CN111103387A - Method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil - Google Patents
Method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil Download PDFInfo
- Publication number
- CN111103387A CN111103387A CN202010021042.9A CN202010021042A CN111103387A CN 111103387 A CN111103387 A CN 111103387A CN 202010021042 A CN202010021042 A CN 202010021042A CN 111103387 A CN111103387 A CN 111103387A
- Authority
- CN
- China
- Prior art keywords
- acid
- mobile phase
- soil
- sample
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- G01N30/89—Inverse chromatography
-
- 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
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, which comprises the following steps: (1) preparing a standard solution and a mobile phase; (2) extracting a sample solution to be detected from a soil sample; (3) respectively detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) by adopting a reversed-phase high performance liquid chromatograph; (4) and (4) calculating the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected according to the detection result obtained in the step (3), and further calculating the corresponding contents in the soil. The determination method can simultaneously determine the contents of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, has the advantages of simple sample processing method, convenient operation in the detection process, high sensitivity, low detection limit, accuracy and high efficiency.
Description
Technical Field
The invention relates to the field of chemical analysis, in particular to a method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil.
Background
The halogenated acetic acid is an important chemical raw material, is an important intermediate in organic synthesis, and has wide application in the aspects of pesticides, medicines, dyes, daily chemicals, surfactants, chemical reagents, papermaking chemicals, oilfield chemicals, textile assistants, rubber assistants, electroplating, perfume and essence and the like.
Chloroacetic acids, which are important component categories of halogenated acetic acids, including chloroacetic acid, dichloroacetic acid and trichloroacetic acid, belong to highly toxic substances, have potential carcinogenic effects on human bodies, and the toxicity of chloroacetic acids is continuously proved in toxicology and physiology, so that the chloroacetic acids attract extensive attention of people. There are many analytical methods for measuring chloroacetic acids in water, such as titration, colorimetry, gas chromatography-mass spectrometry, ion chromatography, high performance liquid chromatography, and high performance liquid chromatography-mass spectrometry. However, the conventional methods have various disadvantages. The titration method is one of the original methods, although the cost is low, the measurement error is large, and the separate determination of the chloroacetic acid substances is difficult; although the colorimetric method is clear and intuitive, the sensitivity is low, the selectivity is poor, and the separate determination of the chloroacetic acid substances is difficult; the gas chromatography is a measuring method adopted by the national standard GB/T5750.10-2006 Drinking Water Standard test method, but extraction and esterification derivative treatment are required, the operation steps are more, the analysis time is longer, and a large amount of toxic and harmful reagents adopted can not only harm the health of testers, but also pollute the environment; although the ion chromatography is simple in pretreatment and does not need to use an organic reagent, the ion chromatography is limited by the complexity of a matrix and also prevents the interference of chloride ions, nitrate ions, sulfate ions and the like in water; although the gas chromatography-mass spectrometry and the high performance liquid chromatography-mass spectrometry have high sensitivity and precision, the application range of the combined method is limited due to high cost of the mass spectrometer, and the combined method cannot be popularized; although high performance liquid chromatography has short analysis time and high sensitivity, the cost of the reagent is relatively high and the influence of matrix effect of a sample to be detected can be possibly caused.
At present, researchers have conducted a great deal of research on the measurement of chloroacetic acids, particularly the separate measurement of dichloroacetic acid and trichloroacetic acid. For example, wujun determined the content of dichloroacetic acid and trichloroacetic acid in drinking water by gas chromatography, in which a water sample was added with sulfuric acid and sodium chloride and shaken and dissolved, methyl tert-butyl ether containing an internal standard substance (1, 2-dibromopropane) was extracted, sulfuric acid-methanol solution was esterified and derivatized, anhydrous sodium sulfate solution was added and shaken and left to stand, and the supernatant was taken and measured by gas chromatography with an electron trap. Although the determination method can realize good separation of the dichloroacetic acid derivative product, the trichloroacetic acid derivative product and the internal standard substance, the operation steps are more, the analysis time is longer, and toxic and harmful reagents such as methyl tert-butyl ether, 1, 2-dibromopropane and methanol are also used, so that the method can not only harm the health of testers, but also pollute the environment (Jun Wu, gas chromatography for determining dichloroacetic acid and trichloroacetic acid in drinking water, China sanitary inspection impurities, 23 rd volume 8 of 7 months in 2013).
CN110346503A discloses an analytical method for detecting dichloroacetic acid and trichloroacetic acid in water, which adopts ion chromatography, and mainly includes determining operating parameters of an ion chromatograph, making a standard curve of dichloroacetic acid and/or trichloroacetic acid, and determining the content in a sample by adopting ion chromatograph analysis. Although the analysis method can separate dichloroacetic acid and trichloroacetic acid on a spectrogram, the problems of peak inclusion, unstable baseline and impurity peak interference obviously exist, and the problem of interference of other ions cannot be effectively avoided.
