CN112946119A - Method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample - Google Patents
Method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample Download PDFInfo
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- 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
-
- 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
- G01N30/06—Preparation
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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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- G01N30/62—Detectors specially adapted therefor
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Abstract
本发明涉及农药检测技术领域，具体为一种环境水样中11种苯氧羧酸类除草剂的分析检测方法，包括：利用分散膜固相萃取法对水样进行前处理，结合超高效液相色谱‑串联质谱对水样中11种苯氧羧酸类除草剂进行分析检测；分散膜固相萃取法中的膜固相萃取材料为阳离子型金属有机骨架材料MIL‑101‑NMe3 +MMM。利用分散膜固相萃取(DME)技术，采用阳离子型金属有机骨架膜材料MIL‑101‑NMe3 +MMM固相萃取，结合超高效液相色谱‑串联质谱法来测定环境水样中11种苯氧羧酸类除草剂，能够实现对水样中11种苯氧羧酸类除草剂的快速富集，萃取剂用量低、毒性低、反应条件简单、设备成本低，建立了一种简单、快速、准确、灵敏度的检测方法。
The invention relates to the technical field of pesticide detection, in particular to a method for analyzing and detecting 11 kinds of phenoxycarboxylic acid herbicides in environmental water samples. Analysis and detection of 11 phenoxycarboxylic acid herbicides in water samples by phase chromatography-tandem mass spectrometry; the membrane solid phase extraction material in the dispersive membrane solid phase extraction method is a cationic metal organic framework material MIL-101-NMe 3 + MMM . Using dispersive membrane solid phase extraction (DME) technology, using cationic metal organic framework membrane material MIL-101-NMe 3 + MMM solid phase extraction, combined with ultra-high performance liquid chromatography-tandem mass spectrometry to determine 11 kinds of benzene in environmental water samples Oxycarboxylic acid herbicides can achieve rapid enrichment of 11 phenoxycarboxylic acid herbicides in water samples, with low extraction agent dosage, low toxicity, simple reaction conditions and low equipment cost. , Accurate and sensitive detection method.
Description
Technical Field
The invention relates to the technical field of pesticide detection, in particular to an analysis and detection method for 11 phenoxy carboxylic acid herbicides in an environmental water sample.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Herbicides play an important role in controlling the growth of weeds and are thus widely used in agriculture and forestry. The phenoxy carboxylic acid herbicides are the first class of herbicides which are put into commercial production, have long use history and second highest use amount, and are used for preventing and removing broadleaf weeds in wheat, corn and paddy fields due to the advantages of low price, quick response, wide weeding spectrum and the like. However, phenoxy carboxylic acid herbicides have potential mutagenicity, can interfere endocrine systems, and harm liver and brain tissues of animals, and metabolites of phenoxy carboxylic acid herbicides can cause great harm to human bodies, and can seriously cause liver damage and nervous lesion of human bodies. Phenoxy carboxylic acid herbicides are very soluble in water and thus migrate in the farmland ecosystem, causing pollution of soil, groundwater and the like.
The phenoxy carboxylic acid herbicide has low content in water, and can be accurately determined only after being subjected to pretreatment, enrichment and concentration on a water sample. The prior pretreatment method for the phenoxy carboxylic acid herbicide in water mainly comprises liquid-liquid extraction, dispersion liquid-liquid microextraction, solid-phase extraction, solid-phase microextraction and the like. Liquid-liquid extraction generally consumes a large amount of solvent, and the use of more solid-phase extraction techniques has the problem that the column is easily clogged. Common separation and detection methods for phenoxy carboxylic acid herbicides in water include liquid chromatography, liquid chromatography-mass spectrometry, gas chromatography and gas chromatography-mass spectrometry. Gas chromatography is the earliest analytical method used to determine the residual amount of phenoxy carboxylic herbicides in water, but derivatization is usually required; and the high performance liquid chromatography and the liquid chromatography-mass spectrometry method do not need derivatization. At present, liquid chromatography or a liquid chromatography-mass spectrometry combined method is adopted to measure phenoxy carboxylic acid herbicides in water, for example, a patent with the application number of 201310026727.2 discloses a method for rapidly detecting 8 phenoxy carboxylic acid herbicides in water, the method adopts solid phase extraction combined with ultra-high performance liquid chromatography-tandem mass spectrometry detection, the detection limit is low, but the extraction process is complex, and the dosage of an extracting agent is large.
