Method for detecting aldehyde compounds in atmospheric fine particulate matters

Abstract

The invention relates to a method for detecting aldehyde compounds in atmospheric fine particulate matters, and belongs to the technical field of aldehyde compound detection. The method for detecting the aldehyde compounds in the atmospheric fine particulate matters comprises the following steps: establishing a library of the aldehyde compounds in the atmospheric fine particulate matters; the method comprises the following steps: collecting a sample, punching the collected sample to obtain a to-be-detected sample, mixing the to-be-detected sample with a derivatization reagent and alkali liquor, and carrying out constant-temperature oscillation derivatization to obtain a derivatization product; the derivatization product is detected through combination of an ultra-high performance liquid chromatography and a triple quadrupole mass spectrometer; and comparing with a library of aldehyde compounds in the atmospheric fine particulate matters so as to confirm the types and relative contents of the aldehyde compounds in the atmospheric fine particulate matters. The perforated sample is directly mixed with the derivatization reagent, and the constant-temperature oscillation metal bath reaction, the oscillation extraction and the derivatization reaction are carried out at the same time, so that the time is saved, and the problem of inaccurate detection result caused by incomplete sample extraction and sample loss when the sample is firstly extracted is avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of aldehyde compound detection, and specifically relates to a method for detecting aldehyde compounds in atmospheric fine particulate matter. Background Art

[0002] The pollution characteristics of aldehyde compounds are one of the important research contents in atmospheric research, and preliminary progress has been made in the research of aldehyde compounds by derivatization technology. 2,4-Dinitrophenylhydrazine, o-phenylenediamine (OPD) reagent, 2-thiobarbituric acid (TBA), etc. can all achieve the derivatization and mass spectrometry quantitative detection of aldehyde substances, but there are varying degrees of differences in derivatization efficiency, the traditional pretreatment process is complex, and derivatization is carried out after extraction. For aldehydes in atmospheric fine particulate matter, direct determination is mostly used, and the determination time required is long. Summary of the Invention

[0003] The first object of the present invention is to provide a method for detecting aldehyde compounds in atmospheric fine particulate matter to solve the technical problem of the complex sample treatment process before the derivatization reaction with existing derivatization reagents.

[0004] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0005] A method for detecting aldehyde compounds in atmospheric fine particulate matter, comprising the following steps:

[0006] S1: Establish a library of aldehyde compounds in atmospheric fine particulate matter;

[0007] S2: Collect samples, punch the collected samples to obtain samples to be detected, mix the samples to be detected with a derivatization reagent and an alkali solution, and perform constant-temperature oscillation derivatization to obtain a derivatized product;

[0008] S3: The derivatized product is detected by the combination of ultra-high performance liquid chromatography and a triple quadrupole mass spectrometer;

[0009] S4: Compare with the library of aldehyde compounds in atmospheric fine particulate matter in S1 to confirm the types and relative contents of aldehyde compounds in atmospheric fine particulate matter.

[0010] Further, the derivatization reagent is 1-(4-ester phenyl)-3-methyl-5-pyrazolone reagent, and the alkali solution is ammonia water; the diameter of the sample to be detected is 3 - 6 mm.

[0011] Further, the molar ratio of the sample to be detected to the derivatization reagent is 1:5 - 1:10; the alkali solution accounts for 0.2 - 1% of the total volume of the derivatization reagent and the alkali solution; the volume fraction of the alkali solution is 20 - 30%.

[0012] Furthermore, the temperature for the constant-temperature oscillating derivatization is 40-70°C, and the time for the constant-temperature oscillating derivatization is 10-60 min.

[0013] Furthermore, after the derivatization product is frozen and concentrated, the excess alkali solution is removed, and then it is redissolved in methanol, and then detected by the combination of ultra-high performance liquid chromatography and triple quadrupole mass spectrometer.

