CN112903856A - Pretreatment method for detecting trace chloroformyl compound in water sample and application thereof - Google Patents
Pretreatment method for detecting trace chloroformyl compound in water sample and application thereof Download PDFInfo
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Abstract
The method discloses a method for determining the residual amount of chloroformyl in water, belongs to the field of analysis and detection, and particularly relates to a high-sensitivity detection method for determining the residual amount of chloroformyl in water by using a liquid chromatography-tandem mass spectrometry method. The method comprises the following specific steps: taking a water sample with a certain volume, adding an organic reagent, performing oscillation extraction, then concentrating, fixing the volume to a certain volume, filtering a membrane, performing computer analysis, and quantifying by an external standard method. The method is suitable for measuring the residual amount of the chloroformyl in water, has the characteristics of high sensitivity, accurate quantification and high recovery rate, and has strong practical significance for compensating and strengthening the detection method of antibiotics in water bodies in China and preventing the antibiotics from polluting the environment.
Description
Technical Field
The invention belongs to the field of analysis and detection, relates to a method for determining the residual amount of chloroformyl in water, and particularly relates to a high-sensitivity detection method for determining chloroformyl in water by using a liquid chromatography-tandem mass spectrometry method.
Background
The chloroformyl is called 1-chloroformyl-3-methylsulfonyl-2-imidazolidinone, is an important medical intermediate, is mainly used for synthesizing medicines such as mezlocillin and the like, has certain toxicity, has irritation to skin, eyes and mucous membranes, and has great harm to the environment by waste and by-products in the production process.
At present, the main content of the chloroformyl compounds is mainly measured, and in Chinese patent application with the application number of 200910241232.5, a method for measuring the content of the chloroformyl groups in the chloroformyl compounds is disclosed, the concentration of the chloride ions is determined by a titration method according to the reaction of silver ions and the chloride ions, and the content of the chloroformyl groups is calculated according to the concentration of the chloride ions; in addition, chinese patent application No. 201410778224.5 discloses a method for detecting the content of 1-chloroformyl-3-methanesulfonyl-2-imidazolidinone, which adopts a potentiometric titration method and adds AgNO into a sample3Solution by consuming AgNO3The content of 1-chloroformyl-3-methanesulfonyl-2-imidazolidinone was calculated from the volume of (a). Both of the above-mentioned prior art methods are intended to analyze the main content of the solution around the chloroformyl compound, and cannot be used for detecting the residual chloroformyl compound in a trace amount in water. Although the trace amount of residual chloroformyl compound in water can not cause great harm to human body directly, the residual amount of chloroformyl compound in water is slightThe amount of the residue can cause the generation of drug resistance of microorganisms and destroy the population balance of the microorganisms, and reports have been made that the drinking water of China mostly detects trace antibiotics and antibiotic intermediates, so that the efficient and sensitive detection of trace chloroformyl residue in water is imperative.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for measuring the residual amount of chloroformyl in water.
The technical problem of the invention can be solved by the following technical scheme:
a pretreatment method for detecting trace chloroformyl compounds in a water sample comprises the following steps:
1) removing suspended particles from a water sample, and placing a certain volume of water sample to be detected in a container;
2) adding a proper amount of soluble salt; by increasing the salt content of the solution, precipitation of the target compound can be promoted
3) Adding a proper amount of extracting solution and a proper amount of organic acid, and extracting by shaking; the extracting solution is an nonpolar organic solvent which is not mutually soluble with water;
4) standing for layering, and transferring to obtain an initial organic phase;
5) repeating the steps 2) -3) on the aqueous phase to obtain a re-extracted organic phase;
6) combining the primary extracted organic phase and the secondary extracted organic phase to obtain an extraction mixed solution;
7) concentrating the extraction mixed solution, fixing the volume with a constant volume solution, uniformly mixing, and filtering through a 0.22-micrometer organic filter membrane to obtain a solution to be detected;
the volume fixing solution is 0.1% formic acid-methanol solution, 1mL of formic acid is taken, dissolved by water and diluted to 1000mL, and the solution is 0.1% formic acid solution; and (3) uniformly mixing 40mL of 0.1% formic acid solution and 60mL of methanol to obtain a mixture, wherein the volume ratio of the 0.1% formic acid solution to the methanol solution is 4: 6.
