the experiment and after the experiment is finished, respectively, so as to evaluate the stability of the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions during the operation of the instrument; the ratio of the nitrogen-containing fragment ions to the ratio of the sulfur-containing fragment ions is analyzed by selecting the high-concentration nitrate and high-concentration sulfate pollution stages during observation and compared with pure ammonium nitrate and pure ammonium sulfate to determine the final ratio of the fragment ions.
Preferably, the TD-HR-AMS system includes a nafion dryer tube, a bypass, a heat diffusion conduit, and an HR-AMS; the nafion drying pipe is connected with the HR-AMS through a bypass and a heat diffusion pipeline; the heat diffusion pipeline continuously heats at constant temperature in a circulating way with different temperature gradients.
Preferably, in the step S2, the loss efficiency of the thermal diffusion tube is calibrated by using a TD-HR-AMS system, a thermal analysis chart of pure ammonium nitrate is obtained, a change chart of the mass residual fraction of the ammonium nitrate along with the temperature is obtained, specifically,
The heat diffusion tube is provided with different temperature gradients from 25 ℃ to 250 ℃, firstly NaCl particles with different particle sizes are selected to pass through the heat diffusion tube and the bypass respectively, the pipeline loss of the heat diffusion tube at different temperatures is calculated through the ratio of the logarithmic concentration, then pure ammonium nitrate particles are alternately introduced into the heat diffusion tube and the bypass, the residual concentration of ammonium nitrate at different temperatures is measured, further a change chart of the mass residual fraction of the ammonium nitrate along with the temperature is obtained, and the total volatilization of the pure ammonium nitrate at 60 ℃ is determined based on the change chart, namely, the inorganic nitrate in the actual atmosphere can be effectively removed when the temperature is higher than the temperature.
Preferably, in step S2, the particulate matter in the atmosphere is passed through a TD-HR-AMS system, and the two paths of particulate chemical components and the organic aerosol mass spectrum are analyzed to determine the optimal temperature for distinguishing the organic nitrate from the inorganic nitrate, specifically,
The method comprises the steps that particles in the atmosphere are dried through a nafion drying pipe and then alternately enter a bypass of direct sample injection and a heat diffusion pipeline of continuous constant-temperature heating, the bypass and the heat diffusion pipeline are switched once at regular intervals, then measurement is carried out by utilizing HR-AMS, the mass concentration of organic nitrogen-containing fragment ions in the actual atmosphere and after heating is obtained through mass spectrogram analysis of two paths of chemical components of the particles and the organic aerosol, the mass residual fraction of each nitrogen-containing fragment ion at different temperatures is obtained, and inorganic nitrate and the actual atmosphere NO + are analyzedThe ratio was determined and 90 ℃ was one of the best temperatures to distinguish between organic nitrate and inorganic nitrate.
Preferably, the residence time of the particulate matter in the thermal diffusion tube should be 20-30 seconds to ensure that the particulate chemical components are allowed to volatilize at the set temperature without excessive losses due to residence time.
Preferably, the sulfur-containing chip concentration is calculated by,
Wherein, [ SO +]measure ], SO +,/>, respectively, measured in the atmospheric environment by HR-AMS Is a concentration of (2); SO +// >, respectively, of pure ammonium sulphate Ratio of; [ SO +]S-containing ],Fragments from organosulfides for SO +,/>, respectivelyThe concentration contributed.
Preferably, the standard deviation of the concentration of sulfur-containing chips is calculated by,
Wherein [ delta SO +]measure ], Respectively represent SO +,/>, measured by HR-AMS in the atmosphere Standard deviation of concentration; /(I)SO +// >, respectively, of pure ammonium sulphateRatio of; [ delta SO +]S-containing ], Fragments from organosulfides for SO +,/>, respectively Standard error of concentration contributed.
The beneficial effects of the invention are as follows: the method is based on observation of a thermal diffusion tube-aerosol mass spectrometer system, and utilizes the difference of the volatility of inorganic nitrate and organic nitrate to separate the contribution of the organic nitrate from ammonium nitrate; the contribution of the organic sulfide is separated from the ammonium sulfate by utilizing the difference of the ratio of the sulfur-containing fragments between the inorganic sulfate and the organic sulfide, and the inorganic sulfate and the organic sulfide are combined with an organic matrix, so that the precise analysis of the SOA in the complex atmospheric environment is realized, and the method is suitable for various scenes including external field observation experiments and laboratory researches. The method has important significance for complex environments, especially for quantitative and real-time change research of SOA in the actual atmosphere of complex precursors.