[0014] Furthermore, the method for establishing the aldehyde compound library in atmospheric fine particulate matter includes the following steps:

[0015] S1: Add d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water to the sample and aldehyde standard respectively, and obtain the sample solution and aldehyde standard solution derivatized by d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone through constant-temperature oscillating derivatization. Then, after removing the excess ammonia water, redissolve it in methanol to obtain the d0-sample solution and d0-aldehyde standard solution;

[0016] S2: Add d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water to the sample and aldehyde standard respectively, and obtain the sample solution and aldehyde standard solution derivatized by d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone through constant-temperature oscillating derivatization. After removing the excess ammonia water, redissolve it in methanol to obtain the d3-sample solution and d3-aldehyde standard solution;

[0017] S3: Mix the d0-sample solution and the d3-sample solution in equal volume to obtain a sample mixture, and mix the d0-aldehyde standard solution and the d3-aldehyde standard solution to obtain an aldehyde standard mixture;

[0018] S4: Detect the sample mixture and the aldehyde standard mixture by the combination of ultra-high performance liquid chromatography and triple quadrupole mass spectrometer to obtain the aldehyde compound library in atmospheric fine particulate matter.

[0019] Furthermore, the temperature of the constant-temperature oscillating reaction is 50-90°C, the time of the constant-temperature oscillating reaction is 0.5-2 h, and the oscillation frequency of the constant-temperature oscillating reaction is 800-1000 r / min.

[0020] Furthermore, the molar ratio of the sample to the d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2-1:100, and the molar ratio of the sample to the d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2-1:100; the molar ratio of the aldehyde standard to the d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2-1:100, and the molar ratio of the aldehyde standard to the d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2-1:100.

[0021] Further, the ammonia water accounts for 1-20% of the total volume of d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water, and the ammonia water accounts for 1-20% of the total volume of d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water.

[0022] Further, the detection conditions for the ultra-high performance liquid chromatography and triple quadrupole mass spectrometer are as follows: the declustering voltage is 90-110 V, the collision energy is 25-35 eV; the injection time is 8 min.

[0023] Beneficial effects of the present invention:

[0024] In the present invention, the punched sample is directly mixed with the derivatization reagent, and the reaction is carried out in a constant temperature oscillating metal bath. The oscillating extraction and derivatization reaction are carried out simultaneously, saving time and avoiding the problems of incomplete sample extraction, sample loss and inaccurate detection results when extracting the sample first.

[0025] In the present invention, the 1-(4-ester phenyl)-3-methyl-5-pyrazolone reagent reacts with aldehyde compounds under the action of ammonia water to obtain various derivatization products. By using the ultra-high performance liquid chromatography and triple quadrupole mass spectrometer coupling (UPLC-MS / MS) technology, the detection of aldehyde compounds in atmospheric fine particulate matter is realized conveniently, quickly, qualitatively and relatively quantitatively.

[0026] The present invention uses 1-(4-ester phenyl)-3-methyl-5-pyrazolone as a derivatization reagent to carry out a derivatization reaction under ammonia water. Ammonia water is volatile and does not involve a desalting step. The operation is simple and no impurities are introduced. Description of the drawings

[0027] Figure 1 It is the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter on sampling membranes with different diameters;

[0028] Figure 2 It is the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter under different reaction devices;

[0029] Figure 3 It is the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter in different solvents;

[0030] Figure 4 It is the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter under different ammonia water contents;

[0031] Figure 5 It is the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter under different molar amounts of aldehyde and derivatization reagent;

[0032] Figure 6 For the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter at different reaction temperatures;

[0033] Figure 7 For the effect diagram of the derivatization reaction of aldehyde compounds in atmospheric fine particulate matter at different reaction times;

[0034] Figure 8 For the chromatographic separation diagram of 16 aldehyde derivatives;

[0035] Figure 9 For the seasonal intensity change diagram of aldehyde compounds;

[0036] Figure 10 For the seasonal proportion of aldehyde compounds;

