CN111307992B - Pre-column derivative liquid chromatography-mass spectrometry analysis method for quantitatively detecting organic acid in PM2.5 - Google Patents
Pre-column derivative liquid chromatography-mass spectrometry analysis method for quantitatively detecting organic acid in PM2.5 Download PDFInfo
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Abstract
The invention belongs to the field of organic acid detection, and relates to a pre-column derivative liquid chromatography-mass spectrometry analysis method for quantitatively detecting organic acid in PM2.5, which comprises the following steps: (1) Extracting and centrifuging a PM2.5 sample by using acetonitrile as an extracting agent, and collecting an extract liquid; (2) Carrying out derivatization reaction on the extract liquor, a Gilard reagent T, 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride and pyridine to obtain a pre-column derivative; (3) And (3) carrying out high performance liquid chromatography-mass spectrometry detection on the pre-column derivative to obtain quantitative information of the organic acid in the PM 2.5. The invention successfully realizes the effective separation of fifteen organic acids in PM2.5 by adopting a pre-column derivative liquid chromatography-mass spectrometry analysis method, achieves the accurate quantitative detection of the components of the organic acids, simplifies the pretreatment process of the sample, and simultaneously improves the reproducibility of the method. Compared with the existing testing technology, the invention realizes the quantitative analysis and detection of the organic acid in the sample and solves the problems of complex sample pretreatment and poor detection stability.
Description
Technical Field
The invention belongs to the field of organic acid detection, and particularly relates to a pre-column derivative liquid chromatography-mass spectrometry analysis method for quantitatively detecting organic acid in PM 2.5.
Background
The fine particulate matter in the atmospheric particulate matter, namely PM2.5, is easy to adsorb toxic and harmful substances due to the characteristics of small particle size, large specific surface area, strong activity and the like, and the PM2.5 has long retention time in the atmosphere and long conveying distance and has great influence on the atmospheric environmental quality and human health. The organic acid is a main polar compound in PM2.5, has low vapor pressure and strong hygroscopicity, can increase the humidity of particles to form cloud condensation nuclei, influences the light radiation balance and reduces the atmospheric visibility. In addition, the organic acid component may also produce side effects on human health, and may easily induce respiratory and cardiovascular diseases. Therefore, the quantitative detection research on the organic acid component in PM2.5 has higher academic value and social significance.
At present, quantitative detection of organic acid in PM2.5 is carried out less, and the main reason is that PM2.5 has the characteristics of complex matrix, strong polarity of organic acid, low content and the like, so that an effective, sensitive and rapid analysis method is lacked. The methods currently available include gas chromatography, ion chromatography, and capillary electrophoresis. Wherein, the gas chromatography needs complicated sample pretreatment process (Atmospheric Chemistry and Physics,2011 11, (5), 2197-2208) because the boiling point of the organic acid is high and the organic acid is not easy to gasify; ion chromatography can detect a small amount of organic acids and is not practical (Atmospheric Research,2007,84, (2), 169-181); the capillary electrophoresis method has high separation degree, but has poor stability compared with other methods (Atmospheric Environment,2005,39, (16), 2819-2827). Therefore, it is important to develop a method capable of easily and stably detecting various organic acids in PM 2.5.
Disclosure of Invention
The invention aims to overcome the defects of complicated pretreatment process, small quantity of detectable organic acid, incapability of detecting low-content organic acid and poor stability when the conventional method is used for quantitatively detecting the organic acid in PM2.5, and provides a method for simply and stably detecting various organic acids in PM2.5 and even organic acids with extremely low content.
After intensive research, the inventor of the invention finds that before PM2.5 is subjected to high performance liquid chromatography-mass spectrometry detection, acetonitrile is adopted to carry out extraction centrifugation, then three specific reagents, namely Gillard reagent T, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and pyridine, are used for carrying out derivatization reaction on the obtained extract liquor, and the obtained derivatization reaction product can accurately feed back qualitative and quantitative information about organic acid in PM2.5 by directly carrying out high performance liquid chromatography-mass spectrometry detection, and the whole process has the advantages of simple operation, high sensitivity and good stability. Based on this, the present invention has been completed.