Disclosure of Invention
In order to solve the problems in the prior art, the disclosure provides an analytical detection method for 11 phenoxy carboxylic acid herbicides in an environmental water sample, which utilizes a dispersion film solid phase extraction (DME) technology and adopts a cationic metal organic framework film material MIL-101-NMe3 +The MMM solid-phase extraction is combined with the ultra-high performance liquid chromatography-tandem mass spectrometry to determine 11 phenoxy carboxylic acid herbicides in an environmental water sample, the rapid enrichment of the 11 phenoxy carboxylic acid herbicides in the water sample can be realized, the dosage of the extractant is low, the toxicity is low, the reaction condition is simple, the equipment cost is low, and a simple, rapid, accurate and sensitive detection method is established.
Specifically, the technical scheme of the present disclosure is as follows:
in a first aspect of the present disclosure, there is provided a method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in an environmental water sample, comprising: pretreating a water sample by using a dispersion film solid phase extraction method, and analyzing and detecting the 11 phenoxy carboxylic acid herbicides in the water sample by combining ultra-high performance liquid chromatography-tandem mass spectrometry; the membrane solid phase extraction material in the dispersion membrane solid phase extraction method is a cationic metal organic framework material MIL-101-NMe3 +MMM。
In a second aspect of the disclosure, an application of an analytical detection method for 11 phenoxy carboxylic acid herbicides in an environmental water sample in pesticide detection is provided.
One or more technical schemes in the disclosure have the following beneficial effects:
(1) adopting cationic metal organic framework membrane material MIL-101-NMe3 +MMM has better adsorption efficiency on 11 phenoxy carboxylic acid herbicides; adopting cationic metal organic framework membrane material MIL-101-NMe3 +MMM is used as a membrane solid phase extraction material, and the ultra-high performance liquid chromatography-tandem mass spectrometry method is adopted for detection, so that the analysis of 11 phenoxy carboxylic acid herbicides in a water sample is establishedThe method is simple and convenient to operate, greatly saves the analysis time and cost, and has good extraction effect, accurate analysis result and good reproducibility; meanwhile, the raw materials used in the invention are cheap and easily available, the preparation process of the materials is simple, the reaction conditions are mild, the application environment is friendly, and the market prospect is wide.
(2) In the specific implementation mode, cationic metal organic framework membrane material MIL-101-NMe is adopted3 +MMM is used as an extractant, and the optimal dosage of the MOF in the extractant is only 40mg, which is lower than that of the extractant in the prior art.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
Embodiments of the present disclosure are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows MIL-101-NMe according to example 13 +Infrared spectrum of MMM (a. PVDF film, b. MIL-101-NH)2Film, c.MIL-101-NMe3 +MMM)。
FIG. 2 is a total ion flow chromatogram of ultra-high performance liquid chromatography-triple quadrupole mass spectrometry of 11 phenoxy carboxylic acid herbicides mixed standard substances according to example 1.
FIG. 3 is a graph showing the effect of the amount of MOF used in example 2 on the extraction efficiency of 11 phenoxy carboxylic acid herbicides.
FIG. 4 is a graph showing the effect of pH on the extraction efficiency of 11 phenoxy carboxylic acid herbicides on water samples in example 2.
FIG. 5 is a graph showing the effect of the extraction time on the extraction efficiency of 11 phenoxy carboxylic acid herbicides in example 2.
FIG. 6 is a graph showing the effect of salinity on the extraction efficiency of 11 phenoxy carboxylic acid herbicides in example 2.
FIG. 7 is a graph showing the effect of the kind of eluent on the extraction efficiency of 11 phenoxy carboxylic acid herbicides in example 2.
FIG. 8 is a graph showing the effect of the amount of eluent used in example 2 on the extraction efficiency of 11 phenoxy carboxylic acid herbicides.
FIG. 9 is a graph showing the effect of elution time on the extraction efficiency of 11 phenoxy carboxylic acid herbicides in example 2.
Detailed Description
The disclosure is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the existing method for determining phenoxy carboxylic acid herbicides in water has the technical problems of complex extraction process, large using amount of an extractant, high toxicity, slow detection, and insufficient accuracy and sensitivity, and the invention provides an analysis and detection method for 11 phenoxy carboxylic acid herbicides in an environmental water sample to solve the problems.