[0037] Figure 11 For the derivatization effect diagram at different ammonia water ratios during the establishment of the aldehyde compound library in atmospheric fine particulate matter;

[0038] Figure 12 For the derivatization effect diagram at different reaction temperatures during the establishment of the aldehyde compound library in atmospheric fine particulate matter;

[0039] Figure 13 For the derivatization effect diagram at different reaction times during the establishment of the aldehyde compound library in atmospheric fine particulate matter;

[0040] Figure 14 For the derivatization effect diagram with different dosages of derivatization reagents during the establishment of the aldehyde compound library in atmospheric fine particulate matter;

[0041] Figure 15 For the secondary mass spectrum diagram of aldehyde compounds;

[0042] Figure 16 For the non-targeted determination flow chart of aldehyde compounds in atmospheric fine particulate matter. Specific implementation mode

[0043] The present invention will be further described below in conjunction with the embodiments of the present invention and the accompanying drawings.

[0044] Instruments used: triple quadrupole mass spectrometer (6500Q-TRAP, AB SCIEX, USA); ultra-high performance liquid chromatograph (SHIMADZU, LC-30AD); metal bath (LEOPARD, China), ultrasonic cleaner (KUDOS SK 2210LHC, KEDAO Ultrasonic, Shanghai), freeze concentrator (LABCONCO, USA).

[0045] The molecular weight of the sample of the present invention is 334. The method for determining the molecular weight is the maximum molecular weight of aldehyde substances in atmospheric particulate matter measured currently, and this molecular weight is recorded in Chemical Fingerprinting of HULIS in Particulate Matters Emitted from Residential Coal and Biomass Combustion.

[0046] Example 1

[0047] The method for establishing the aldehyde compound library in fine atmospheric particulate matter of Example 1 is as follows:

[0048] S1: Sample pretreatment: Scrub the scissors with methanol to avoid contaminating the sample. Cut one-fourth (4.9 cm 2 ) of the sampling membrane into pieces and put them into a 15 mL centrifuge tube. Add 10 mL of methanol to the centrifuge tube containing the sample fragments, and place it in an ultrasonic cleaner for ice bath and ultrasonic treatment for 15 min, repeating three times. During the ultrasonic treatment, replace the ice bag in time to ensure the temperature is about 25 °C. After ultrasonic treatment, centrifuge, and use a 0.22 μm polytetrafluoroethylene filter to aspirate 1 mL of the supernatant and filter it into a centrifuge tube, and spin-dry it with a freeze concentrator for subsequent analysis. Weigh the centrifuge tube before filtration and after spin-drying respectively, and calculate the mass difference.

[0049] Δm = m1 - m2, Equation (1);

[0050] In the formula, Δm is the mass difference between the two weighings, m1 is the mass of the centrifuge tube before adding the solution, and m2 is the mass of the centrifuge tube after spin-drying.

[0051] Taking the sample from 10:00 on April 15, 2023 to 9:00 on April 16, 2023 as an example, weigh a 1.5 mL centrifuge tube before filtration, and the weight is 995.9 mg. After spin-drying, the weighed weight is 996.1 mg. Calculate the mass difference of 0.2 mg according to Equation (1).

[0052] S2: The sample processed in S1 is evenly divided into two parts. 495 μL of 0.003 mM d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone (d0-PMP-OMe) and 5 μL of ammonia water are added to one part of the sample; 495 μL of 0.009 mM d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone (d3-PMP-OMe) and 5 μL of ammonia water are added to the remaining part of the sample. The metal bath is shaken at a constant temperature of 50 °C for 1 h at 800 r / min for the derivatization reaction to obtain the sample solution derivatized with d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone and the sample solution derivatized with d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone. After the derivatization reaction, it is frozen and concentrated, then 1 mL of methanol is added and it is rotary evaporated and concentrated to remove ammonia water. The derivatization reactions of d0-PMP-OMe and d3-PMP-OMe with aldehyde compounds are shown in Formulas (2) and (3); the volume fraction of ammonia water is 25%. The molar ratio of the sample to be detected to the derivatization reagent is 1:25.