Drawings
FIG. 1 is a flow chart of an parsing method in an embodiment of the invention;
FIG. 2 is a schematic diagram of the structure of a TD-HR-AMS in an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description is presented by way of example only and is not intended to limit the invention.
As shown in fig. 1, in this embodiment, a source analysis method for subdividing secondary organic aerosol in combination with contribution of organic matters in an inorganic matrix is provided, the method is based on a thermal diffusion tube-high resolution time-of-flight aerosol mass spectrometer system (TD-HR-AMS) to measure fragment ions at different temperatures, mainly using the difference of volatility of organic nitrate and nitrate to introduce nitrogen-containing fragments, using the difference of fragment ratio between inorganic sulfate and organic sulfide to introduce sulfur-containing fragments, finally separating contribution of organic matters in the inorganic matrix, and combining the organic matrix to synthesize a specific matrix together to perform source analysis on the organic aerosol by using a PMF method. The method comprises the following parts:
1. Calibrating the ratio of the nitrogenous chips to the sulfur-containing chips:
The method comprises the steps of respectively generating nitrate particles and sulfate particles by using pure ammonium nitrate and pure ammonium sulfate solutions with different concentrations through an aerosol generator, measuring the dried nitrate particles and sulfate particles through HR-AMS, and obtaining the ratio of nitrogen-containing fragment ions and the ratio of sulfur-containing fragment ions of the pure ammonium nitrate and the pure ammonium sulfate under different concentrations through analysis of mass spectrogram data.
In this example, the nitrate-produced nitrogen-containing fragments include NO + andSulfate-produced sulfur-containing fragments include SO +,/>The determination of the nitrogen-containing chips and sulfur-containing chips is an important precondition for measuring the ratio of organic nitrate to nitrate and the ratio of organic sulfur to sulfate, and therefore, the calibration of pure ammonium sulfate and pure ammonium nitrate is required.
The calibration method specifically comprises the following steps: preparing pure ammonium nitrate and ammonium sulfate solution with certain concentration, wherein the concentration of the solution is not more than 5mM in order to reduce the influence of double charged particles, respectively generating nitrate particles and sulfate particles by using an aerosol generator, drying the nitrate particles and the sulfate particles by using a drying system (such as a silica gel drying agent), screening nitrate particles with the particle size of 250-300nm based on a differential particle electromigration device (the particle size of the sulfate particles can not be required) after the nitrate particles and the sulfate particles are dried by using the drying system, measuring the nitrate particles and the sulfate particles by using an HR-AMS, and obtaining SO + and SO + under the pure ammonium nitrate and pure ammonium sulfate by analyzing mass spectrogram dataConcentration and ratio, and SO + - In order to ensure the reliability of the data, the concentrations of the ammonium nitrate and the ammonium sulfate are adjusted during calibration, and the ratio of the nitrogen-containing fragment ions to the ratio of the sulfur-containing fragment ions under pure ammonium nitrate and pure ammonium sulfate with different concentrations are obtained.
In this embodiment, for the external field observation, calibration of pure ammonium nitrate and pure ammonium sulfate is recommended to be performed three times, before observation, during observation and after observation, respectively, so as to evaluate the stability of the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions during the operation of the instrument. In laboratory experiments, the calibration of the ratio of the nitrogen-containing fragment ions in the pure nitrate and the ratio of the sulfur-containing fragment ions in the pure ammonium sulfate comprises two times, namely before the experiment, after the stabilization of the instrument and after the end of the experiment, so as to evaluate the stability of the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions during the operation of the instrument.
The ratio of the nitrogen-containing fragment ions to the ratio of the sulfur-containing fragment ions is analyzed by selecting the high-concentration nitrate and high-concentration sulfate pollution stages during observation and compared with pure ammonium nitrate and pure ammonium sulfate to determine the final ratio of the fragment ions.
2. Optimum temperature determination to distinguish organic nitrate from inorganic nitrate:
calibrating the loss efficiency of a thermal diffusion tube by using a TD-HR-AMS system, obtaining a thermal analysis chart of pure ammonium nitrate, obtaining a change chart of the mass residual fraction of the ammonium nitrate along with the temperature, and determining the volatilization temperature of the pure ammonium nitrate based on the change chart; the particles in the atmosphere are analyzed by a TD-HR-AMS system through the two-path particle chemical composition and an organic aerosol mass spectrogram to determine the optimal temperature for distinguishing the organic nitrate and the inorganic nitrate.
