CN112198249B - Detection method of ethanolamine compound in soil - Google Patents
Detection method of ethanolamine compound in soil Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention discloses a method for detecting ethanolamine compounds in soil. The method comprises the following steps: the method comprises the steps of measuring the water content of a soil sample, pretreating the soil sample, preparing a standard working solution, detecting and detecting the standard working solution by high performance liquid chromatography-mass spectrometry, detecting the actual sample solution to be detected under the same conditions, and calculating the content of the ethanolamine compound in the soil sample by a formula. The invention establishes a rapid, high-efficiency and high-recovery extraction method by using an ultrasonic extraction technology, and after synchronous purification, the high performance liquid chromatography-triple quadrupole mass spectrometer is used for detection, so that matrix interference is effectively eliminated, and qualitative and quantitative analysis of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil is realized.
Description
Technical Field
The invention belongs to the field of analysis and test, particularly relates to a detection method of ethanolamine compounds in soil, and particularly relates to a detection method of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil.
Background
At present, detection research on ethanolamine compounds mainly focuses on the fields of cosmetics, foods and the like, but no detection method and standard aiming at the ethanolamine compounds in the environment exist. The ethanolamine compound generally has amino and hydroxyl, so the ethanolamine compound has strong polarity, the matrix of soil is complex, the ethanolamine compound is difficult to extract by an organic solvent, the recovery rate is generally low, and the phenomenon of unstable sample parallelism can occur. The ethanolamine compound has low vapor pressure and a boiling point of 170 ℃ or higher, so that the ethanolamine compound cannot be detected by directly using a headspace pretreatment method.
The response of the gas phase or gas chromatography-mass spectrometry method used in the existing detection technology is in the mg/L level, and the main reasons are that the molecular weight of the ethanolamine compound is small, the retention time is short, the degree of interference by impurities is large, and the peak type is trailing due to the fact that hydroxyl and amino carried by ethanolamine and diethanolamine easily form hydrogen bonds with silanol groups of a chromatographic column stationary phase, and the accuracy of quantification is influenced. Therefore, it may be necessary to use a specially treated column, such as a column with its stationary phase being inert, or a column with low polarity to reduce the hydrogen bond formed between the carrier and the target compound, so as to obtain a better peak pattern, and these factors may increase the final detection cost.
Ethanolamine compounds are important chemical raw materials and are mainly used as adsorbents and medical intermediates for adsorbing acidic gases, modifiers for resin synthesis, washing products, pH balancing agents in cosmetics and the like. Ethanolamine substances have irritation to the skin and mucous membranes of human bodies, and after being absorbed by the human bodies, the ethanolamine substances can cause damage to the liver and the kidney to different degrees. In addition, ethanolamine compounds also react with a nitritation system to generate nitrosamine carcinogens, so that the risk of carcinogenesis is greatly increased. The mode of the ethanolamine compounds entering the environment is mainly along with the manufacture, use and disposal of the products, and the ethanolamine compounds directly enter the environment, thereby influencing the health and survival of human beings.
In summary, in order to understand the concentration level and accumulation of ethanolamine compounds in soil, a highly sensitive analytical detection means is required to be established for detecting ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for detecting ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil. The detection method adopts water ultrasonic extraction acidified by organic acid, ethyl acetate purification and high performance liquid chromatography-triple quadrupole mass spectrometer (LC-MS/MS) to qualitatively and quantitatively measure the contents of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil, and realizes the rapid, high-sensitivity and low-cost detection of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil.