[0053] S3: The d0-sample solution and the d3-sample solution are reconstituted with 500 μL of methanol. The d0-sample solution and the d3-sample solution of equal volume are used to obtain a sample mixture, and the supernatant is taken by centrifugation for UPLC-MS / MS detection.

[0054] It is diluted 5 times and then injected into the instrument in sequence. The declustering potential (DP, Dynamic Pneumatic) is 100 V, and the collision energy (CE, Collision Energy) is 30 eV. The results are shown in Table 1. For the results, the peak area ratio range of d0-PMP-OMe and d3-PMP-OMe is around 1, and their peak emergence times are the same, indicating the presence of a certain aldehyde substance.

[0055]

[0056] The preparation method of the aldehyde standard mixture is the same as that of the sample mixture. The aldehyde standards are nonanal, propionaldehyde, butyraldehyde, decanal, 10-undecenal, undecanal, peach aldehyde, 2-hydroxy-3-(2-propenyl) benzaldehyde, syringaldehyde, 4-hydroxy-3-methylbenzaldehyde, coniferyl aldehyde, trans-3,5-dimethoxy-4-hydroxycinnamaldehyde, vanillin, 4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 3-(4-methylphenyl)-2-propenal.

[0057] Detection conditions of ultra-high performance liquid chromatography and triple quadrupole mass spectrometer: The ultra-high performance liquid chromatography is the Shimadzu LC-30AD system, where the pump is LC-30AD, the model of the autosampler is SIL-30AC, and the column oven is CTO-30A. The chromatographic column used for separation is the Phonex (USA) EVO C18 column (2.1 mm × 150 mm, 1.7 μm); column temperature: 40 °C; with mobile phase A: 0.1% formic acid water, mobile phase B: acetonitrile; flow rate 0.3 mL / min; injection volume: 10 μL. The chromatographic elution method adopts gradient elution, and the specific time program is: 0 min, 75% B; 0 - 3 min, 75 - 90% B; 3 - 4 min, 90% B; 4 - 5 min, 90 - 75% B, and finally the chromatographic column is equilibrated with the initial mobile phase for 3 min.

[0058] Table 1 Aldehyde compound library in atmospheric fine particulate matter

[0059]

[0060]

[0061]

[0062]

[0063] Example 2

[0064] The detection method of aldehyde compounds in atmospheric fine particulate matter includes the following steps:

[0065] Detect the aldehyde compounds in the atmospheric fine particulate matter in 2023: Use a 3 mm punch to extract the quartz filter membrane and place it in a 1.5 mL centrifuge tube. Wipe it with methanol before punching to avoid contamination. Add 499 μL of d0-1-(4-esterylphenyl)-3-methyl-5-pyrazolone reagent with a concentration of 0.0005 mM and 1 μL of ammonia water to the centrifuge tube containing the sample fragments, and obtain the derivatization product by shaking in a metal bath at 40 °C for 10 min, followed by freeze concentration. Then add 1 mL of methanol to the centrifuge tube for concentration, remove ammonia water, and redissolve with 500 μL of methanol. Centrifuge and take the supernatant for detection; the volume fraction of ammonia water is 25%. The molar ratio of the sample to be detected to d0-1-(4-esterylphenyl)-3-methyl-5-pyrazolone is 1:10.

[0066] According to the aldehyde compound library in atmospheric fine particulate matter established in Example 1, by comparing the retention time and Q1 / Q3, confirm the aldehyde substances present in the atmospheric fine particulate matter, and by comparing the peak areas, test the relative content of aldehyde compounds in the sample.