Specifically, the invention provides a method for quantitatively detecting organic acid in PM2.5, which comprises the following steps:
(1) And (3) extraction: extracting and centrifuging a PM2.5 sample by adopting acetonitrile as an extracting agent, and collecting an extract liquor;
(2) Pre-column derivatization: carrying out derivatization reaction on the extract liquor, a Gilard reagent T, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and pyridine to obtain a pre-column derivative;
(3) High performance liquid chromatography-mass spectrometry detection: and (3) carrying out high performance liquid chromatography-mass spectrometry detection on the pre-column derivative to obtain quantitative information of the organic acid in the PM 2.5.
Further, the organic acid contained in the PM2.5 is selected from one or more of caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearl acid, stearic acid, oleic acid, and linoleic acid.
Further, the condition of the extraction centrifugation comprises that the rotating speed is 10000-15000 r/min, and the most preferable rotating speed is 12000r/min; the time is 4-6 min, most preferably 5min.
Further, the Girard reagent T and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are used in the form of an aqueous solution having a concentration of 20X 10 -3 mol/L～30×10 -3 mol/L (most preferably 25X 10) -3 mol/L), the concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution is 1mol/L to 3mol/L (most preferably 2 mol/L), and the body of the extract, the Gilard reagent T aqueous solution, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution and pyridineThe volume ratio is 100 (80-120) (5-10) (15-25) (most preferably 100. When the dosage ratio of the raffinate to the Gilard reagent T, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the pyridine is controlled in the range, the matrix interference can be reduced to the greatest extent, the detection sensitivity and stability of the organic acid are improved, and the obtained quantitative information is more accurate.
Further, the conditions of the derivatization reaction include a temperature of 35 to 45 ℃, and most preferably 40 ℃; the time is 25-35 min, and the most preferable time is 30min.
According to an embodiment of the present invention, the method for quantitatively detecting organic acid in PM2.5 comprises the following steps:
(1) And (3) extraction: placing 1.0-10.0 mg of PM2.5 sample at the bottom of a glass bottle, adding 1.0mL of acetonitrile, ultrasonically dispersing for 5-20 min, centrifuging 500 mu L of ultrasonic dispersion liquid for 4-6 min at the rotating speed of 10000-15000 r/min, and collecting clear extract liquid;
(2) Pre-column derivatization: mixing 100 μ L of the extract, 100 μ L of the extract with a concentration of 25 × 10 -3 Putting 7.5 mu L of Gilard reagent T aqueous solution with the concentration of 2mol/L, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution with the concentration of 2mol/L and 20 mu L of pyridine into a 1.5mL centrifuge tube, diluting to 500 mu L by using acetonitrile, sealing, shaking up, and reacting in a water bath at 40 ℃ for 30min to obtain a pre-column derivative;
(3) High performance liquid chromatography-mass spectrometry detection: and (3) carrying out high performance liquid chromatography-mass spectrometry detection on the pre-column derivative under the set high performance liquid chromatography-mass spectrometry conditions, and then calculating the content of the organic acid in the pre-column derivative according to a standard curve to obtain quantitative information of the organic acid in the PM 2.5.
In the invention, the instrument specifically used for the high performance liquid chromatography-mass spectrometry detection can be a high performance liquid triple quadrupole linear ion trap mass spectrometer, for example.
Further, the conditions for the high performance liquid chromatography detection in the high performance liquid chromatography-mass spectrometry detection include: c18 chromatographic column or equivalent, with sample amount of 10 μ L, mobile phase A being acetonitrile, and mobile phase B being 0.1vt% formic acid aqueous solution; gradient elution is carried out by adopting mixed eluent compounded by mobile phase A and mobile phase B, wherein, in the elution process of 0-5 min, the concentration of the mobile phase A is increased from 30vt% to 60vt% and the concentration of the mobile phase B is reduced from 70vt% to 40vt%, in the elution process of 6-20 min, the concentration of the mobile phase A is 60vt% and the concentration of the mobile phase B is 40vt%, the total flow rate of the mobile phase is 0.4-1 mL/min (most preferably 0.6 mL/min), and the column temperature is 35-45 ℃ (most preferably 40 ℃).