The purpose of the invention is realized by the following technical scheme:
a method for detecting ethanolamine compounds in soil comprises the following steps:
(1) Determination of water content of soil sample
Taking part of soil to be measured, measuring the dry matter content, and calculating the water content of the soil sample;
(2) Pretreatment of soil samples
Adding a formic acid aqueous solution into a soil sample, performing ultrasonic extraction after the sample is dispersed by vortex, then adding ethyl acetate for vortex purification, performing refrigerated centrifugation, taking a lower-layer water phase, and filtering to obtain an actual sample solution to be detected;
(3) Preparation of standard working solutions
Weighing target objects of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine, and preparing different concentration gradient standard working solutions corresponding to the target objects by respectively using formic acid aqueous solution as a solvent;
(4) High performance liquid chromatography-triple quadrupole mass spectrometer detection
Detecting each concentration gradient standard working solution in the step (3) by adopting a high performance liquid chromatography-triple quadrupole mass spectrometry method, and establishing a standard working curve corresponding to the target by using an external standard method; detecting the actual sample solution to be detected in the step (2) by adopting a high performance liquid chromatography-triple quadrupole mass spectrometry method under the same condition, comparing with a standard working curve corresponding to a target object, calculating the concentration of the target object in the actual sample solution to be detected, and finally calculating the content of the target object in the soil sample according to a formula A.1 by combining the water content and the dry matter content of the soil sample in the step (1) and the mass of the soil sample in the step (2):
in the formula A.1, omega 1i The concentration of the ith target substance in the soil sample is [ mu ] g/kg; rho 1i The concentration of the ith target object in the actual sample solution to be detected in the step (2) is [ mu ] g/L; v 1 The volume of the formic acid aqueous solution in the step (2), mL; v s The water content of the soil sample in the step (1) is mL; m is 1 Mass (wet weight) of the soil sample in step (2), g; omega dm Is the dry matter content,%, in the soil sample.
The determination of the dry matter content in the step (1) is referred to HJ613-2011.
Preferably, the water content of the soil sample in the step (1) is calculated according to the following formula:
in the formula A.2, V S Water content of the soil sample, mL; m is a unit of 1 Soil sample mass (wet weight), g; omega dm Is the dry matter content,%, in the soil sample; ρ is a unit of a gradient H2O Is the density of water at 20 ℃, g/mL.
Preferably, the ratio of the soil sample, the aqueous solution of formic acid and the ethyl acetate in the step (2) is 1g: 2-4 mL: 2-4 mL; the volume concentration of the formic acid aqueous solution is 0.1-3%.
More preferably, the volumes of the aqueous formic acid solution and the ethyl acetate are the same.
Preferably, the volume concentration of the formic acid aqueous solution in the step (3) is 0.1-3%.
In the step (2), the time of the first vortex is 5-15 min, and the time of the second vortex is 10-20 min.
Preferably, the time of the ultrasonic extraction in the step (2) is 20-60 min.
Preferably, the freezing centrifugation in the step (2) refers to centrifugation at 5-15 ℃ and 5000-8000 r/min for 5-15 min.
Preferably, the filtration in the step (2) is performed by using a polytetrafluoroethylene or nylon filter membrane; the pore diameters of the polytetrafluoroethylene filter membrane and the nylon filter membrane are respectively 0.45 mu m and 0.22 mu m.
Preferably, the concentrations of the standard working solutions corresponding to the targets in step (3) are 5. Mu.g/L, 10. Mu.g/L, 20. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L and 200. Mu.g/L.
Preferably, the high performance liquid chromatography-triple quadrupole mass spectrometry of the step (4) is performed by using a high performance liquid chromatography-triple quadrupole mass spectrometer.
Preferably, the detection conditions of the high performance liquid chromatography in the step (4) are as follows: a chromatographic column: shimadzu Shim-pack Velox PFPP has an inner diameter of 2.1mm, a column length of 100mm and a particle size of 1.8 μm; the mobile phase A is a formic acid aqueous solution with the volume concentration of 0.1 percent; the mobile phase B is acetonitrile, the flow rate is 0.4mL/min, the column temperature is 40 ℃, and the sample injection amount is 2 mu L.
Preferably, the detection conditions of the triple quadrupole mass spectrometry in the step (4) are as follows: flow rate of atomizing gas: 3L/min; heating air flow: 10L/min; interface temperature: 300 ℃; DL temperature: 250 ℃; temperature of the heating block: 400 ℃; flow rate of drying gas: 10L/min; the detection mode is multi-reaction monitoring and positive ion mode.