[0067] Example 3

[0068] The method for detecting aldehyde compounds in fine particulate matter in the atmosphere of Example 3 is the same as that of Example 2. The difference between the method for detecting aldehyde compounds in fine particulate matter in the atmosphere of Example 3 and that of Example 2 is that in Example 3, the aldehyde compounds in the fine particulate matter in the atmosphere in 2024 are detected. The detection results of Example 2 and Example 3 are as Figure 9 and Figure 10 shown.

[0069] Test Example 1

[0070] Weigh 1.78 mg of coniferyl aldehyde (0.01 mmol), 9 μL of butyraldehyde (0.1 mmol), and 1.36 mg of the standard of 4-hydroxy-3-methylbenzaldehyde (0.01 mmol) into a 1.5 mL centrifuge tube, add 1 mL of methanol respectively, then dilute 10, 100, 10 times, and then mix them together to obtain an aldehyde mixed standard solution with a total concentration of 0.003 mM. Take the 0.003 mM aldehyde mixed standard solution, drop it onto sampling membranes with different pore sizes, add d0-PMP-OMe and ammonia water for derivatization reaction to obtain derivatized products, and detect them by UPLC-MS. The detection results are as Figure 1 shown. It can be seen from Figure 1 that the effect of directly performing the derivatization reaction on the sampling membrane is better than that in solution, and when the pore size of the punching machine is 3 mm, the detection effect is the best.

[0071] Test Example 2

[0072] Select a sampling membrane with a pore size of 3 mm, keep other conditions unchanged, react the sampling membrane dropped with the aldehyde mixed standard solution with d0-PMP-OMe under extraction conditions, and the detection results are as Figure 2 shown. It can be seen from Figure 2 that the overall signal intensity of the derivatized product is the strongest under the oscillation condition.

[0073] Test Example 3

[0074] Select a sampling membrane with a pore size of 3 mm, extract and derivatize the sampling membrane dropped with the aldehyde mixed standard solution with d0-PMP-OMe under the oscillation condition, keep the rest of the conditions unchanged, and explore the influence of the solvent on the signal of the derivatized product. The detection results are as Figure 3 shown. It can be seen from Figure 3 that when the solvent is methanol, the overall signal intensity of the derivatized product is the strongest.

[0075] Test Example 4

[0076] A sampling membrane with a pore size of 3 mm was selected. The sampling membrane with the aldehyde mixed standard solution added was extracted and derivatized with d0-PMP-OMe under oscillating conditions. The solvent was methanol, and the other conditions remained unchanged. The effect of the amount of ammonia water added on the signal of the derivatization product was explored. The detection results are as Figure 4 shown. From Figure 4 it can be seen that when the volume of ammonia water is 1 μL, the overall intensity of the signal of the derivatization product is the strongest.

[0077] Test Example 5

[0078] A sampling membrane with a pore size of 3 mm was selected. The sampling membrane with the aldehyde mixed standard solution added was extracted and derivatized with d0-PMP-OMe under oscillating conditions. The solvent was methanol, the amount of ammonia water added was 1 μL, and the other conditions remained unchanged. The effect of the molar amount of aldehyde and derivatization reagent on the signal of the derivatization product was explored. The detection results are as Figure 5 shown. From Figure 5 it can be seen that when the molar ratio of aldehyde to derivatization reagent is 1:10, the overall intensity of the signal of the derivatization product is the strongest.

[0079] Test Example 6

[0080] A sampling membrane with a pore size of 3 mm was selected. The sampling membrane with the aldehyde mixed standard solution added was extracted and derivatized with d0-PMP-OMe under oscillating conditions. The solvent was methanol, the amount of ammonia water added was 1 μL, the molar ratio of aldehyde to derivatization reagent was 1:10, and the other conditions remained unchanged. The effect of the derivatization reaction temperature on the signal of the derivatization product was explored. The detection results are as Figure 6 shown. From Figure 6 it can be seen that when the derivatization reaction temperature is 40 °C, the overall intensity of the signal of the derivatization product is the strongest.