in one embodiment according to the invention, the soluble salt is a sodium or potassium salt;
preferably, the soluble salt is a mixture of sodium chloride and sodium L-ascorbate, and the mass ratio of the sodium chloride to the sodium L-ascorbate is 2-4: 1. the sodium ascorbate is added to protect the target compound from oxidative decomposition and promote the precipitation of the target compound.
In one embodiment according to the present invention, the extraction liquid is selected from one of ethyl acetate, carbon tetrachloride, petroleum ether, or ethyl acetate and carbon tetrachloride in a volume ratio of 1: 1-2, and mixing the obtained mixed solvent.
In one embodiment according to the present invention, the organic acid is formic acid or acetic acid.
In one embodiment of the present invention, the volume ratio of the extracting solution to the water sample to be tested is 1: 1-3; the volume ratio of the organic acid to the water sample to be detected is 1: 50-200.
In one embodiment according to the invention, the concentration is achieved by concentration under reduced pressure in a rotary evaporator in a water bath at 30-50 ℃; preferably 40 deg.c.
The invention further provides application of the pretreatment method in detecting the residual amount of chloroformyl compounds in a water sample.
The invention also provides a determination method for detecting the residual amount of chloroformyl compounds in a water sample, which comprises the following steps:
a) the pretreatment method according to any one of claims 1 to 6, wherein a water sample is pretreated to obtain a liquid to be detected;
b) and (3) determining the content of the chloroformyl compound in the solution to be detected by using a liquid chromatography-tandem mass spectrometry method.
In one embodiment of the present invention, the liquid chromatography-tandem mass spectrometry conditions are as follows: a chromatographic column: MG S-3 column, 3.0X 35mm, 3 μm; the mobile phase is methanol and 0.1% formic acid, gradient elution is carried out for 0-0.5 min, and 5% methanol is used; 0.5-1 min, 5% -40% methanol; 1-1.5 min, 40-80% methanol; 1.5-3 min, 80-80% methanol; 3-4 min, 5% -5% methanol; the sample introduction amount was 5. mu.L, the flow rate was 0.3mL/min, and the column temperature was 40 ℃.
In one embodiment of the present invention, the mass spectrometry conditions of the liquid chromatography-tandem mass spectrometry are as follows: an ion source: ESI; the scanning mode is as follows: a positive ion; ion source temperature: 150 ℃; capillary voltage: 0.5 kv; the quantitative ion pair of the chloroformyl is 223.07/78.98, the qualitative ion pair is 223.07/113.03, the cone voltage is 41V, and the collision energy is 21eV and 19eV respectively.
The invention has the beneficial effects that:
the detection method adopts the advanced liquid chromatography-tandem mass spectrometry technology to detect the residual amount of the chloroformyl compounds in the water, adopts ethyl acetate to directly extract, and has the advantages of simple method, easy operation, high analysis speed, high sensitivity and good reproducibility. The method has important significance for making up and strengthening the detection method of antibiotics in water samples in China and improving the detection capability in China.
Drawings
FIG. 1 is a total ion flow diagram in a liquid chromatography-tandem mass spectrometer for the determination of a chloroformyl standard according to the method of the present invention;
FIG. 2 is a schematic diagram of a working curve for the chloroformyl chloride standard.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1 measurement of the residual amount of chloroformyl compounds in surface Water of a certain market
(1) Filtering a water sample to remove suspended particles, adding 100.0mL of the water sample into a separating funnel, adding 10g of salt, adding 50mL of extracting solution, oscillating for 10min, standing for 30min for layering, transferring the upper layer extracting solution into a 150mL chicken heart bottle by using a tip pipette, adding 50mL of ethyl acetate, repeating the above operations, combining the two extracting solutions, performing reduced pressure concentration on the upper layer extracting solution in a water bath at 40 ℃ by using a rotary evaporator until the upper layer extracting solution is nearly dry, performing constant volume on the upper layer extracting solution to 1mL by using 0.1% formic acid methanol solution, uniformly mixing, and filtering the solution through a 0.22 mu m organic filter membrane to form a solution to be detected.