In the method of the invention, the concentration of the target in the actual sample solution to be tested in the step (2) should be within the linear range of the standard curve, and if the measured concentration of the target is beyond the linear range, the soil sample in the step (2) needs to be extracted again after the sample weighing amount is reduced, or a certain amount of extracted actual sample solution to be tested is diluted and then is subjected to sample injection analysis.
The invention utilizes an ultrasonic extraction technology to establish rapid and efficient extraction and purification, and utilizes a high performance liquid chromatography-triple quadrupole mass spectrometer to effectively carry out qualitative and quantitative analysis on ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts formic acid acidified water for extraction, promotes the ionization of amine substances, increases the solubility of the target compounds in water, reduces the volatilization of the target compounds in the extraction process, and obviously improves the recovery rate.
(2) According to the invention, the ethyl acetate is used for purifying the extracting solution, so that impurities with medium polarity to weak polarity are effectively adsorbed, and the matrix effect interference caused by soil is effectively reduced; the extraction process is synchronous in purification, and the extract can be directly put on a computer for analysis after centrifugal filtration, so that the experimental time is saved, the experimental efficiency is improved, and the method is suitable for large-batch sample analysis.
(3) The method adopts the MRM (multiple reaction monitoring) mode of the triple quadrupole gas chromatography-mass spectrometer, optimizes and selects the characteristic ion pair with specificity, reduces matrix interference, increases sensitivity, and can reduce the risk of false positive in the sample compared with methods such as gas chromatography and gas chromatography-mass spectrometer and the like, thereby improving the detection accuracy.
(4) According to the invention, a PFPP chromatographic column is selected, and pentafluorophenylpropyl is bonded in the column, so that the problems that a C18 chromatographic column is not strong in retention of polar compounds and hydrophilic chromatographic columns such as Amide and HILIC are unstable in chromatographic peaks under an acidic condition are solved, under an optimized chromatographic condition, an acidic extract can be directly loaded on a machine, a stable chromatographic peak can be obtained without adjusting pH, the analysis requirements are met, and the method is more convenient and efficient.
(5) The detection method provided by the invention fills the blank of the ethanolamine detection technology in the environment, the standard recovery rate of the obtained ethanolamine is 80%, the standard deviation RSD is 8.1%, the detection limit is 8.41 mug/kg, and the quantification limit is 33.6 mug/kg; the standardized recovery rate of diethanolamine is 106%, the standard deviation RSD is 9.8%, the detection limit is 16.8 μ g/kg, the quantification limit is 67.3 μ g/kg, the standardized recovery rate of N, N-dimethylethanolamine is 70%, the standard deviation RSD is 6.4%, the detection limit is 2.07 μ g/kg, the quantification limit is 8.28 μ g/kg, the standardized recovery rate of N-methyl-2-hydroxyethylamine is 74%, the standard deviation RSD is 4.4%, the detection limit is 2.24 μ g/kg, the quantification limit is 8.96 μ g/kg, the standardized recovery rate of triisopropanolamine is 80%, the standard deviation RSD is 0.46%, the detection limit is 1.92 μ g/kg, and the quantification limit is 7.68 μ g/kg. The method is suitable for detecting ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine in soil.
Drawings
Fig. 1 is a total ion flow diagram of 5 targets in soil.
Fig. 2 is a total ion flowsheet of 5 targets in sample a (N = 1) in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Instruments and reagents used in the examples
Ethanolamine (98.05%) was purchased from CATO Research Chemicals Inc, diethanolamine (98.7%) was purchased from Chem Service Inc, N-dimethylethanolamine (99.0%) was purchased from meclin, N-methyl-2-hydroxyethylamine (99.0%) was purchased from alatin, and triisopropanolamine (95%) was purchased from alatin. The acetonitrile brand used in the experiment was MERCK, the ethyl acetate brand was CNW, the formic acid brand was Koimeu, and the purity was HPLC. The water used is primary water specified in GB/T6682-2008.