[0081] Test Example 7

[0082] A sampling membrane with a pore size of 3 mm was selected. The sampling membrane with the aldehyde mixed standard solution added was extracted and derivatized with d0-PMP-OMe under oscillating conditions. The solvent was methanol, the amount of ammonia water added was 1 μL, the molar ratio of aldehyde to derivatization reagent was 1:10, and the derivatization reaction temperature was 40 °C. The other conditions remained unchanged. The effect of the derivatization reaction time on the signal of the derivatization product was explored. The detection results are as Figure 7 shown. From Figure 7 it can be seen that when the derivatization reaction time is 10 min, the overall intensity of the signal of the derivatization product is the strongest.

[0083] Test Examples 1-7 explored the reaction conditions for detecting aldehyde compounds in atmospheric fine particulate matter; Examples 8-11 explored the conditions for establishing a library of aldehyde compounds in atmospheric fine particulate matter. Figures 1 - 7The solution in refers to the solution obtained by directly mixing with the derivatization reagent and the alkali solution for the derivatization reaction without dropping onto the membrane after being prepared according to the standard solution in Test Example 1.

[0084] Test Example 8

[0085] Standard nonanal, syringaldehyde, 10-undecenal, undecanal, and peach aldehyde were derivatized with the derivatization reagent d0-PMP-OMe under different ammonia water ratio conditions, and the results are as Figure 11 shown. When the ammonia water accounts for 1% of the total volume of the alkali solution and the derivatization reagent, the overall intensity of the derivatization product signal is the highest.

[0086] Test Example 9

[0087] Selecting an ammonia water ratio of 1%, with other conditions unchanged, standard nonanal, syringaldehyde, 10-undecenal, undecanal, and peach aldehyde were derivatized with d0-PMP-OMe at different reaction temperatures, and the results are as Figure 12 shown. For syringaldehyde and 10-undecenal, the derivatization effect first decreases and then increases with the increase of temperature. The derivatization effects of nonanal and undecanal increase with the increase of temperature, while that of peach aldehyde increases first and then decreases. Therefore, the optimal reaction temperature should be selected as 50 °C.

[0088] Test Example 10

[0089] Selecting an ammonia water ratio of 1%, a reaction temperature of 50 °C, and other conditions unchanged, the mass spectrometry signals of the derivatization products of standard nonanal, syringaldehyde, 10-undecenal, undecanal, and peach aldehyde with d0-PMP-OMe at different reaction times of 0.5 h, 1 h, 1.5 h, and 2 h were compared, and the results are as Figure 13 shown. For syringaldehyde and 10-undecenal, the derivatization effect decreases with the increase of temperature, and the decrease is the largest between 1 h and 1.5 h. The derivatization effects of nonanal and undecanal increase with the increase of temperature, while that of peach aldehyde increases first and then decreases. Therefore, the optimal reaction time should be selected as 1 h.

[0090] Test Example 11

[0091] Selecting an ammonia water ratio of 1%, a reaction temperature of 50 °C, and a reaction time of 1 h, the ratios of standard nonanal, syringaldehyde, 10-undecenal, undecanal, and peach aldehyde to the derivatization reagent d0-PMP-OMe were 1:2, 1:5, 1:10, 1:25, 1:50, and 1:100. The results are as Figure 14 shown. When the molar ratio of the standard aldehyde to d0-PMP-OMe is 1:25, the overall signal of the derivatization product is the best and the relative standard deviation is the smallest.

[0092] Test Example 12

[0093] To verify the stability of the measurement results, the standard samples of 16 aldehyde compounds were measured at intervals in the same batch. A mixed standard sample was inserted after every ten samples to obtain the coefficient of variation (CV). When the coefficient of variation was less than 10%, the data was considered relatively stable with a low degree of dispersion; when the coefficient of variation was between 10% and 30%, the data was considered moderately discrete; and when the coefficient of variation was greater than 30%, the data was considered highly discrete. It can be seen that the CVs of the 16 standard samples after derivatization were all less than 15%, indicating the accuracy of the experimental results.