CN108008061A discloses a method for detecting monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and sulfate radicals in chloroacetic acid by ion chromatography, wherein an ion chromatograph is adopted in the detection method to analyze diluted sample liquid to be detected, and the concentrations of monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and sulfate radicals in the sample liquid to be detected can be obtained by comparing the obtained peak area with a standard correction curve, so that the corresponding content of the sample to be detected before dilution is obtained. Although the detection method can separate monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and sulfate radicals on a spectrogram, the problems of peak inclusion, unstable baseline and impurity peak interference obviously exist, and the problem of interference of other ions cannot be effectively avoided.
Lily et al determined the contents of dichloroacetic acid and trichloroacetic acid in drinking water by ultra performance liquid chromatography-tandem mass spectrometry, in which a sample to be tested was filtered through a 0.2 μm filter membrane, separated on an HSS T3 chromatographic column, gradient eluted with acetonitrile-0.1% formic acid aqueous solution, and detected in a Multiple Reaction Monitoring (MRM) mode under an electrospray anion mode. Although the determination method optimizes chromatographic conditions and mass spectrum conditions and improves precision and recovery rate, the adopted mass spectrometer has higher cost and limited application range (Lily et al, ultra performance liquid chromatography-tandem mass spectrometry for determining dichloroacetic acid and trichloroacetic acid in drinking water, volume 23, 2 nd of 2016 (practical preventive medicine)).
The main consumption field of the halogenated acetic acid in China is pesticide and pesticide industry, more than twenty kinds of commonly used pesticides, weeding and plant production regulators can be synthesized, so that the halogenated acetic acid can cause pollution in soil, and the halogenated acetic acid can also migrate into the soil from a water body, so that the pollution problem of the halogenated acetic acid in the soil is further serious, and the great threat is caused to the health of human beings. Relatively, reports about methods for analyzing halogenated acetic acid in soil are few, and once a soil pollution event occurs, problems of lack of efficient and accurate measurement methods, lack of relevant detection and analysis bases, incapability of accurate judgment and the like are caused. The prior art not only has various measurement defects, but also mainly focuses on measuring the content of heavy water, so that a method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil is urgently needed to be developed.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, which comprises the following steps: (1) preparing a standard solution and a mobile phase; (2) extracting a sample solution to be detected from a soil sample; (3) respectively detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) by adopting a reversed-phase high performance liquid chromatograph; (4) and (4) calculating the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected according to the detection result obtained in the step (3), and further calculating the corresponding contents in the soil. The determination method can simultaneously determine the contents of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, has the advantages of simple sample processing method, convenient operation in the detection process, high sensitivity, low detection limit, accuracy and high efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, which comprises the following steps:
(1) preparing a mobile phase and a standard solution containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid, wherein the mobile phase consists of acetonitrile and a phosphoric acid solution according to a volume ratio of 2:98, and the volume fraction of the phosphoric acid solution is 0.1%;
(2) adding a soil sample into the mobile phase obtained in the step (1) to extract a sample solution to be detected;
(3) detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) respectively by adopting a reversed-phase high performance liquid chromatograph with a Zorbax Eclipse Plus C18 chromatographic column;
(4) and (4) calculating the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected according to the detection result obtained in the step (3), and further calculating the corresponding contents in the soil.
The reversed-phase high performance liquid chromatography method adopts a mobile phase consisting of acetonitrile and phosphoric acid solution according to the volume ratio of 2:98, adopts a Zorbax Eclipse Plus C18 chromatographic column, can effectively separate chloroacetic acid, dichloroacetic acid and trichloroacetic acid through synergistic action, further can obtain corresponding content in soil according to a detection result, and has the advantages of high sensitivity, low detection limit, accuracy and high efficiency.
As a preferred technical scheme of the invention, the mobile phase in the step (1) needs to be filtered by a 0.45 μm organic phase filter membrane and subjected to ultrasonic treatment for at least 20min, such as 20min, 22min, 25min, 27min, 30min, 32min, 35min and the like, but the mobile phase is not limited to the numerical values listed, and other non-listed numerical values in the numerical value range are also applicable.
The filtration of the 0.45 mu m organic phase filter membrane and the ultrasonic treatment for at least 20min can ensure that the mobile phase is uniformly mixed without insoluble substances and impurities, and can effectively drive away bubbles in water.
As a preferred technical scheme of the invention, the standard solution in the step (1) is prepared by taking the mobile phase as a solvent.
The standard solution is prepared by adopting a mobile phase, so that the interference of liquid of a non-mobile phase on a measurement process can be avoided, and the influence of a solvent effect on detection is avoided.
Preferably, the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the standard solution of step (1) are each in the range of 1.0-20.0. mu.g/mL, such as 1.0. mu.g/mL, 3.0. mu.g/mL, 5.0. mu.g/mL, 7.5. mu.g/mL, 10.0. mu.g/mL, 12.5. mu.g/mL, 15.0. mu.g/mL, 17.0. mu.g/mL or 20.0. mu.g/mL, but are not limited to the values listed, and other values not listed in this range of values are equally applicable.