In this embodiment, the TD-HR-AMS system architecture is shown in FIG. 2, including nafion drying tubes, bypasses, heat diffusion lines, and HR-AMS; the nafion drying pipe is connected with the HR-AMS through a bypass and a heat diffusion pipeline; the heat diffusion pipeline continuously heats at constant temperature in a circulating way with different temperature gradients.
In the embodiment, the TD-HR-AMS system is utilized to calibrate the loss efficiency of the heat diffusion tube, and a thermal analysis chart of pure ammonium nitrate is obtained, so that a change chart of the mass residual fraction of the ammonium nitrate along with the temperature is obtained, specifically: the thermal diffusion tube is provided with different temperature gradients from 25 ℃ to 250 ℃, naCl particles with different particle sizes are firstly selected to pass through the thermal diffusion tube and the bypass respectively, the pipeline loss of the thermal diffusion tube at different temperatures is calculated through the ratio of the logarithmic concentration, then pure ammonium nitrate particles are alternately introduced into the thermal diffusion tube and the bypass, the residual concentration of ammonium nitrate at different temperatures is measured, and further a change chart of the mass residual fraction (MFR) of the ammonium nitrate along with the temperature is obtained, and the pure ammonium nitrate is found to be volatilized all at 60 ℃ through the test based on the change chart, namely, the inorganic nitrate in the actual atmosphere can be effectively removed when the temperature is higher than the temperature.
In this example, the specific procedure for determining the temperature to distinguish between organic nitrate and inorganic nitrate is: the particles in the atmosphere are dried by a nafion drying pipe and then alternately enter a bypass of direct sample injection and a heat diffusion pipeline of continuous constant temperature heating (the bypass of direct sample injection is used for collecting environmental samples), the bypass and the heat diffusion pipeline are switched once at regular intervals (15 minutes), and then the measurement is carried out by utilizing the HR-AMS.
The two paths of particle chemical components and the organic aerosol mass spectrogram are analyzed to obtain organic nitrogen-containing fragment ions (C xHyNp + and C xHyOzNp +)NO+,The mass concentration after actual atmosphere and heating, and thus the mass residual fraction of each nitrogen-containing fragment ion at different temperatures. The key to the system is to determine the optimal temperature to distinguish between inorganic nitrate and organic nitrate by analyzing inorganic nitrate and actual atmospheric NO +// >The ratio found that at a temperature of 90 ℃, the inorganic nitrate can be totally volatilized, and the organic nitrate can retain higher residual mass, so that the 90 ℃ can be determined as one of the optimal temperatures for distinguishing the organic nitrate from the inorganic nitrate.
When the system is used for observation, the residence time of the particles in the thermal diffusion tube is about 20-30 seconds so as to ensure that the chemical components of the particles are fully volatilized at the set temperature, but the loss is not excessive due to the overlong residence time. In addition, the airflow disturbance in the two-way switching process can have a certain influence on the quantification of aerosol, so that the data of the switching period are removed in analysis.
3. Concentration matrix determination of PMF:
The concentration matrix of PMF is determined based on the conventional organic matrix, the mass concentration of nitrogen-containing chips remaining after the thermal diffusion line is heated to an optimal temperature, and the concentration of sulfur-containing chips.
The concentration matrix of PMF consists of the following three parts, the first part being a conventional organic matrix; the second part is the nitrogen-containing chips [ NO +]T＝90℃ ] remaining after TD is heated to 90℃,[ NO +]T＝90℃ ] represents the mass concentration of NO + remaining after heating to 90 ℃,/>Represents the/>, remaining after heating to 90 °cIs a mass concentration of (2); the third part is sulfur-containing fragments, the concentration of the sulfur-containing fragments is calculated in a way,
Wherein, [ SO +]measure ], SO +,/>, respectively, measured in the atmospheric environment (laboratory) by HR-AMS Is a concentration of (2); /(I)SO + +.Ratio of; [ SO +]S-containing ],Fragments from organosulfides for SO +,/>, respectivelyThe concentration contributed.
4. Error matrix determination of PMF:
The error matrix of the PMF is determined based on the error matrix of the conventional organic matrix, the standard error of the mass concentration of the nitrogen-containing chips remaining after the thermal diffusion line is heated to the optimal temperature, and the standard error of the concentration of the sulfur-containing chips.