[0094] The specific steps are as follows: Take 0.1 mmol of nonanal, propionaldehyde, butyraldehyde, decanal, 10-undecenal, undecanal, peach aldehyde, 2-hydroxy-3-(2-propenyl) benzaldehyde, and syringaldehyde and place them in 1.5 mL centrifuge tubes. Add methanol to 1 mL to dilute 500 times. Weigh 0.01 mmol of 4-hydroxy-3-methylbenzaldehyde, coniferyl aldehyde, trans-3,5-dimethoxy-4-hydroxycinnamaldehyde, vanillin, 4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and 3-(4-methylphenyl)-2-propenal and add them to 1 mL of methanol to dilute 50 times. Take 500 μL of each and mix them. Then take 400 μL and add 400 μL of the d0-PMP-OMe stock solution (0.001 mM), add 5 μL of ammonia water and 195 μL of methanol, and react in a 1.5 mL centrifuge tube (metal bath at 50 °C for 1 h). After the reaction, spin-dry and concentrate to remove the ammonia water in the sample. Then redissolve with 500 μL of methanol, centrifuge, and take the supernatant for LC-MS detection, as shown below Figure 8 as follows.

[0095] Table 2 Coefficient of Variation of Standard Samples of 16 Aldehyde Compounds

[0096]

[0097] Table 3 Peak Areas of Standard Samples of 16 Aldehyde Compounds after Derivatization

[0098]

[0099]

[0100] The present invention uses a single-variable optimization method for experiments. Referring to the recommended parameters of the instrument and relevant literature, the ranges of DP and CE are initially set, and screening is carried out on the premise of fixing other mass spectrometry parameters (such as ion source temperature, drying gas flow rate, collision energy, etc.). During the optimization process, DP is adjusted by the stepwise increment method, with a step size of 10 V each time. The signal intensities of the parent ion (M+H+) of the target compound and its main fragment ions under each voltage condition are tested. After obtaining the DP range with the highest signal response, the variable interval is further narrowed, and fine adjustment is carried out with a step size of 5 V or smaller to ensure that the target compound has the highest signal intensity under the optimized conditions. It is found that all 16 derivatized products produce the main fragment ion at m / z 233 from the OMe-PMP part, then the optimal CE value is determined, and finally the optimal DP value is confirmed in reverse. The optimized optimal DP and CE values are summarized in Table 4, and the secondary mass spectrometry diagrams are used to show the changes in fragment ions before and after optimization to visually present the optimization effect.

[0101] Other mass spectrometry conditions: Liquid chromatography-tandem mass spectrometry (LC-MS / MS) is a powerful tool for simultaneously identifying, structurally characterizing, and quantifying carbohydrate compounds. The multiple reaction monitoring (MRM) mode tracks multiple fragmentation ion pairs of potential multiple analytes during the analysis run. For analytes, two or more product ions can be collected simultaneously for quantification and verification purposes. The liquid phase part of LC-MRM uses a Shimadzu ultra-high performance liquid chromatography LC-30AD system, and the mass spectrometry part uses a 6500Q-TRAP mass spectrometer equipped with an ion drive turbo V source from AB SCIEX, USA. All experimental samples are collected and analyzed in the positive ion mode of analytes in the multiple reaction monitoring (MRM) mode. The mass spectrometry instrument parameters are as follows: the ion source temperature (TEM) is 550 °C, the ion spray voltage (ISVF) is 5500 V, and Gas 1, Gas 2, and Curtain gas are 30, 15, and 20 psi, respectively. When optimizing each mass spectrometry parameter, an automatic syringe pump is used for injection with a standard derivatization solution concentration of 1.0 μg / mL, and the injection speed is 3.0 μL / min. The LC-MRM raw data are processed by Analyst (version 1.7.2), Peakview (2.1), and Multi Quant (version 3.0.2) respectively.