The method can simultaneously determine the contents of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the soil, so that the prepared standard solution simultaneously contains three substances of chloroacetic acid, dichloroacetic acid and trichloroacetic acid.
Preferably, the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the standard solution of step (1) are the same, e.g., 10.0. mu.g/mL.
In a preferred embodiment of the present invention, the ratio of the weight of the soil sample to the volume of the mobile phase in step (2) is 1:1 to 1:3, wherein the weight is g and the volume is mL, such as 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferable technical scheme of the invention, the soil sample in the step (2) needs to be subjected to ultrasonic treatment twice after being added into the mobile phase, each ultrasonic treatment lasts for at least 15min, and the soil sample is kept stand for 20-40min after each ultrasonic treatment.
The ultrasonic treatment according to the present invention is performed for at least 15min, such as 15min, 17min, 20min, 22min, 25min, 28min, 30min, 35min or 40min, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
The ultrasonic treatment is performed for 20-40min, such as 20min, 25min, 30min, 35min or 40min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferable technical scheme of the invention, if suspended matters exist in the supernatant after the standing in the step (2), the centrifugation operation is required.
Preferably, the centrifugation is carried out at a speed of 3000-4500r/min, such as 3000r/min, 3200r/min, 3400r/min, 3500r/min, 3700r/min, 3900r/min, 4000r/min, 4200r/min or 4500r/min, but not limited to the values listed, and other values not listed in the numerical range are equally suitable.
Preferably, the centrifugation is carried out for a period of time of 2 to 10min, for example 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the supernatant after centrifugation is filtered through a 0.22 μm aqueous phase filter.
Preferably, the filtered supernatant is diluted according to actual conditions, so that the concentration of chloroacetic acids to be measured is within the range of a standard curve, and the measurement accuracy is higher.
As a preferred technical scheme of the invention, the Zorbax Eclipse Plus C18 chromatographic column in the step (3) has the size of 4.6X 250mm and 5.0 μm.
In a preferred embodiment of the present invention, the reversed-phase hplc in step (3) performs detection under the following conditions: the column temperature is 40 ℃, the sample injection volume is 20.0 mu L, and the flow rate of the mobile phase is 1.0 mL/min; the detector is a diode array detector with a 3D acquisition function, the acquisition wavelength is 214nm, the scanning range is 200-400nm, the acquisition frequency is 5Hz, and the acquisition time is 20 min.
As a preferable technical scheme of the invention, the concentration of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected is calculated in the step (4) by adopting an external standard method, and then the corresponding content in the soil is calculated.
The external standard method of the invention draws a standard curve by using the peak area detected by a reversed-phase high performance liquid chromatograph and the corresponding concentration of a standard solution, and then calculates the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in a sample solution to be detected through the standard curve, thereby calculating the corresponding content in soil.
As a preferred embodiment of the present invention, the measurement method comprises the steps of:
(1) preparing a mobile phase and a standard solution containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid, wherein the mobile phase consists of acetonitrile and a phosphoric acid solution according to a volume ratio of 2:98, and the volume fraction of the phosphoric acid solution is 0.1%;
wherein the mobile phase needs to be filtered by a 0.45 mu m organic phase filter membrane and subjected to ultrasonic treatment for at least 20 min;
the standard solution is prepared by taking the mobile phase as a solvent, wherein the concentration ranges of chloroacetic acid, dichloroacetic acid and trichloroacetic acid are all 1.0-20.0 mu g/mL;
(2) adding a soil sample into the mobile phase obtained in the step (1) to extract a sample solution to be detected;
wherein the ratio of the weight of the soil sample to the volume of the mobile phase is 1:1-1:3, wherein the weight unit is g, and the volume unit is mL;
after the soil sample is added into the mobile phase, carrying out ultrasonic treatment twice, wherein each ultrasonic treatment is at least 15min, and standing for 20-40min after each ultrasonic treatment;
(3) detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) respectively by adopting a reversed-phase high performance liquid chromatograph with a Zorbax Eclipse Plus C18 chromatographic column;
wherein the Zorbax Eclipse Plus C18 chromatography column has a size of 4.6X 250mm, 5.0 μm;
(4) and (4) calculating the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected by adopting an external standard method according to the detection result obtained in the step (3), and further calculating the corresponding content in the soil.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the determination method can simultaneously determine the contents of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the soil, has the advantages of simple sample processing method, convenient operation in the detection process, high sensitivity, low detection limit, accuracy and high efficiency;
(2) the determination method of the invention develops a pretreatment method of the soil sample, and carries out sample labeling comparison, thereby proving the feasibility of the determination method, the detection limits of chloroacetic acid, dichloroacetic acid and trichloroacetic acid are in the range of 0.13-0.25mg/Kg, the determination lower limit is 0.50-1.02mg/Kg, and the requirement of soil detection is met;
(3) the measuring method optimizes the parameters of the detector, so that the detection sensitivity reaches 0.5 mg/Kg;
(4) the determination method provided by the invention adopts the mobile phase to extract chloroacetic acid substances in the soil sample, so that the use of a pH regulator is omitted, and the interference of other solvents to the measurement process is avoided.