The preparation method of the constant volume liquid comprises the following steps:
1mL of formic acid is taken, dissolved by water and diluted to 1000mL, thus obtaining 0.1% formic acid solution; 40mL of 0.1 percent formic acid solution and 60mL of methanol are uniformly mixed to obtain 0.1 percent formic acid methanol solution.
(2) Liquid chromatography tandem mass spectrometry: establishing liquid phase condition and mass spectrum condition, measuring standard working solution and solution to be measured according to corresponding conditions, and performing qualitative and quantitative analysis by adopting an external standard-standard curve method.
The liquid phase conditions were: a chromatographic column: MG S-3 column, 2.1X 50mm, 1.8 μm; the mobile phase is methanol and 0.1% formic acid, gradient elution is carried out for 0-0.5 min, and 5% methanol is used; 0.5-1 min, 5% -40% methanol; 1-1.5 min, 40-80% methanol; 1.5-3 min, 80-80% methanol; 3-4 min, 5% -5% methanol; the sample introduction amount was 5. mu.L, the flow rate was 0.3mL/min, and the column temperature was 40 ℃.
(3) The mass spectrum conditions are as follows: an ion source: ESI; the scanning mode is as follows: a positive ion; ion source temperature: 150 ℃; capillary voltage: 0.5 kv; the quantitative ion pair of the chloroformyl is 223.07/78.98, the qualitative ion pair is 223.07/113.03, the cone voltage is 41V, and the collision energy is 21eV and 19eV respectively.
(4) And (3) qualitative determination: the sample and standard working solution are measured according to the above liquid phase condition and mass spectrum condition, if the relative deviation of the retention time of the detected chromatographic peak and the retention time of the standard substance is not more than 2.5%, and the relative abundance ratio of two daughter ions of the target compound is compared with that of the standard solution with the equivalent concentration, the allowable deviation should be within a reasonable range.
(5) The linear relationship is: the standard stock solution is diluted step by step to prepare five series working solutions with different concentrations, namely 1.0 mu g/L, 5.0 mu g/L, 10.0 mu g/L, 20.0 mu g/L and 50.0 mu g/L. The concentration was measured in the order of low to high according to the chromatographic conditions and mass spectrometric conditions described above. Taking the concentration X of the standard solution and the corresponding peak area Y as a standard curve graph, and calculating a regression equation and a correlation coefficient, wherein the regression equation is Y which is 3775.2X-2866.1, and the correlation coefficient is R2The linearity is good when the value is 0.9998.
(6) Accuracy and precision: accurately weighing a negative water sample, adding 3 chloroformyl substance standard solutions with different content levels, measuring 6 parallel samples in each concentration, analyzing according to the chromatographic conditions and the mass spectrum conditions, wherein the accuracy is represented by the recovery rate, and the precision is represented by the relative standard deviation. The accuracy and precision calculations are shown in table 1.
TABLE 1 test results of accuracy and precision of addition of chloroformyl compounds in surface water
As can be seen from Table 1, the accuracy of the method of the invention is between 70% and 100%, and the precision is below 10%. The method has high accuracy and good reproducibility.
(7) Detection limit and quantification limit: the detection limit and the quantitative limit are determined by a method of adding chloroformyl substances into blank tissues, the lowest concentration of the method is 0.01 mu g/L, the signal-to-noise ratio of the characteristic ion chromatographic peak is greater than or equal to 3(S/N is greater than or equal to 3), namely the detection limit of the method, the signal-to-noise ratio is greater than or equal to 10(S/N is greater than or equal to 10), and the concentration with better recovery rate and precision is 0.02 mu g/L, namely the quantitative limit of the method.