Example 1
(1) Measurement of Water content of sample
Taking a part of the soil sample to be referenced to the standard HJ613-2011 to measure the dry matter content, and calculating the water content of the soil sample according to the formula A.2.
(2) Pretreatment of a sample:
adding 5.0g of soil into a 50mL centrifuge tube, adding 20mL of 1% formic acid aqueous solution, performing vortex extraction for 5min, performing ultrasonic extraction for 30min, adding 20mL of ethyl acetate, and performing vortex extraction for 15min at a rotating speed. Freezing and centrifuging at 8000r/min at 10 deg.C for 5min, sucking lower water phase, filtering with 0.22 μm organic phase nylon filter membrane to obtain actual sample solution to be tested, transferring to sample injection vial, and waiting for on-machine analysis.
(3) Preparation of standard working solutions
Respectively weighing 1mg of standard substances of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine by using an analytical balance, respectively preparing standard stock solutions with the concentration of 1000mg/L corresponding to each standard substance by using methanol, respectively preparing the standard stock solutions into 1mg/L working solutions by diluting the standard stock solutions by using 1% formic acid aqueous solutions, and finally respectively preparing the standard working solutions with the concentrations of 5 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L, 100 mu g/L and 200 mu g/L by using 1% formic acid aqueous solutions.
(4) High performance liquid chromatography-triple quadrupole mass spectrometry combined instrument detection
The liquid chromatography conditions were: a chromatographic column: shimadzu Shim-pack Velox PFPP has an inner diameter of 2.1mm, a column length of 100mm and a particle size of 1.8 μm; the mobile phase A is a formic acid aqueous solution with the volume concentration of 0.1 percent; the mobile phase B is acetonitrile, the flow rate is 0.4mL/min, the column temperature is 40 ℃, and the sample injection amount is 2 mu L. The gradient elution conditions are shown in table 1.
TABLE 1 gradient elution conditions
The mass spectrometric conditions of the target compound under the above conditions were: flow rate of atomizing gas: 3L/min; heating air flow: 10L/min; interface temperature: 300 ℃; DL temperature: 250 ℃; temperature of the heating block: 400 ℃; flow rate of drying gas: 10L/min; the detection mode is multi-reaction monitoring and positive ion mode. The mass spectral parameters of the target compounds under the above conditions are shown in table 2.
TABLE 2 Mass Spectrometry parameters for Ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine
Measuring the standard working solution of each concentration gradient in the step (3) in a high performance liquid chromatography-triple quadrupole mass spectrometer, and establishing a standard working curve corresponding to the target compound by using an external standard method; and (3) injecting the actual sample solution to be detected in the step (2) into a high performance liquid chromatography-triple quadrupole mass spectrometer for determination under the same conditions, comparing the obtained detection result with the standard working curve of the corresponding target compound, thus calculating the concentration of the target compound in the actual sample solution to be detected, and then calculating the content of the target compound in the soil sample according to the mass, the water content and the dry matter content of the soil sample in the step (2).
And (3) qualitative identification: under the condition of the same instrument, if the retention time of the chromatographic peak of the target compound in the actual sample solution to be detected is consistent with the retention time of the corresponding target compound in the standard working solution, and the abundance ratio of the qualitative and quantitative ion pairs is the same as that of the standard solution, the target compound to be detected in the sample can be judged.
Quantitative analysis: and establishing a standard working curve corresponding to the target compound according to the result of the standard working solution, wherein the linear range is 5-200 mu g/L, the correlation coefficient of the standard curve is greater than 0.9997, calculating the concentration of the target compound according to the ratio of the peak area of the target compound to the concentration, and finally calculating the concentration of the target compound in the sample according to the mass, the water content and the dry matter content of the soil sample.