Drawings
FIG. 1 is a chromatogram of a standard solution of chloroacetic acid, dichloroacetic acid, trichloroacetic acid (for example, 10.0. mu.g/mL) in example 1 of the present invention;
FIG. 2 is a standard curve for chloroacetic acid in example 1 of the present invention;
FIG. 3 is a standard curve of dichloroacetic acid in example 1 of the present invention;
FIG. 4 is a standard curve for trichloroacetic acid in example 1 of the present invention;
FIG. 5 is a chromatogram of a sample solution to be tested in example 1 of the present invention;
FIG. 6 is a chromatogram of a sample solution to be tested in example 2 of the present invention;
FIG. 7 is a chromatogram of a sample solution to be tested in example 3 of the present invention;
FIG. 8 is a chromatogram of a standard solution in comparative example 1 of the present invention (taking 10.0. mu.g/mL as an example);
FIG. 9 is a chromatogram of a standard solution in comparative example 2 of the present invention (taking 10.0. mu.g/mL as an example);
FIG. 10 is a chromatogram of a standard solution in comparative example 3 of the present invention (taking 10.0. mu.g/mL as an example).
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, wherein a soil sample is derived from B, C plot soil in Suning electric business industrial park of Shanghai, the point position number is GW18-2, the dry matter content is 80.0%, and the method specifically comprises the following steps:
(1) taking a phosphoric acid solution with the volume fraction of 0.1%, offline mixing acetonitrile and the phosphoric acid solution according to the volume ratio of 2:98, filtering the mixed solution through a 0.45-micrometer organic phase filter membrane and carrying out ultrasonic treatment for 20min to obtain a mobile phase; respectively preparing a series of standard solutions with different concentrations and containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid by using the mobile phase, wherein the concentrations of the chloroacetic acid, the dichloroacetic acid and the trichloroacetic acid in each standard solution are the same, and totally preparing five standard solutions of which the concentrations are 1.0 mu g/mL, 2.0 mu g/mL, 5.0 mu g/mL, 10.0 mu g/mL and 20.0 mu g/mL;
(2) accurately weighing 10.0g of soil sample, placing the soil sample in a 40mL brown glass bottle, adding 10mL of the mobile phase obtained in the step (1), placing the glass bottle added with the mobile phase in an ultrasonic cleaning machine for ultrasonic treatment twice, performing ultrasonic treatment for 15min each time, and standing for 30min after each ultrasonic treatment; visually finding suspended matters in the supernatant after standing, placing the supernatant in a centrifugal tube, centrifuging for 5min at the rotating speed of 4000r/min, collecting the centrifuged supernatant, filtering the centrifuged supernatant by a 0.22-micron water-phase filter membrane, and diluting by 10 times to obtain a sample solution to be detected; adding 1mL of the sample solution to be detected into a clean sample introduction bottle for sample introduction;
(3) detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) respectively by adopting a reversed-phase high performance liquid chromatograph with a Zorbax Eclipse Plus C18 chromatographic column;
wherein the Zorbax Eclipse Plus C18 chromatography column has a size of 4.6X 250mm, 5.0 μm;
the reversed-phase high performance liquid chromatograph performs detection according to the following conditions: the column temperature is 40 ℃, the sample injection volume is 20.0 mu L, and the flow rate of the mobile phase is 1.0 mL/min; the detector is a diode array detector with a 3D acquisition function, the acquisition wavelength is 214nm, the scanning range is 200-400nm, the acquisition frequency is 5Hz, and the acquisition time is 20 min;
(4) detecting a series of chloroacetic acid, dichloroacetic acid and trichloroacetic acid according to the step (3)The peak area of the standard solution is an ordinate Y axis, the concentrations of the standard solutions of chloroacetic acid, dichloroacetic acid and trichloroacetic acid are abscissa X axes, a standard curve is drawn, the slope and the intercept are calculated, and the linear regression equations are obtained as follows: y isChloroacetic acid0.0109X +0.0005 where R2＝0.9998；YDichloroacetic acid0.049X-0.0039, wherein R2＝0.9999；YTrichloroacetic acid0.0732X-0.0089, wherein R21.0000; the linear regression equation shows that the detected peak area has a good linear relation with the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid;
fig. 5 is a chromatogram of the sample solution to be detected obtained in this embodiment, which can obtain that the concentration of chloroacetic acid in the sample solution to be detected is 2.89mg/L, the concentration of dichloroacetic acid is 41.7mg/L, and the concentration of trichloroacetic acid is 0.00mg/L, and further calculate that the content of chloroacetic acid in soil is 36.1mg/Kg, the content of dichloroacetic acid is 521mg/Kg, and the soil sample does not contain trichloroacetic acid.