Further, the conditions for mass spectrometry detection in the high performance liquid chromatography-mass spectrometry detection comprise: the air flow of the atomizing gas (GS 1) of the electrospray ionization ion source is 40-60 mL/min (most preferably 50 mL/min), the air flow of the auxiliary heating gas (GS 2) is 50-70 mL/min (most preferably 60 mL/min), the ionization voltage is 5000-6000V (most preferably 5500V), and the temperature of the auxiliary heating gas is 500-600 ℃ (most preferably 550 ℃).
Aiming at the characteristics of complex matrix, strong polarity and low content of organic acid of PM2.5, the effective separation of fifteen organic acids in PM2.5 is successfully realized by adopting a pre-column derivative liquid chromatography-mass spectrometry analysis method, so that the accurate quantitative detection of the organic acid components is realized, the sample pretreatment process is simplified, and the reproducibility of the method is improved. Compared with the existing testing technology, the invention realizes the quantitative analysis and detection of the organic acid in the sample and solves the problems of complex sample pretreatment and poor detection stability.
Drawings
FIG. 1 is a chromatogram of the organic acid detected in example 2.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1 detection of organic acid content in ambient air PM2.5
(1) Instruments and reagents:
a high performance liquid triple quadrupole linear ion trap mass spectrometer (ABI 3200Q TRAP, USA) equipped with an autosampler and a column oven; the column was a Phenomenex Kinetex 2.6u C18 100A liquid chromatography column (4.6X 100 mm).
Pyridine: analytically pure, purchased from chemical reagents of the national drug group, ltd (shanghai, china);
gilard reagent T: analytically pure, purchased from echiei corporation (shanghai, china);
1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC): analytically pure, purchased from sigma (usa);
methanol, acetonitrile: HPLC grade, available from merck corporation (usa).
(2) The instrument conditions were as follows:
high performance liquid chromatography conditions: c18 column: phenomenex Kinetex 2.6u C18 100A (4.6 x 100 mm) with the sample injection amount of 10 mu L, the mobile phase A is acetonitrile, the mobile phase B is 0.1vt% formic acid aqueous solution, and gradient elution is carried out by adopting a mixed eluent compounded by the mobile phase A and the mobile phase B, wherein in the elution process of 0-5 min, the concentration of the mobile phase A is uniformly increased from 30vt% to 60vt% while the concentration of the mobile phase B is uniformly decreased from 70vt% to 40vt%, in the elution process of 6-20 min, the concentration of the mobile phase A is 60vt% while the concentration of the mobile phase B is 40vt%, the total flow rate of the mobile phase is 0.6mL/min, and the column temperature is 40 ℃.
Mass spectrum detection conditions: the gas flow of the electrospray ionization ion source atomization gas (GS 1) is 50mL/min, the gas flow of the auxiliary heating gas (GS 2) is 60mL/min, the ionization voltage is 5500V, and the temperature of the auxiliary heating gas is 550 ℃. Parameters of the positive ion mode declustering voltage (DP), the injection voltage (EP), the collision voltage (CE), the collision cell injection voltage (CEP), and the collision cell ejection voltage (CXP) of caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, nacreous acid, stearic acid, oleic acid, linoleic acid are shown in table 1 below.
(3) Collecting an ambient air PM2.5 sample:
collecting PM2.5 samples of ambient air at 2 time points in Xiamen city, wherein the collected air volume is 1373m 3 And 1445m 3 The sample weights were 43.13mg and 76.90mg, respectively。
(4) Analysis of organic acid:
2.0mg of PM2.5 sample was placed at the bottom of a glass bottle, 1.0mL of acetonitrile was added, ultrasonic dispersion was performed for 10min, then 500. Mu.L of ultrasonic dispersion was centrifuged at 12000r/min for 5min, and the supernatant (extract) was used for the derivatization reaction.