In one embodiment of the present disclosure, a method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in an environmental water sample is provided, which includes: using dispersionThe membrane solid phase extraction method is used for pretreating a water sample, and the ultra-high performance liquid chromatography-tandem mass spectrometry is used for analyzing and detecting the 11 phenoxy carboxylic acid herbicides in the water sample; the membrane solid phase extraction material in the dispersion membrane solid phase extraction method is a cationic metal organic framework material MIL-101-NMe3 +MMM。
Further, the 11 phenoxy carboxylic acid herbicides are 2, 4-dichlorophenoxyacetic acid, 2- (2, 4-dichlorophenoxy) -propionic acid, 4- (2, 4-chlorophenoxy) -butyric acid, 2-methyl-4-chlorophenoxy acetic acid, 2- (2-methyl-4-chlorophenoxy) propionic acid, 2,4, 5-trichlorophenoxy acetic acid, 2- (2,4, 5-trichlorophenoxy) -propionic acid, phenoxyacetic acid, 4-phenoxybutyric acid, 4-chlorophenoxy acetic acid and dicamba.
Further, the cationic metal organic framework material MIL-101-NMe3 +The preparation process of the MMM comprises the following steps:
(1) preparation of MIL-101-NH2: adding 2-amino terephthalic acid, chromium nitrate nonahydrate and sodium hydroxide into ultrapure water, ultrasonically mixing uniformly, transferring the mixture into a solvothermal reaction kettle, and reacting at the temperature of 120-; cooling to room temperature, centrifuging to collect a crude product, then washing with DMF and ethanol, and drying;
(2) preparation of MIL-101-NH2Film formation: mixing MIL-101-NH2Dispersing in acetone, dissolving polyvinylidene fluoride (PVDF) in DMF, adding DMF solution containing PVDF to MIL-101-NH2In the acetone solution, evenly mixing by ultrasonic; then, volatilizing the acetone by adopting a rotary evaporation method for the mixed solution, coating the residual mixed solution on a glass plate, and heating in an oven to volatilize the solvent;
(3) preparation of MIL-101-NMe3 +MMM: the obtained MIL-101-NH2The membrane bubble is put into dichloromethane, methyl trifluoromethanesulfonate is dripped into the dichloromethane and reacts for 8 to 15 hours to obtain MIL-101-NMe3A film; then replacing dichloromethane once every 8-15 hours to remove unreacted methyl trifluoromethanesulfonate; finally, MIL-101-NMe is added3Soaking in hydrochloric acid solution, washing with ultrapure water repeatedly until the pH value of eluate is neutral to obtain cationForm MIL-101-NMe3 +MMM。
Further, the pretreatment process comprises: mixing MIL-101-NMe3 +The MMM is placed in a container, a water sample containing a substance to be detected is added, and the mixture is subjected to constant-temperature oscillation extraction; then, MIL-101-NMe3 +Taking out the MMM membrane, and eluting with ammonia water/methanol solution; the collected eluent is dried by nitrogen at room temperature, redissolved by acetonitrile/water solution, vortexed, mixed and filtered.
Furthermore, in the pretreatment process, MIL-101-NH2The amount of (B) is 5-60mg, preferably 40 mg.
Furthermore, in the pretreatment process, the concentration of the substance to be detected in the water sample is 1-500 ng/L.
Further, the volume of the water sample during the pretreatment is 40-60mL, preferably 50 mL.
Furthermore, in the pretreatment process, the temperature of constant temperature oscillation is kept at 30 ℃, and the extraction time is 10-50min, preferably 30 min.
Furthermore, in the pretreatment process, the ammonia/methanol solution is 1.5% ammonia/methanol solution; alternatively, the ammonia/methanol solution is used in an amount of 1 to 3mL, preferably 2.5 mL.
Furthermore, in the pretreatment process, the elution times are at least two, each elution time is 3-20min, preferably 15 min.
Furthermore, in the pretreatment process, the acetonitrile/water solution is 20% acetonitrile/water solution; alternatively, the amount of acetonitrile/water solution used is 0.3-1mL, preferably 0.5 mL.
The disclosure uses cationic metal organic framework membrane material MIL-101-NMe3 +MMM is used as an adsorbent, and adsorption of anionic phenoxy carboxylic acid is realized mainly through electrostatic interaction between anions and cations. In the pretreatment process, the pH value of a water sample does not need to be adjusted, adsorption and elution can be directly carried out, the MOF membrane is simply and quickly separated from the water sample, auxiliary equipment such as a centrifugal machine is not needed, and the pretreatment time is saved.