The above examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention; it should be noted that various changes and modifications can be made by those skilled in the art without departing from the scope of the inventive concept, which falls within the scope of the invention; therefore, all equivalent changes and modifications within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (10)
1. A pretreatment method for detecting trace chloroformyl compounds in a water sample is characterized by comprising the following steps:
1) removing suspended particles from a water sample, and placing a certain volume of water sample to be detected in a container;
2) adding a proper amount of soluble salt;
3) adding a proper amount of extracting solution and a proper amount of organic acid, and extracting by shaking; the extracting solution is an nonpolar organic solvent which is not mutually soluble with water;
4) standing for layering, and transferring to obtain an initial organic phase;
5) repeating the steps 2) -3) on the aqueous phase to obtain a re-extracted organic phase;
6) combining the primary extracted organic phase and the secondary extracted organic phase to obtain an extraction mixed solution;
7) concentrating the extraction mixed solution, fixing the volume with a constant volume solution, uniformly mixing, and filtering through a 0.22-micrometer organic filter membrane to obtain a solution to be detected;
the constant volume liquid is a 0.1% formic acid-methanol solution, and preferably, the constant volume liquid is prepared by mixing methanol and a 0.1% formic acid aqueous solution according to a volume ratio of 6: 4, mixing and preparing.
2. The pretreatment method according to claim 1, wherein the soluble salt is a sodium salt or a potassium salt;
preferably, the soluble salt is a mixture of sodium chloride and sodium L-ascorbate, and the mass ratio of the sodium chloride to the sodium L-ascorbate in the mixture is 2-4: 1.
3. the pretreatment method according to claim 1, wherein the extraction liquid is one or more selected from the group consisting of ethyl acetate, carbon tetrachloride and petroleum ether.
4. The pretreatment method according to claim 1, wherein the organic acid is formic acid or acetic acid.
5. The pretreatment method according to claim 1, wherein a volume ratio of the extraction liquid to the sample solution to be tested is 1: 1-3; the volume ratio of the organic acid to the water sample to be detected is 1: 50-200.
6. The pretreatment method according to claim 1, wherein the concentration is carried out by concentration under reduced pressure in a water bath at 30 to 50 ℃ in a rotary evaporator.
7. Use of the pretreatment method according to any one of claims 1 to 6 for detecting the residual amount of chloroformyl compounds in a water sample.
8. A determination method for detecting the residual amount of chloroformyl compounds in a water sample is characterized by comprising the following steps:
a) the pretreatment method according to any one of claims 1 to 6, wherein a water sample is pretreated to obtain a liquid to be detected;
b) and (3) determining the content of the chloroformyl compound in the solution to be detected by using a liquid chromatography-tandem mass spectrometry method.
9. The assay of claim 8, wherein the liquid chromatography-tandem mass spectrometry conditions are: a chromatographic column: MG S-3 column, 3.0X 35mm, 3 μm; the mobile phase is methanol and 0.1% formic acid, gradient elution is carried out for 0-0.5 min, and 5% methanol is used; 0.5-1 min, 5% -40% methanol; 1-1.5 min, 40-80% methanol; 1.5-3 min, 80-80% methanol; 3-4 min, 5% -5% methanol; the sample introduction amount was 5. mu.L, the flow rate was 0.3mL/min, and the column temperature was 40 ℃.
10. The assay of claim 7 or 8, wherein the mass spectrometric conditions of the liquid chromatography-tandem mass spectrometry are: an ion source: ESI; the scanning mode is as follows: a positive ion; ion source temperature: 150 ℃; capillary voltage: 0.5 kv; the quantitative ion pair of the chloroformyl is 223.07/78.98, the qualitative ion pair is 223.07/113.03, the cone voltage is 41V, and the collision energy is 21eV and 19eV respectively.
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