The water content of the fresh soil sample is calculated according to the following formula:
in the formula: v S Water content of the soil sample, mL; m is 1 Soil sample mass (wet weight), g; omega dm Is the dry matter content,%, in the soil sample; rho H2O Is the density of water at 20 ℃, g/mL.
The mass concentration of the target compound in the soil sample is calculated according to the following formula:
in the formula: omega 1i The concentration of the ith target substance in the soil sample is [ mu ] g/kg; ρ is a unit of a gradient 1i The concentration of the ith target object in the sample solution to be actually detected in the step (2) is mu g/L; v 1 The volume of the formic acid aqueous solution in the step (2) is mL; v s The water content of the soil sample in the step (1) is mL; m is a unit of 1 Mass (wet weight) of the soil sample in step (2), g; omega dm Is the dry matter content,%, in the soil sample.
And (3) standard recovery rate and precision:
the recovery rate adopts 6 times of parallel standard addition, and the standard addition method comprises the following steps: adding 400 mu L of mixed standard solution with the concentration of 1mg/L of the target compound into 5.0g of soil sample to ensure that the target concentration is 80 mu g/kg, adsorbing the target compound into the soil sample after 1h of solvent evaporation is completed, and extracting and measuring according to the step (2) and the step (4). The recovery of the target compound was obtained by subtracting the blank sample concentration (i.e. the concentration measured for the soil sample without the standard) from the standard concentration and comparing it with the theoretical additive concentration (i.e. 80. Mu.g/kg), the method precision being expressed as the standard deviation of the 6 parallel standard results.
Determination of detection limit and quantification limit: reference is made to the standard HJ168-2010.
And selecting a soil sample without a target object to perform a method detection limit test experiment.
Weighing 7 parts of 5.0g soil sample, respectively adding a certain amount of standard mixed solution of the target compound into the 7 parts of soil sample, adsorbing the target compound in the soil sample after the solvent is completely volatilized for 1 hour, and extracting according to the step (2) and determining according to the step (4). And (4) detecting the limit according to a formula (A.3) calculation method, and judging the reasonability of the limit. It is appropriate to specify a primary sample concentration for determining the detection limit of the method if 50% of the target compound concentration (concentration in the soil sample) is within the range of 3 to 5 times the calculated detection limit of the method, while at least 90% of the target compound concentration (concentration in the soil sample) is within the range of 1 to 10 times the calculated detection limit of the method and the remaining not more than 10% of the target compound concentration (concentration in the soil sample) should not exceed 20 times the calculated detection limit of the method. For compounds whose ratio of the measured average value of the primary standard sample to the detection limit of the method is not between 3 and 5, the concentration is increased or decreased, and the parallel analysis is repeated until the ratio is between 3 and 5. The method detection limit for the target compound is selected to be the method detection limit for the target compound at a ratio between 3 and 5.
MDL＝t (n-1，0.99) ×S (A.3)
In the formula: MDL is the detection limit of the method; n is the number of parallel determinations of the soil sample; t is the t distribution (one side) with the degree of freedom of n-1 and the confidence of 99%; s is the standard deviation of n parallel measurements; wherein when n =7 with a confidence of 99%, t =3.143.
And (3) weighing 7 parts of 5.0g of the soil sample without the target object, adding a certain amount of standard mixed solution of the target compound into the 7 parts of the soil sample, adsorbing the target compound in the soil sample after completely volatilizing the solvent for 1h, and extracting according to the step (2) and measuring according to the step (4). Comparing the variance (S2) of the previous batch with the variance of the current batch, and the larger is recorded as S A 2 The smaller is denoted as S B 2 . If S A 2 /S B 2 If the variance is more than 3.05, the variance measured in the current batch is marked as the variance measured in the previous batch, and the sample concentration is readjusted for measurement. If S A 2 /S B 2 If the detection limit is less than 3.05, the detection limit is calculated according to the following formula:
in the formula: v a The degrees of freedom of the lot with larger variance, n A -1；V b For the degree of freedom of the batch with smaller variance, n B -1；S p Is the combined standard deviation; t is a degree of freedom V a +V b T distribution with a confidence of 99%.