[0102] Table 4 Parent ions, main product ions, DP values, and CE values of aldehyde derivatized products

[0103]

[0104]

Claims

1. Detection method for aldehyde compounds in atmospheric fine particulate matter, characterized in that, It includes the following steps: S1: Establish a library of aldehyde compounds in atmospheric fine particulate matter; S2: Collect samples, punch the collected samples to obtain samples to be detected, mix the samples to be detected with a derivatization reagent and an alkali solution, and perform derivatization by constant temperature oscillation to obtain a derivatized product; S3: The derivatized product is detected by hyphenated ultra-high performance liquid chromatography and triple quadrupole mass spectrometer; S4: Compare with the library of aldehyde compounds in atmospheric fine particulate matter in S1 to confirm the types and relative contents of aldehyde compounds in atmospheric fine particulate matter.

2. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 1, characterized in that, The derivatization reagent is 1-(4-ester phenyl)-3-methyl-5-pyrazolone reagent, and the alkali solution is ammonia water; the diameter of the sample to be detected is 3-6 mm.

3. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 1 or 2, characterized in that, The molar ratio of the sample to be detected to the derivatization reagent is 1:5-1:10; the alkali solution accounts for 0.2-1% of the total volume of the derivatization reagent and the alkali solution; the volume fraction of the alkali solution is 20-30%.

4. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 1, wherein The temperature of the constant temperature oscillation derivatization is 40-70 °C, and the time of the constant temperature oscillation derivatization is 10-60 min.

5. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 1, characterized in that, In S3, the derivatized product is freeze-concentrated to remove the excess alkali solution, then redissolved in methanol, and then detected by hyphenated ultra-high performance liquid chromatography and triple quadrupole mass spectrometer.

6. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 1, characterized in that The method for establishing the library of aldehyde compounds in atmospheric fine particulate matter includes the following steps: S1: Add d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water to the sample and the aldehyde standard respectively, perform derivatization by constant temperature oscillation to obtain a d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone-derived sample solution and an aldehyde standard solution, and then remove the excess ammonia water and redissolve with methanol to obtain a d0-sample solution and a d0-aldehyde standard solution; S2: Add d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water to the sample and the aldehyde standard respectively, perform derivatization by constant temperature oscillation to obtain a d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone-derived sample solution and an aldehyde standard solution, remove the excess ammonia water and redissolve with methanol to obtain a d3-sample solution and a d3-aldehyde standard solution; S3: Mix the d0-sample solution and the d3-sample solution in equal volume to obtain a sample mixture, and mix the d0-aldehyde standard solution and the d3-aldehyde standard solution to obtain an aldehyde standard mixture; S4: Detect the sample mixture and the aldehyde standard mixture by hyphenated ultra-high performance liquid chromatography and triple quadrupole mass spectrometer to obtain the library of aldehyde compounds in atmospheric fine particulate matter.

7. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 6, characterized in that The temperature of the constant temperature oscillation reaction is 50-90 °C, the time of the constant temperature oscillation reaction is 0.5-2 h, and the oscillation frequency of the constant temperature oscillation reaction is 800-1000 r / min.

8. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 6, characterized in that, The molar ratio of the sample to d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2 to 1:100, and the molar ratio of the sample to d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2 to 1:100; the molar ratio of the aldehyde standard to d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2 to 1:100, and the molar ratio of the aldehyde standard to d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone is 1:2 to 1:

100.

9. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 6, characterized in that, The ammonia water accounts for 1-20% of the total volume of d0-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water, and the ammonia water accounts for 1-20% of the total volume of d3-1-(4-ester phenyl)-3-methyl-5-pyrazolone and ammonia water.

10. The detection method of aldehyde compounds in atmospheric fine particulate matter according to claim 6, wherein The detection conditions for the ultra-high performance liquid chromatography and triple quadrupole mass spectrometer are as follows: the declustering voltage is 90-110 V, the collision energy is 25-35 eV; the injection time is 8 min.

Images