In order to further judge the sensitivity of the determination method, known amounts of chloroacetic acid, dichloroacetic acid and trichloroacetic acid are respectively added into a blank soil sample to obtain a standard soil sample with the standard concentration of 1.0 mg/Kg. And (3) carrying out sample treatment operation and detection analysis operation on the standard soil sample according to the embodiment 1, carrying out the operation for seven times, and then respectively substituting the peak areas of the three measured standard curves into the respective standard curves to obtain the experimental contents of the three in the standard soil sample. By comparing the known standard concentration and the experimental content, the detection limit of chloroacetic acid, dichloroacetic acid and trichloroacetic acid is found to be in the range of 0.13-0.25mg/Kg, and the lower detection limit is 0.50-1.02mg/Kg, so that the requirement of soil detection is met. The data relating to the sample spiking comparison is shown in table 1.
TABLE 1
Example 2
A method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil, wherein a soil sample is from B, C plot soil in Suning electric business industrial park of Shanghai city, the point number is SS53-5, the dry matter content is 74.5%, and the method specifically comprises the following steps:
(1) taking a phosphoric acid solution with the volume fraction of 0.1%, offline mixing acetonitrile and the phosphoric acid solution according to the volume ratio of 2:98, filtering the mixed solution through a 0.45-micrometer organic phase filter membrane and carrying out ultrasonic treatment for 30min to obtain a mobile phase; respectively preparing a series of standard solutions with different concentrations and containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid by using the mobile phase, wherein the concentrations of the chloroacetic acid, the dichloroacetic acid and the trichloroacetic acid in each standard solution are the same, and totally preparing five standard solutions of which the concentrations are 1.0 mu g/mL, 2.0 mu g/mL, 5.0 mu g/mL, 10.0 mu g/mL and 20.0 mu g/mL;
(2) accurately weighing 10.0g of soil sample, placing the soil sample in a 40mL brown glass bottle, adding 20mL of the mobile phase obtained in the step (1), placing the glass bottle added with the mobile phase in an ultrasonic cleaning machine for ultrasonic treatment twice, performing ultrasonic treatment for 20min each time, and standing for 40min after each ultrasonic treatment; visually finding suspended matters in the supernatant after standing, placing the supernatant in a centrifuge tube, centrifuging for 10min at the rotating speed of 3000r/min, collecting the centrifuged supernatant, filtering the centrifuged supernatant by a 0.22 mu m water-phase filter membrane, and diluting by 100 times to obtain a sample solution to be detected; adding 1mL of the sample solution to be detected into a clean sample introduction bottle for sample introduction;
steps (3) and (4) were the same as in example 1.
Fig. 6 is a chromatogram of the sample solution to be detected obtained in this embodiment, which can obtain that the concentration of chloroacetic acid in the sample solution to be detected is 0.00mg/L, the concentration of dichloroacetic acid is 5.30mg/L, and the concentration of trichloroacetic acid is 0.00mg/L, and further calculate that the content of dichloroacetic acid in soil is 711mg/Kg, and the soil sample does not contain chloroacetic acid and trichloroacetic acid.
Example 3
A method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil is provided, a soil sample is from a retired site of a Hangzhou Hongbo new material limited company, the point number is S63.0-4.0 m, and the dry matter content is 74.6%, and the method specifically comprises the following steps:
(1) taking a phosphoric acid solution with the volume fraction of 0.1%, offline mixing acetonitrile and the phosphoric acid solution according to the volume ratio of 2:98, filtering the mixed solution through a 0.45-micrometer organic phase filter membrane and carrying out ultrasonic treatment for 30min to obtain a mobile phase; respectively preparing a series of standard solutions with different concentrations and containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid by using the mobile phase, wherein the concentrations of the chloroacetic acid, the dichloroacetic acid and the trichloroacetic acid in each standard solution are the same, and totally preparing five standard solutions of which the concentrations are 1.0 mu g/mL, 2.0 mu g/mL, 5.0 mu g/mL, 10.0 mu g/mL and 20.0 mu g/mL;
(2) accurately weighing 10.0g of soil sample, placing the soil sample in a 40mL brown glass bottle, adding 30mL of the mobile phase obtained in the step (1), placing the glass bottle added with the mobile phase in an ultrasonic cleaning machine for ultrasonic treatment twice, performing ultrasonic treatment for 20min each time, and standing for 30min after each ultrasonic treatment; visually finding suspended matters in the supernatant after standing, placing the supernatant in a centrifuge tube, centrifuging for 2min at the rotating speed of 4500r/min, collecting the centrifuged supernatant, and filtering by using a 0.22-micron water-phase filter membrane to obtain a sample solution to be detected; adding 1mL of the sample solution to be detected into a clean sample introduction bottle for sample introduction;
steps (3) and (4) were the same as in example 1.