Further, in the detection of ultra performance liquid chromatography-tandem mass spectrometry: chromatographic conditions are as follows: the chromatographic column is an ACQUITY UPLC BEH chromatographic column (100 mm. times.2.1 mm. times.1.7 μm); the mobile phase adopts 0.01 percent formic acid water solution (A) and acetonitrile (B); the column temperature is 40 ℃; the flow rate is 0.4 mL/min; the sample injection amount is 5 mu L; the gradient elution procedure was as follows:
further, in the detection of ultra performance liquid chromatography-tandem mass spectrometry: mass spectrum conditions: a negative ion mode; the ESI source parameters are: the power voltage is-4500V, the air curtain pressure is 30psi, the atomization air pressure is 50psi, the auxiliary device pressure is 60psi, and the ionization temperature is 300 ℃; multiple reaction monitoring is adopted, and the specific conditions are as follows:
in one embodiment of the disclosure, an application of an analysis and detection method for 11 phenoxy carboxylic acid herbicides in an environmental water sample in pesticide detection is provided.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1
The method for analyzing and detecting the 11 phenoxy carboxylic acid herbicides in the environmental water sample specifically comprises the following steps:
the method comprises the following steps: preparation of cationic metal organic framework membrane material MIL-101-NMe3 +MMM：
(1) Adding 0.36g of 2-amino terephthalic acid, 0.8g of chromium nitrate nonahydrate and 0.2mg of sodium hydroxide into 15mL of ultrapure water, ultrasonically mixing uniformly, transferring the mixture into a solvothermal reaction kettle, reacting for 12 hours at 150 ℃, cooling to room temperature,centrifuging at 8000 rpm for 10min to collect crude product, washing with DMF and ethanol, and drying in vacuum drying oven for 12 hr to obtain metal organic framework material MIL-101-NH2；
(2) The obtained MIL-101-NH2Ultrasonically dispersed in acetone, 50mg of polyvinylidene fluoride (PVDF) was dissolved in 1mL of DMF, and the DMF solution with PVDF dissolved therein was added to MIL-101-NH2And uniformly mixing the mixture by ultrasonic waves in the acetone solution. Then evaporating the mixed solution by rotary evaporation method to volatilize acetone, coating the rest mixed solution on a glass plate, heating in a 70 deg.C oven to volatilize solvent to obtain MIL-101-NH2Membrane (see fig. 1 b);
(3) the obtained MIL-101-NH2The membrane bubble is put into dichloromethane, methyl trifluoromethanesulfonate is dripped into the dichloromethane and reacts for 12 hours to obtain MIL-101-NMe3And (3) a membrane. The dichloromethane was then replaced every 12 hours to remove unreacted methyl triflate. Finally, MIL-101-NMe is added3Soaking in hydrochloric acid solution for 12 hr, repeatedly washing acidified membrane material with ultrapure water until pH value of eluate reaches neutral to obtain cationic MIL-101-NMe3 +MMM (fig. 1 c).
Step two: the method comprises the following steps of (1) pretreating a water sample by using a dispersion film solid-phase extraction method, and analyzing and detecting 11 phenoxy carboxylic acid herbicides in the water sample by combining ultra-high performance liquid chromatography-tandem mass spectrometry:
(1) mixing MIL-101-NMe3 +The MMM is placed in a beaker, 50mL of water sample is added into the beaker, and the concentration of the 11 phenoxy carboxylic acid herbicides in the water sample is 150 ng/L. Then the water sample is shaken and extracted for 30min in a constant temperature oscillator.