100. Mu.L of the centrifuged supernatant and 100. Mu.L of the centrifuged supernatant were sequentially added to a 1.5mL centrifuge tube, and the concentration was 25.0X 10 -3 Diluting Girard reagent T water solution of mol/L, EDC water solution of 7.5 μ L concentration of 2.0mol/L and pyridine of 20 μ L to 500 μ L with acetonitrile, sealing, shaking, and reacting in water bath at 40 deg.C for 30min to obtain pre-column derivative.
The organic acids in the pre-column derivatives were subjected to high performance liquid chromatography-mass spectrometry, and the concentrations of the respective organic acids were calculated from peak areas by comparison with a standard curve, and the results are shown in table 2.
TABLE 1
TABLE 2
The results in table 2 show that five organic acids were detected in the ambient air PM 2.5.
Example 2 construction and detection limits of organic acid Standard Curve
Fifteen organic acid standard substances are prepared into 1.0 multiplied by 10 by acetonitrile -3 A mol/L stock solution; and gradually diluting with acetonitrile. 100. Mu.L of the standard solution was mixed at a concentration of 25.0X 10 -3 A Gilard reagent T aqueous solution of mol/L, EDC aqueous solution of 7.5. Mu.L concentration of 2.0mol/L and pyridine of 20. Mu.L were mixed, diluted to 500. Mu.L with acetonitrile, sealed, shaken up and reacted in a water bath at 40 ℃ for 30min. Measuring the organic acid in the standard solution by using high performance liquid chromatography-mass spectrometry, wherein the detection result of the high performance liquid chromatography is shown in figure 1, and in figure 1, hexanoic acid is 1; 2, heptanoic acid; 3, octanoic acid; 4, nonanoic acid; 5 part of fructus decanoiAn acid; 6, undecanoic acid; 7, lauric acid; 8, tridecanoic acid; myristic acid 9; pentadecanoic acid 10; 11, linoleic acid; palmitic acid 12; 13 is oleic acid; 14, pearl acid; 15, stearic acid. As can be seen from the results in FIG. 1, the method provided by the invention successfully realizes effective separation of fifteen organic acids, and can achieve accurate quantitative detection of organic acid components. And (3) drawing a standard curve according to the peak area of the derived product of each target compound and the corresponding concentration, wherein the obtained linear range, regression equation, correlation coefficient, detection limit and relative standard deviation are shown in Table 3.
TABLE 3
a x: organic acid concentration (10) -6 mol/L); y: peak area of organic acid-derived product;
b S/N (signal-to-noise ratio) =3.
EXAMPLE 8978 method for determining the content of organic acids in Zxft 8978 sample recovery and precision
The instrument conditions for detecting the content of organic acid in the PM2.5 sample were the same as in example 1. A spiked PM2.5 sample was prepared by adding 0.5. Mu.g of the target compound (i.e., 15 compounds in Table 3) to a 2.0mg of the PM2.5 sample, and the spiked PM2.5 sample was used to determine the organic acid content according to the procedure of example 1, and the results of the substrate spiking recovery and relative standard deviation determination are shown in Table 4. Wherein, the recovery rate refers to the ratio of the content of the target compound detected by adopting liquid chromatography-mass spectrometry to the content of the target compound in the standard PM2.5 sample. From the results in table 4, it can be seen that the detection of the organic acid content in PM2.5 by the method provided by the present invention can eliminate the matrix interference, and has high stability and precision.