Fig. 7 is a chromatogram of the sample solution to be detected obtained in this embodiment, which can obtain that the concentration of chloroacetic acid in the sample solution to be detected is 3.05mg/L, the concentration of dichloroacetic acid is 0.00mg/L, and the concentration of trichloroacetic acid is 0.00mg/L, and further calculate that the content of chloroacetic acid in soil is 4.1mg/Kg, and the soil sample does not contain dichloroacetic acid and trichloroacetic acid.
Comparative example 1
This comparative example was conducted in such a manner that a mobile phase was prepared at a volume ratio of acetonitrile to phosphoric acid solution of 10:90, and then a standard solution having chloroacetic acid, dichloroacetic acid and trichloroacetic acid concentrations of 10.0. mu.g/mL was measured using this mobile phase, and the same was applied to the other points as in example 1.
As can be seen from fig. 8, the sample peaks of chloroacetic acid and dichloroacetic acid cannot be separated, and the accurate concentrations of chloroacetic acid and dichloroacetic acid in the sample solution to be measured cannot be obtained.
Comparative example 2
This comparative example was a mobile phase prepared by mixing acetonitrile and phosphoric acid at a volume ratio of 5:95, and then a standard solution having chloroacetic acid, dichloroacetic acid and trichloroacetic acid concentrations of 10.0. mu.g/mL was measured using the mobile phase, and the same was applied to the other points as in example 1.
As can be seen from fig. 9, the separation degrees of the sample peaks of chloroacetic acid and dichloroacetic acid are not good enough, and the accurate concentrations of chloroacetic acid and dichloroacetic acid in the sample solution to be measured cannot be obtained.
Comparative example 3
This comparative example was conducted by replacing acetonitrile in the mobile phase with methanol, and measuring a standard solution of chloroacetic acid, dichloroacetic acid and trichloroacetic acid each having a concentration of 10.0. mu.g/mL in the mobile phase, which was otherwise identical to that of example 1.
As can be seen from fig. 10, the sample peaks of chloroacetic acid and dichloroacetic acid cannot be separated, and the accurate concentrations of chloroacetic acid and dichloroacetic acid in the sample solution to be measured cannot be obtained.
As can be seen from the above examples and comparative examples, the measurement method of the present invention employs a mobile phase composed of acetonitrile and phosphoric acid solution in a volume ratio of 2:98, the volume fraction of the phosphoric acid solution is 0.1%, and employs a Zorbax eclipse plus C18 chromatographic column, through the synergistic effect of the two, chloroacetic acid, dichloroacetic acid and trichloroacetic acid can be effectively separated, and then the corresponding content in soil can be obtained according to the detection result; however, changing the volume ratio of the mobile phase and using other organic solvents to prepare the mobile phase all result in partial coincidence of sample peaks of chloroacetic acid and dichloroacetic acid or insufficient separation degree, and the accurate concentrations of chloroacetic acid and dichloroacetic acid in the sample solution to be detected cannot be obtained, and further the accurate contents of both in the soil cannot be obtained.
The measuring method of the invention not only has simple sample processing method and convenient operation in the detection process, but also has the advantages of high sensitivity, low detection limit, accuracy and high efficiency, and the detection limit of chloroacetic acid, dichloroacetic acid and trichloroacetic acid is in the range of 0.13-0.25mg/Kg, the lower limit of measurement is 0.50-1.02mg/Kg, thus meeting the requirement of soil detection.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil is characterized by comprising the following steps:
(1) preparing a mobile phase and a standard solution containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid, wherein the mobile phase consists of acetonitrile and a phosphoric acid solution according to a volume ratio of 2:98, and the volume fraction of the phosphoric acid solution is 0.1%;
(2) adding a soil sample into the mobile phase obtained in the step (1) to extract a sample solution to be detected;
(3) detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) respectively by adopting a reversed-phase high performance liquid chromatograph with a Zorbax Eclipse Plus C18 chromatographic column;
(4) and (4) calculating the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected according to the detection result obtained in the step (3), and further calculating the corresponding contents in the soil.
2. The assay method according to claim 1, wherein the mobile phase of step (1) is subjected to filtration through a 0.45 μm organic phase filter and sonication for at least 20 min.
3. The assay method according to claim 1 or 2, wherein the standard solution of step (1) is formulated with the mobile phase as a solvent;
preferably, the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the standard solution in the step (1) are all in the range of 1.0-20.0. mu.g/mL.
4. The assay of any one of claims 1 to 3, wherein the ratio of the weight of the soil sample to the volume of the mobile phase in step (2) is from 1:1 to 1:3, wherein the units of weight are g and the units of volume are mL.