(2) The membrane was taken out of the water sample and placed in a beaker and eluted with 2.5mL of 1.5% strength ammonia/methanol solution twice for 15min each. The collected eluent is blown to near dryness by nitrogen at room temperature, and is redissolved by 0.5mL of acetonitrile/water solution with the concentration of 20 percent, is filtered by a filter head with the thickness of 0.22 mu m after being evenly mixed by vortex, and is detected by ultra performance liquid chromatography-tandem mass spectrometry (the detection chromatogram is shown in figure 2). The detection conditions of the ultra-high performance liquid chromatography-tandem mass spectrometry are as follows:
chromatographic conditions are as follows: the chromatographic column is ACQUITYUPLCBEH chromatographic column (100mm × 2.1mm × 1.7 μm); the mobile phase adopts 0.01 percent formic acid water solution (A) and acetonitrile (B); the column temperature is 40 ℃; the flow rate is 0.4 mL/min; the sample injection amount is 5 mu L; the gradient elution procedure was as follows:
mass spectrum conditions: a negative ion mode; the ESI source parameters are: the power voltage is-4500V, the air curtain pressure is 30psi, the atomization air pressure is 50psi, the auxiliary device pressure is 60psi, and the ionization temperature is 300 ℃; multiple reaction monitoring is adopted, and the specific conditions are as follows:
example 2:
in this embodiment, main factors influencing the extraction recovery rate of 11 phenoxy carboxylic acid herbicides are examined, the optimal values of the factors when the extraction recovery rate is the highest are calculated, and parameters related to the working curves of the 11 phenoxy carboxylic acid herbicides, the detection limit of the method and the precision are determined under the condition of the optimal values of the factors, and the specific process comprises the following steps:
the method comprises the following steps: calculating the optimal values of all factors when the extraction recovery rate of the 11 phenoxy carboxylic acid herbicides is highest:
(1) investigation of MOF dosage on extraction recovery
This example examines the MOF (MIL-101-NH)2) The influence of the dosage on the extraction recovery rate is measured by respectively weighing 5, 10, 20, 40 and 60mg of metal organic framework material MIL-101-NH2The MOF mixed matrix membrane is prepared by mixing 50mg of PVDF, the concentration of the 11 phenoxy carboxylic acid herbicides in a water sample is 150ng/L, the result is shown in figure 3, and when the dosage of the MOF is increased from 5mg to 20mg, the extraction efficiency of the 11 phenoxy carboxylic acids is gradually improvedThe extraction efficiency of only 2 phenoxy carboxylic acids is slightly reduced when the amount is increased from 20mg to 40mg, which shows that the adsorption sites are increased and the adsorption quantity is increased along with the increase of the MOF dosage; however, when the amount of the MOF is increased to 60mg, the extraction efficiency of 11 phenoxy carboxylic acids is reduced, so that 40mg of the MOF is selected in the embodiment.
(2) Investigation of water sample pH on extraction recovery rate
In the embodiment, the influence of the pH of the water sample on the activity of the surface adsorption sites of the extraction material is examined, and the extraction recovery rate results under the conditions that the pH of the water sample is 3, 4, 6, 7 and 8 are respectively examined, as can be seen from fig. 4, when the pH is from 3 to 6, the extraction recovery rate gradually increases, the recovery rate change is not large within the range of 6 to 8, which indicates that the optimal pH of the material for extracting 11 phenoxy carboxylic acids is near neutral, and the pH is not adjusted in the embodiment.
(3) Investigation of extraction recovery from extraction time
In the embodiment, the influence of the extraction time on the extraction recovery rate is examined, the insufficient extraction time can cause that the adsorption between the target compound and the material cannot reach the balance, and the extraction recovery rate is influenced, the embodiment examines the recovery rate conditions of 11 phenoxy carboxylic acids when the extraction time is respectively 10min, 20min, 30min, 40 min and 50min, and as a result, as shown in fig. 5, when the extraction time is increased from 10min to 30min, the extraction recovery rate is obviously increased, the extraction time is continuously prolonged, the recovery rate is not obviously increased, and the adsorption is shown to reach the balance, so that the extraction time is selected to be 30min in the embodiment.
(4) Examination of ion intensity on extraction recovery
In this example, the effect of the ionic strength of the sample solution on the adsorption of the target analyte is examined, and in this example, 0, 1, 5, 10 and 20mmol/L sodium chloride (NaCl) is added to the water sample, and as shown in FIG. 6, the recovery rates of 11 phenoxy carboxylic acids decrease with the increase of NaCl concentration, indicating that the addition of salt is not beneficial to the extraction of the target substance, so the present example selects not to add NaCl.
(5) Investigation of eluent species on extraction recovery
In this embodiment, the effect of the eluent on the elution efficiency of the substance to be detected is examined, and ammonia with four concentrations of 0.5%, 1%, 1.5% and 2% by volume of ammonia water/methanol is respectively examined, and as shown in fig. 7, as the ammonia concentration is increased from 0.5% to 1.5%, the extraction rate of 11 phenoxy carboxylic acids is gradually increased, and after the ammonia concentration is continuously increased, the extraction efficiency of 9 phenoxy carboxylic acids is decreased, so that 1.5% ammonia water/methanol is selected as the eluent in this embodiment.