Lower limit of measurement of method: referring to HJ168-2010, the detection limit was determined as the lower limit of the measurement (limit of quantitation) of the target in the method at 4-fold. The detection limits of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine were 8.41. Mu.g/kg, 16.8. Mu.g/kg, 2.07. Mu.g/kg, 2.24. Mu.g/kg and 1.92. Mu.g/kg, respectively, and the measurement lower limits (quantitation limits) were 33.6. Mu.g/kg, 67.3. Mu.g/kg, 8.28. Mu.g/kg, 8.96. Mu.g/kg and 7.68. Mu.g/kg, respectively.
TABLE 3 method recovery, detection limit and quantitation limit
In the table, a is the mean. + -. Standard deviation (%) (n = 6)
Example 2
(1) Measurement of Water content of sample
Taking a part of the soil sample of the sample A, measuring the dry matter content by referring to the standard HJ613-2011, and calculating the water content of the soil sample according to the formula A.2.
(2) Pretreatment of a sample:
weighing 2 parts of sample A with the mass of 5.0847g (N = 1) and 5.0234g (N = 2) into 250 mL centrifuge tubes, adding 20mL of 1% formic acid aqueous solution respectively, performing vortex extraction for 5min, performing ultrasonic extraction for 30min, and adding 20mL of ethyl acetate respectively, and performing vortex extraction for 15min at the rotating speed. Performing refrigerated centrifugation at 8000r/min for 5min at 10 ℃, sucking a lower-layer water phase, filtering with a 0.22-micron organic-phase nylon filter membrane to obtain a practical sample solution to be detected, transferring to a sample injection vial, taking 2.0 μ L of the sample solution to perform high performance liquid chromatography-triple quadrupole mass spectrometer detection according to the method established in the step (4) of the example 1, calculating the concentration of a target through the ratio of the peak area to the concentration of the target compound, and calculating the concentration of the target through the ratio of the peak area to the concentration of the target compound, wherein the detection result is shown in Table 4.
TABLE 4 content of 5 Ethanolamine Compounds in sample A
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for detecting ethanolamine compounds in soil is characterized by comprising the following steps:
(1) Determination of soil sample water content
Taking part of soil to be measured, measuring the dry matter content, and calculating the water content of the soil sample;
(2) Pretreatment of soil samples
Adding a formic acid aqueous solution into a soil sample, performing ultrasonic extraction after the sample is dispersed by vortex, then adding ethyl acetate for vortex purification, performing refrigerated centrifugation, taking a lower-layer water phase, and filtering to obtain an actual sample solution to be detected;
(3) Preparation of standard working solutions
Weighing target objects of ethanolamine, diethanolamine, N-dimethylethanolamine, N-methyl-2-hydroxyethylamine and triisopropanolamine, and preparing standard working solutions with different concentration gradients corresponding to the target objects by respectively using formic acid aqueous solution as a solvent;
(4) High performance liquid chromatography-triple quadrupole mass spectrometer detection
Detecting each concentration gradient standard working solution in the step (3) by adopting a high performance liquid chromatography-triple quadrupole mass spectrometry method, and establishing a standard working curve corresponding to the target by using an external standard method; detecting the actual sample solution to be detected in the step (2) by adopting a high performance liquid chromatography-triple quadrupole mass spectrometry method under the same condition, comparing the detected sample solution with a standard working curve corresponding to a target object, calculating the concentration of the target object in the actual sample solution to be detected, and finally calculating the content of the target object in the soil sample according to a formula A.1 by combining the water content and the dry matter content of the soil sample in the step (1) and the mass of the soil sample in the step (2):