TABLE 4 recovery of substrate spiking and relative standard deviation
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (6)
1. A method for quantitatively detecting organic acids in PM2.5 is characterized by comprising the following steps:
(1) And (3) extraction: extracting and centrifuging a PM2.5 sample by adopting acetonitrile as an extracting agent, and collecting an extract liquor;
(2) Pre-column derivatization: carrying out derivatization reaction on the extract liquor, a Gilard reagent T, 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride and pyridine to obtain a pre-column derivative;
(3) High performance liquid chromatography-mass spectrometry detection: performing high performance liquid chromatography-mass spectrometry detection on the pre-column derivative to obtain quantitative information of organic acid in PM 2.5;
the conditions for high performance liquid chromatography detection in the high performance liquid chromatography-mass spectrometry detection comprise: c18 chromatographic column, the sample amount is 10 μ L, the mobile phase A is acetonitrile, the mobile phase B is 0.1vt% formic acid water solution; gradient elution is carried out by adopting a mixed eluent compounded by a mobile phase A and a mobile phase B, wherein in the elution process of 0-5 min, the concentration of the mobile phase A is increased from 30vt% to 60vt%, the concentration of the mobile phase B is decreased from 70vt% to 40vt%, in the elution process of 6-20 min, the concentration of the mobile phase A is vt%, the concentration of the mobile phase B is 40vt%, the total flow rate of the mobile phase is 0.4-1 mL/min, and the column temperature is 35-45 ℃;
the organic acid contained in the PM2.5 is selected from one or more of caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearl acid, stearic acid, oleic acid, and linoleic acid.
2. The method for quantitatively detecting the organic acid in the PM2.5 is characterized in that the conditions of the extraction centrifugation comprise that the rotating speed is 10000 to 15000r/min, and the time is 4 to 6 min.
3. The method for quantitatively detecting an organic acid in PM2.5 as claimed in claim 1, wherein the girard reagent T and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are used in the form of an aqueous solution having a concentration of 20 x 10 of the girard reagent T -3 mol/L~30×10 -3 The concentration of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution is 1-3 mol/L, and the volume ratio of the extract, the Gilard reagent T aqueous solution, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution and the pyridine is 100 (80-120): 5-10): 15-25).
4. The method for quantitatively detecting the organic acid in the PM2.5, as claimed in claim 1, wherein the conditions of the derivatization reaction include a temperature of 35 to 45 ℃ and a time of 25 to 35 min.
5. The method for quantitatively detecting organic acids in PM2.5 according to claim 1, characterized in that it comprises the following steps:
(1) Extraction: putting a 1.0-10.0 mg PM2.5 sample at the bottom of a glass bottle, adding 1.0mL acetonitrile, carrying out ultrasonic dispersion for 5-20 min, centrifuging 500 mu L of ultrasonic dispersion for 4-6 min at the rotating speed of 10000-15000 r/min, and collecting clear extract liquor;
(2) Pre-column derivatization: mixing 100 μ L of the extract, 100 μ L of the extract with a concentration of 25 × 10 -3 Putting 7.5 mu L of Gilard reagent T aqueous solution with the concentration of 2mol/L, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride aqueous solution with the concentration of 2mol/L and 20 mu L of pyridine into a 1.5mL centrifuge tube, diluting to 500 mu L by using acetonitrile, sealing, shaking up, and reacting in a water bath at 40 ℃ for 30min to obtain a derivative before the column;
(3) High performance liquid chromatography-mass spectrometry detection: and (3) carrying out high performance liquid chromatography-mass spectrometry detection on the pre-column derivative under the set high performance liquid chromatography-mass spectrometry conditions, and then calculating the content of the organic acid in the pre-column derivative according to a standard curve to obtain quantitative information of the organic acid in the PM 2.5.
6. The method for the quantitative detection of organic acids in PM2.5 as claimed in any one of claims 1~5 wherein the conditions for mass spectrometric detection in high performance liquid chromatography-mass spectrometric detection comprise: the air flow of the atomizing air of the electrospray ionization ion source is 40-60 mL/min, the air flow of the auxiliary heating air is 50-70 mL/min, the ionization voltage is 5000-6000V, and the temperature of the auxiliary heating air is 500-600.
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| CN109828073A (en) * | 2019-04-01 | 2019-05-31 | 成都益康谱科技有限公司 | The method for qualitative and quantitative detection of several steroid hormones in saliva |
| CN110907565A (en) * | 2019-11-19 | 2020-03-24 | 国家烟草质量监督检验中心 | Method for measuring carbonyl-containing aroma components in smoke of cigarette heated without combustion |
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