Similarly, the error matrix of the PMF consists of the following three parts: the first part is an error matrix of a conventional organic matrix; the second part is the nitrogen-containing fragments [ delta NO +]T＝90℃ ] left after TD is heated to 90 DEG,[ Delta NO +]T＝90℃ ] represents the standard deviation of the mass concentration of NO + remaining after heating to 90 ℃,/>Represents the/>, remaining after heating to 90 °cStandard deviation of mass concentration of (2); the third part is the standard error of the concentration of sulfur-containing fragments, which is calculated in such a way that,
Wherein [ delta SO +]measure ], Respectively represent SO +,/>, measured by HR-AMS in the atmospheric environment (laboratory) Standard deviation of concentration; [ delta SO +]S-containing ] Fragments from organosulfides for SO +,Standard error of concentration contributed.
By adopting the technical scheme disclosed by the invention, the following beneficial effects are obtained:
The invention provides a source analysis method for finely dividing secondary organic aerosol by combining the contribution of organic matters in an inorganic matrix, which is based on the observation of a thermal diffusion tube-aerosol mass spectrometer system and separates the contribution of organic nitrate from ammonium nitrate by utilizing the volatility difference of inorganic nitrate and organic nitrate; the contribution of the organic sulfide is separated from the ammonium sulfate by utilizing the difference of the ratio of the sulfur-containing fragments between the inorganic sulfate and the organic sulfide, and the inorganic sulfate and the organic sulfide are combined with an organic matrix, so that the precise analysis of the SOA in the complex atmospheric environment is realized, and the method is suitable for various scenes including external field observation experiments and laboratory researches. The method has important significance for complex environments, especially for quantitative and real-time change research of SOA in the actual atmosphere of complex precursors.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which is also intended to be covered by the present invention.
Claims (8)
1. A source analysis method for subdividing secondary organic aerosol by combining contributions of organic matters in an inorganic matrix is characterized by comprising the following steps of: comprises the following steps of the method,
S1, calibrating the ratio of the nitrogenous chips to the sulfur-containing chips:
respectively generating nitrate particles and sulfate particles from pure ammonium nitrate and pure ammonium sulfate solutions with different concentrations by utilizing an aerosol generator, measuring the dried nitrate particles and sulfate particles by utilizing an HR-AMS, and obtaining the ratio of nitrogen-containing fragment ions and the ratio of sulfur-containing fragment ions of the pure ammonium nitrate and the pure ammonium sulfate under different concentrations by analyzing mass spectrogram data;
S2, determining the optimal temperature for distinguishing organic nitrate and inorganic nitrate:
Calibrating the loss efficiency of the thermal diffusion tube by using a TD-HR-AMS system, obtaining a thermal analysis chart of pure ammonium nitrate, obtaining a change chart of the mass residual fraction of the ammonium nitrate along with the temperature, and determining the volatilization temperature of the pure ammonium nitrate based on the change chart; the method comprises the steps of (1) determining the optimal temperature for distinguishing organic nitrate from inorganic nitrate by analyzing two paths of particle chemical components and an organic aerosol mass spectrogram through a TD-HR-AMS system;
The TD-HR-AMS system comprises a nafion drying pipe, a bypass, a heat diffusion pipeline and an HR-AMS; the nafion drying pipe is connected with the HR-AMS through a bypass and a heat diffusion pipeline; the heat diffusion pipeline continuously heats at constant temperature in a circulating way with different temperature gradients;
In step S2, the particulate matter in the atmosphere is analyzed by a TD-HR-AMS system through a two-path mass spectrum analysis of the chemical components of the particulate matter and the organic aerosol so as to determine the optimal temperature for distinguishing the organic nitrate and the inorganic nitrate, specifically,
The method comprises the steps that particles in the atmosphere are dried through a nafion drying pipe and then alternately enter a bypass of direct sample injection and a heat diffusion pipeline of continuous constant-temperature heating, the bypass and the heat diffusion pipeline are switched once at regular intervals, then measurement is carried out by utilizing HR-AMS, the mass concentration of organic nitrogen-containing fragment ions in the actual atmosphere and after heating is obtained through mass spectrogram analysis of two paths of chemical components of the particles and the organic aerosol, the mass residual fraction of each nitrogen-containing fragment ion at different temperatures is obtained, and inorganic nitrate and the actual atmosphere are analyzedThe ratio is determined, and the temperature of 90 ℃ is one of the optimal temperatures for distinguishing organic nitrate and inorganic nitrate;
S3, determining a concentration matrix of PMF:
Determining a concentration matrix of PMF based on the conventional organic matrix, the mass concentration of nitrogen-containing fragments remaining after the thermal diffusion pipeline is heated to an optimal temperature, and the concentration of sulfur-containing fragments;
S4, determining an error matrix of the PMF:
The error matrix of the PMF is determined based on the error matrix of the conventional organic matrix, the standard error of the mass concentration of the nitrogen-containing chips remaining after the thermal diffusion line is heated to the optimal temperature, and the standard error of the concentration of the sulfur-containing chips.
2. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 1, wherein the method comprises the following steps: the method comprises the steps of S1, preparing pure ammonium nitrate and ammonium sulfate solution with a certain concentration, wherein the concentration of the solution is not more than 5mM, respectively generating nitrate particles and sulfate particles from the prepared solution by using an aerosol generator, drying the nitrate particles and the sulfate particles by using a drying system, screening out nitrate particles with the concentration of 250-300nm from the dried nitrate particles based on a differential particle electromigration device, measuring the nitrate particles and the sulfate particles by using an HR-AMS, and obtaining the ratio of nitrogen-containing fragment ions to the ratio of sulfur-containing fragment ions under the pure ammonium nitrate and the pure ammonium sulfate by analyzing mass spectrogram data; and obtaining the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions under the pure ammonium nitrate and the pure ammonium sulfate with different concentrations by adjusting the concentrations of the pure ammonium nitrate and the pure ammonium sulfate solution.
3. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 2, wherein: nitrate-generated nitrogen-containing fragment ions include NO + andSulfate-generated sulfur-containing fragment ions include/>
4. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 2, wherein: for external field observation, calibrating the ratio of the nitrogen-containing fragment ions in the pure nitrate and the ratio of the sulfur-containing fragment ions in the pure ammonium sulfate for three times respectively before, during and after observation to evaluate the stability of the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions during the operation of the instrument; in laboratory experiments, the ratio of the nitrogen-containing fragment ions in the pure nitrate and the ratio of the sulfur-containing fragment ions in the pure ammonium sulfate are calibrated twice, namely after the instrument is stabilized before the experiment and after the experiment is finished, respectively, so as to evaluate the stability of the ratio of the nitrogen-containing fragment ions and the ratio of the sulfur-containing fragment ions during the operation of the instrument; the ratio of the nitrogen-containing fragment ions to the ratio of the sulfur-containing fragment ions is analyzed by selecting the high-concentration nitrate and high-concentration sulfate pollution stages during observation and compared with pure ammonium nitrate and pure ammonium sulfate to determine the final ratio of the fragment ions.
5. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 1, wherein the method comprises the following steps: in the step S2, the loss efficiency of the thermal diffusion tube is calibrated by utilizing a TD-HR-AMS system, a thermal analysis chart of pure ammonium nitrate is obtained, a change chart of the mass residual fraction of the ammonium nitrate along with the temperature is obtained, specifically,
The heat diffusion tube is provided with different temperature gradients from 25 ℃ to 250 ℃, firstly NaCl particles with different particle sizes are selected to pass through the heat diffusion tube and the bypass respectively, the pipeline loss of the heat diffusion tube at different temperatures is calculated through the ratio of the logarithmic concentration, then pure ammonium nitrate particles are alternately introduced into the heat diffusion tube and the bypass, the residual concentration of ammonium nitrate at different temperatures is measured, further a change chart of the mass residual fraction of the ammonium nitrate along with the temperature is obtained, and the total volatilization of the pure ammonium nitrate at 60 ℃ is determined based on the change chart, namely, the inorganic nitrate in the actual atmosphere can be effectively removed when the temperature is higher than the temperature.
6. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 1, wherein the method comprises the following steps: the residence time of the particulate matter in the thermal diffusion tube should be 20-30 seconds to ensure that the particulate matter chemical components are allowed to volatilize at the set temperature without excessive losses due to residence time.
7. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 1, wherein the method comprises the following steps: the sulfur-containing chip concentration is calculated in such a way that,
Wherein, Measured in the atmosphere by HR-AMS respectively- Is a concentration of (2); /(I)Respectively pure ammonium sulfateRatio of; The pair/>, respectively, of fragments derived from organosulfides The concentration contributed.
8. The method for analyzing the source of the finely divided secondary organic aerosol by combining the contributions of the organic matters in the inorganic matrix according to claim 1, wherein the method comprises the following steps: the standard deviation of the concentration of sulfur-containing chips is calculated in such a way that,
Wherein, Respectively represent the measured/> of the HR-AMS in the atmosphere Standard deviation of concentration; /(I)Respectively pure ammonium sulfateRatio of;
The pair/>, respectively, of fragments derived from organosulfides Standard error of concentration contributed.
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