in the formula A.1, omega 1i The concentration of the ith target substance in the soil sample is [ mu ] g/kg; rho 1i The concentration of the ith target object in the sample solution to be actually detected in the step (2) is mu g/L; v 1 The volume of the formic acid aqueous solution in the step (2) is mL; v s The water content of the soil sample in the step (1) is mL; m is a unit of 1 Is the wet weight, g, of the soil sample of step (2); omega dm Is the dry matter content,%, in the soil sample;
performing the high performance liquid chromatography-triple quadrupole mass spectrometry by using a high performance liquid chromatography-triple quadrupole mass spectrometry instrument;
the detection conditions of the high performance liquid chromatography are as follows: a chromatographic column: shimadzu Shim-pack Velock PFPP has an inner diameter of 2.1mm, a column length of 100mm and a particle size of 1.8 μm; the mobile phase A is a formic acid aqueous solution with the volume concentration of 0.1 percent; the mobile phase B is acetonitrile, the flow rate is 0.4mL/min, the column temperature is 40 ℃, and the sample injection amount is 2 mu L;
the detection conditions of the triple quadrupole mass spectrometry are as follows: flow rate of atomizing gas: 3L/min; heating air flow: 10L/min; interface temperature: 300 ℃; DL temperature: 250 ℃; temperature of the heating block: 400 ℃; flow rate of drying gas: 10L/min; the detection mode is multi-reaction monitoring and positive ion mode; the gradient elution conditions were:
2. the method for detecting ethanolamine compounds in soil according to claim 1, wherein the ratio of the soil sample, the aqueous solution of formic acid and the ethyl acetate in the step (2) is 1g: 2-4 mL: 2-4 mL.
3. The method for detecting ethanolamine compounds in soil according to claim 1, wherein the formic acid aqueous solution in steps (2) and (3) has a volume concentration of 0.1-3%.
4. The method for detecting ethanolamine compounds in soil according to claim 1, wherein the water content of the soil sample obtained in the step (1) is calculated according to the following formula:
in the formula A.2, V S Water content of the soil sample, mL; m is a unit of 1 Is the soil sample wet weight, g; omega dm Is the dry matter content,%, in the soil sample; ρ is a unit of a gradient H2O Is the density of water at 20 ℃, g/mL.
5. The method for detecting ethanolamine compounds in soil according to claim 1, wherein in the step (2), the time for the first vortex is 5-15 min, and the time for the second vortex is 10-20 min; the ultrasonic extraction time is 20-60 min.
6. The method for detecting ethanolamine compounds in soil according to claim 1, wherein the step (2) of refrigerated centrifugation refers to centrifugation at 5000-8000 r/min at 5-15 ℃ for 5-15 min; the filtration is carried out by using a polytetrafluoroethylene or nylon filter membrane; the pore diameters of the polytetrafluoroethylene filter membrane and the nylon filter membrane are respectively 0.45 mu m and 0.22 mu m.
7. The method for detecting ethanolamine compounds in soil according to claim 1, wherein the concentrations of the standard working solutions corresponding to the targets in step (3) are 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L and 200 μ g/L.
8. The method according to claim 1, wherein the concentration of the target in the actual sample solution to be tested in step (2) is within a linear range of a standard curve, and if the measured concentration of the target is out of the linear range, the soil sample in step (2) needs to be extracted again after the sample weight is reduced, or a certain amount of the extracted actual sample solution to be tested is diluted and then subjected to sample injection analysis.
9. The method for detecting ethanolamine compounds in soil according to claim 2, wherein the volumes of the aqueous formic acid solution and the ethyl acetate in the step (2) are the same.
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| CN103760261A (en) * | 2014-01-07 | 2014-04-30 | 深圳市谱尼测试科技有限公司 | Method for measuring ethanolamine substance residual quantity in cosmetics |
| CN105891341A (en) * | 2014-09-10 | 2016-08-24 | 南京大学 | Method for measuring content of triethanolamine in cement grinding aid |
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| CN105891341A (en) * | 2014-09-10 | 2016-08-24 | 南京大学 | Method for measuring content of triethanolamine in cement grinding aid |
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