5. The assay of any one of claims 1 to 4, wherein the soil sample is subjected to two sonications after the addition of the mobile phase in step (2), each sonication for at least 15min and each sonication followed by a rest period of 20-40 min.
6. The method according to claim 5, wherein if suspended matter is present in the supernatant after the standing in the step (2), a centrifugation operation is required;
preferably, the rotating speed of the centrifugal operation is 3000-4500 r/min;
preferably, the time of the centrifugal operation is 2-10 min;
preferably, the supernatant after centrifugation is filtered through a 0.22 μm aqueous phase filter.
7. The assay of any one of claims 1 to 6, wherein the Zorbax eclipse Plus C18 chromatography column of step (3) has a size of 4.6 x 250mm, 5.0 μm.
8. The method according to any one of claims 1 to 7, wherein the reversed-phase high performance liquid chromatograph of step (3) performs detection under the following conditions: the column temperature is 40 ℃, the sample injection volume is 20.0 mu L, and the flow rate of the mobile phase is 1.0 mL/min; the detector is a diode array detector with a 3D acquisition function, the acquisition wavelength is 214nm, the scanning range is 200-400nm, the acquisition frequency is 5Hz, and the acquisition time is 20 min.
9. The determination method according to any one of claims 1 to 8, wherein in the step (4), the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be determined are calculated by an external standard method, and then the corresponding contents in the soil are calculated.
10. The assay according to any one of claims 1 to 9, characterized in that it comprises the steps of:
(1) preparing a mobile phase and a standard solution containing chloroacetic acid, dichloroacetic acid and trichloroacetic acid, wherein the mobile phase consists of acetonitrile and a phosphoric acid solution according to a volume ratio of 2:98, and the volume fraction of the phosphoric acid solution is 0.1%;
wherein the mobile phase needs to be filtered by a 0.45 mu m organic phase filter membrane and subjected to ultrasonic treatment for at least 20 min;
the standard solution is prepared by taking the mobile phase as a solvent, wherein the concentration ranges of chloroacetic acid, dichloroacetic acid and trichloroacetic acid are all 1.0-20.0 mu g/mL;
(2) adding a soil sample into the mobile phase obtained in the step (1) to extract a sample solution to be detected;
wherein the ratio of the weight of the soil sample to the volume of the mobile phase is 1:1-1:3, wherein the weight unit is g, and the volume unit is mL;
after the soil sample is added into the mobile phase, carrying out ultrasonic treatment twice, wherein each ultrasonic treatment is at least 15min, and standing for 20-40min after each ultrasonic treatment;
(3) detecting and analyzing the standard solution in the step (1) and the sample solution to be detected in the step (2) respectively by adopting a reversed-phase high performance liquid chromatograph with a Zorbax Eclipse Plus C18 chromatographic column;
wherein the Zorbax Eclipse Plus C18 chromatography column has a size of 4.6X 250mm, 5.0 μm;
(4) and (4) calculating the concentrations of chloroacetic acid, dichloroacetic acid and trichloroacetic acid in the sample solution to be detected by adopting an external standard method according to the detection result obtained in the step (3), and further calculating the corresponding content in the soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010021042.9A CN111103387A (en) | 2020-01-09 | 2020-01-09 | Method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010021042.9A CN111103387A (en) | 2020-01-09 | 2020-01-09 | Method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111103387A true CN111103387A (en) | 2020-05-05 |
Family
ID=70425886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010021042.9A Pending CN111103387A (en) | 2020-01-09 | 2020-01-09 | Method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111103387A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112014510A (en) * | 2020-09-07 | 2020-12-01 | 瀚盟测试科技（天津）有限公司 | Detection method for determining chloroacetic acid residue in cinepazide maleate intermediate by HPLC (high performance liquid chromatography) method |
| CN113109462A (en) * | 2021-03-10 | 2021-07-13 | 南京海纳医药科技股份有限公司 | Method for detecting chloroacetic acid in lidocaine |
| CN114002335A (en) * | 2020-07-28 | 2022-02-01 | 武汉武药制药有限公司 | Method for analyzing and detecting methyl dichloroacetate and related substances thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102520083A (en) * | 2011-12-05 | 2012-06-27 | 西安建筑科技大学 | Method for quickly detecting haloacetic acids serving as disinfection byproducts in drinking water |
| CN204255918U (en) * | 2011-05-18 | 2015-04-08 | 博尔特有限公司 | For determining the equipment of the concentration of the halogenated acetic acids in aqueous solution |