(6) Investigation of eluent dosage on extraction recovery
In this embodiment, the single-eluent dosages of 1, 1.5, 2, 2.5, and 3mL are examined, and the elution effect under the condition of two-time elution is shown in fig. 8, where the single-eluent dosage is increased from 1mL to 2.5mL, the recovery rates of 11 phenoxy carboxylic acids gradually increase, and after the dosage continues to increase, the extraction recovery rate does not increase significantly, so that the single-eluent dosage selected in this embodiment is 2.5 mL.
(7) Examination of elution time on extraction recovery
In this embodiment, the elution time of 3min, 6 min, 10min, 15min and 20min is considered, and the elution effect under the condition of twice elution is considered, as shown in fig. 9, when the single elution time is increased from 3min to 15min, the extraction recovery rate is in an upward trend, the elution time is continuously increased, and the recovery rate is not increased, so that the single elution time is selected to be 15min in this embodiment.
Step two: the method for measuring the working curve related parameters of the 11 phenoxy carboxylic acid herbicides has the following detection limits and precision:
(1) preparing 50mL water samples with the concentrations of 11 phenoxy carboxylic acid herbicides of 1ng/L, 5ng/L, 10ng/L, 50ng/L, 100ng/L, 200ng/L and 500ng/L, and performing ultra performance liquid chromatography-tandem mass spectrometry under the optimized membrane solid phase extraction condition to obtain a regression equation, a linear range and correlation coefficients (R) of the working curves of the 11 phenoxy carboxylic acid herbicides2) The instrument detection limits and method detection limits are shown in table 1.
(2) Preparing 50mL of simulated water samples with 11 phenoxy carboxylic acid herbicides of low, medium and high concentrations of 5ng/L, 50ng/L and 200ng/L, determining according to a membrane solid phase extraction step, parallelly determining the precision within 5 investigation days at each concentration point within one day and expressing the precision by relative standard deviation, determining the precision within 5 investigation days once per day and expressing the precision by relative standard deviation, and the result is shown in Table 2, wherein the relative standard deviation of the precision within 11 phenoxy carboxylic acid herbicides is within the range of 1.38-12.06% and the relative standard deviation of the precision within 2.27-13.92%, and the requirement of analysis accuracy is met.
TABLE 111 work Curve-related parameters and method detection limits for phenoxy carboxylic acid herbicides
TABLE 211 phenoxy carboxylic acid herbicides day by day precision and day by day precision
Example 3:
measuring the residual quantity of 11 phenoxy carboxylic acid herbicides in water of a reservoir of a flood plain in Qingdao city, collecting the water sample, filtering the water sample by using rapid qualitative filter paper with the aperture of 80-120 mu m, and then filtering the water sample by using a filter membrane with the aperture of 0.45 mu m; measuring the filtered water sample by the method of example 1, performing accuracy test by the method of example 2, preparing 11 phenoxy carboxylic acid herbicide low, medium and high concentration actual water samples with the concentrations of 5ng/L, 50ng/L and 200ng/L respectively, performing a standard addition recovery rate test, measuring each concentration point for 3 times, and calculating the average value, the relative standard deviation and the standard addition recovery rate of the 3 times of measurement; the results are shown in Table 3, from which it can be seen that the relative standard deviation of this example is 1.22% to 13.83%; therefore, the embodiment has good extraction effect, accurate analysis result and good reproducibility.
TABLE 3 Standard recovery rate of reservoir water of Kanghong beach (n is 3, ng/L)
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An analytical detection method of 11 phenoxy carboxylic acid herbicides in an environmental water sample is characterized by comprising the following steps: pretreating a water sample by using a dispersion film solid phase extraction method, and analyzing and detecting the 11 phenoxy carboxylic acid herbicides in the water sample by combining ultra-high performance liquid chromatography-tandem mass spectrometry; the membrane solid phase extraction material in the dispersion membrane solid phase extraction method is a cationic metal organic framework material MIL-101-NMe3 +MMM。
2. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in an environmental water sample according to claim 1, wherein the 11 phenoxy carboxylic acid herbicides are 2, 4-dichlorophenoxyacetic acid, 2- (2, 4-dichlorophenoxy) -propionic acid, 4- (2, 4-chlorophenoxy) -butyric acid, 2-methyl-4-chlorophenoxyacetic acid, 2- (2-methyl-4-chlorophenoxy) propionic acid, 2,4, 5-trichlorophenoxy acetic acid, 2- (2,4, 5-trichlorophenoxy) -propionic acid, phenoxyacetic acid, 4-phenoxybutyric acid, 4-chlorophenoxy acetic acid and dicamba.
3. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample as claimed in claim 1, wherein the cationic metal organic framework material MIL-101-NMe3 +The preparation process of the MMM comprises the following steps:
(1) preparation of MIL-101-NH2: adding 2-amino terephthalic acid, chromium nitrate nonahydrate and sodium hydroxide into ultrapure water, ultrasonically mixing uniformly, transferring the mixture into a solvothermal reaction kettle, and reacting at the temperature of 120-; cooling to room temperature, centrifuging to collect a crude product, then washing with DMF and ethanol, and drying;
(2) preparation of MIL-101-NH2Film formation: mixing MIL-101-NH2Dispersing in acetone, dissolving polyvinylidene fluoride (PVDF) in DMF, adding DMF solution containing PVDF to MIL-101-NH2In the acetone solution, evenly mixing by ultrasonic; then, volatilizing the acetone by adopting a rotary evaporation method for the mixed solution, coating the residual mixed solution on a glass plate, and heating in an oven to volatilize the solvent;
(3) preparation of MIL-101-NMe3 +MMM: the obtained MIL-101-NH2The membrane bubble is put into dichloromethane, methyl trifluoromethanesulfonate is dripped into the dichloromethane and reacts for 8 to 15 hours to obtain MIL-101-NMe3A film; then replacing dichloromethane once every 8-15 hours to remove unreacted methyl trifluoromethanesulfonate; finally, MIL-101-NMe is added3Soaking in hydrochloric acid solution, repeatedly washing acidified membrane material with ultrapure water until pH value of eluate reaches neutral to obtain cationic MIL-101-NMe3 +MMM。
4. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample according to claim 1The method is characterized in that the pretreatment process comprises the following steps: mixing MIL-101-NMe3 +The MMM is placed in a container, a water sample containing a substance to be detected is added, and the mixture is subjected to constant-temperature oscillation extraction; then, MIL-101-NMe3 +Taking out the MMM membrane, and eluting with ammonia water/methanol solution; the collected eluent is dried by nitrogen at room temperature, redissolved by acetonitrile/water solution, vortexed, mixed and filtered.
5. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample as claimed in claim 4, wherein in the pretreatment process, MIL-101-NH2The dosage of the compound is 5-60mg, preferably 40 mg;
furthermore, in the pretreatment process, the concentration of the substance to be detected in the water sample is 1-500 ng/L.
6. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in an environmental water sample according to claim 4, wherein in the pretreatment process, the volume of the water sample is 40-60mL, preferably 50 mL; furthermore, in the pretreatment process, the temperature of constant temperature oscillation is kept at 30 ℃, and the extraction time is 10-50min, preferably 30 min.
7. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in an environmental water sample according to claim 4, wherein in the pretreatment process, the ammonia/methanol solution is 1.5% ammonia/methanol solution; alternatively, the ammonia/methanol solution is used in an amount of 1 to 3mL, preferably 2.5 mL.
8. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample according to claim 4, wherein in the pretreatment process, the elution times are at least twice, each elution time is 3-20min, preferably 15 min; furthermore, in the pretreatment process, the acetonitrile/water solution is 20% acetonitrile/water solution; alternatively, the amount of acetonitrile/water solution used is 0.3-1mL, preferably 0.5 mL.
9. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in an environmental water sample according to claim 1, wherein in the ultra-high performance liquid chromatography-tandem mass spectrometry detection: chromatographic conditions are as follows: the chromatographic column is an ACQUITY UPLC BEH chromatographic column (100 mm. times.2.1 mm. times.1.7 μm); the mobile phase adopts 0.01 percent formic acid water solution (A) and acetonitrile (B); the column temperature is 40 ℃; the flow rate is 0.4 mL/min; the sample injection amount is 5 mu L;
or, mass spectrometry conditions: a negative ion mode; the ESI source parameters are: the power voltage is-4500V, the air curtain pressure is 30psi, the atomization air pressure is 50psi, the auxiliary device pressure is 60psi, and the ionization temperature is 300 ℃; multiple reaction monitoring is used.
10. The method for analyzing and detecting 11 phenoxy carboxylic acid herbicides in environmental water sample as claimed in any one of claims 1 to 9, for use in pesticide detection.
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