| CN108828081A (en) * | 2018-04-17 | 2018-11-16 | 南京大学 | Analysis method that is a kind of while detecting nine kinds of halogen acetic acids and three kinds of oxyhalides in water |
| CN109991358A (en) * | 2019-04-09 | 2019-07-09 | 上海实朴检测技术服务有限公司 | Measure chloroacetic method in soil |
-
2020
- 2020-01-09 CN CN202010021042.9A patent/CN111103387A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204255918U (en) * | 2011-05-18 | 2015-04-08 | 博尔特有限公司 | For determining the equipment of the concentration of the halogenated acetic acids in aqueous solution |
| CN102520083A (en) * | 2011-12-05 | 2012-06-27 | 西安建筑科技大学 | Method for quickly detecting haloacetic acids serving as disinfection byproducts in drinking water |
| CN108828081A (en) * | 2018-04-17 | 2018-11-16 | 南京大学 | Analysis method that is a kind of while detecting nine kinds of halogen acetic acids and three kinds of oxyhalides in water |
| CN109991358A (en) * | 2019-04-09 | 2019-07-09 | 上海实朴检测技术服务有限公司 | Measure chloroacetic method in soil |
Non-Patent Citations (9)
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114002335A (en) * | 2020-07-28 | 2022-02-01 | 武汉武药制药有限公司 | Method for analyzing and detecting methyl dichloroacetate and related substances thereof |
| CN114002335B (en) * | 2020-07-28 | 2023-11-14 | 武汉武药制药有限公司 | Method for analyzing and detecting methyl dichloroacetate and related substances thereof |
| CN112014510A (en) * | 2020-09-07 | 2020-12-01 | 瀚盟测试科技（天津）有限公司 | Detection method for determining chloroacetic acid residue in cinepazide maleate intermediate by HPLC (high performance liquid chromatography) method |
| CN112014510B (en) * | 2020-09-07 | 2022-07-05 | 瀚盟测试科技（天津）有限公司 | Detection method for determining chloroacetic acid residue in cinepazide maleate intermediate by HPLC (high performance liquid chromatography) method |
| CN113109462A (en) * | 2021-03-10 | 2021-07-13 | 南京海纳医药科技股份有限公司 | Method for detecting chloroacetic acid in lidocaine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111103387A (en) | Method for measuring chloroacetic acid, dichloroacetic acid and trichloroacetic acid in soil | |
| CN106124678B (en) | The quick screening method of perfluorochemical and its precursor substance in the flesh of fish | |
| CN111562327A (en) | Molecular network-based non-target screening and analyzing method for toxic organic pollutants in wastewater | |
| CN103592399A (en) | Method capable of simultaneously measuring organochlorine pesticide concentration and synthetic musk concentration in human serum | |
| CN111307966A (en) | HPLC (high Performance liquid chromatography) determination method for triterpenoid components in ganoderma lucidum spore powder and product thereof | |
| CN102928528A (en) | High performance liquid chromatography mass spectrometry detecting method of 16 fat soluble saxitoxins in shellfish meet | |
| JP2023501837A (en) | METHOD FOR SIMULTANEOUSLY DETECTING VITAMIN K1 AND VITAMIN K2 IN MINIMUM BLOOD | |
| CN1332199C (en) | GC/MS inner scaling detection method for simultaneous investigating residual multiple organophosphorus in food | |
| CN112362772A (en) | Method for detecting residual organic solvent in soil | |
| CN109991358A (en) | Measure chloroacetic method in soil | |
| CN113791146B (en) | Method for detecting organic phosphate pollutants in food and sample treatment method thereof | |
| CN103226138A (en) | Method for fast detecting phenoxy carboxylic acid herbicide in water | |
| CN103115994A (en) | Method for rapidly measuring Cr(III) and Cr(VI) ion in tipping paper for cigarette | |
| CN107422053B (en) | Method for detecting trichloroacetic acid in cosmetics by liquid chromatography-mass spectrometry | |
| CN108760920A (en) | A method of cyazofamid and its metabolite residue amount are measured based on HPLC-MSMS methods | |
| CN105388243A (en) | Method for measuring hexamidine, chlorhexidine, and salts thereof in cosmetics | |
| CN110887911B (en) | Gas chromatography-tandem mass spectrometry detection method for clotrimazole residues in animal-derived food | |
| CN101865887A (en) | Method for detecting nitromidazole residue in royal jelly by using high performance liquid chromatography tandem mass spectrum | |
| CN105158372A (en) | Method for determining urocanic acid and ethyl ester thereof in cosmetics | |
| CN110045043A (en) | Method for determining content of 4-nonyl phenol and/or 4-nonyl phenol ethoxy compound | |
| CN105203694A (en) | Method for measuring 3, 4-benzopyrene in edible oil | |
| CN104215614A (en) | Method for detecting aloin A, aloin B and aloe-emodin in series through high performance liquid chromatography-diode array/fluorescent detector | |
| CN1261749C (en) | Method for rapidly and quantitatively determining the triterpenoid content in ganoderma lucidum | |
| CN103235052A (en) | Determination method for 2,4-dinitrophenol in dry food packaging paper | |
| CN114609295A (en) | High performance liquid chromatography analysis method for quinic acid content in tala enzymolysis waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200505 |