CN114660190A - Method for detecting pesticide residue of weedicide in soil - Google Patents
Method for detecting pesticide residue of weedicide in soil Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000284 extract Substances 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001819 mass spectrum Methods 0.000 claims abstract description 14
- 238000000638 solvent extraction Methods 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 74
- 150000002500 ions Chemical class 0.000 claims description 43
- 230000002363 herbicidal effect Effects 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002890 Aclonifen Substances 0.000 claims description 25
- DDBMQDADIHOWIC-UHFFFAOYSA-N aclonifen Chemical compound C1=C([N+]([O-])=O)C(N)=C(Cl)C(OC=2C=CC=CC=2)=C1 DDBMQDADIHOWIC-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 230000014759 maintenance of location Effects 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- YNPNZTXNASCQKK-LHNTUAQVSA-N 1,2,3,4,5,6,7,8,9,10-decadeuteriophenanthrene Chemical compound [2H]C1=C([2H])C([2H])=C2C3=C([2H])C([2H])=C([2H])C([2H])=C3C([2H])=C([2H])C2=C1[2H] YNPNZTXNASCQKK-LHNTUAQVSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 5
- 239000012634 fragment Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 239000013582 standard series solution Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- -1 aminopropyl Chemical group 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005227 gel permeation chromatography Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000010813 internal standard method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 17
- 238000005259 measurement Methods 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 9
- 238000011156 evaluation Methods 0.000 abstract description 5
- 238000011835 investigation Methods 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 3
- 238000002372 labelling Methods 0.000 abstract description 3
- 238000003900 soil pollution Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000012502 risk assessment Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005070 sampling Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000575 pesticide Substances 0.000 description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000013076 target substance Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IHHMUBRVTJMLQO-UHFFFAOYSA-N Pyraclonil Chemical compound C#CCN(C)C1=C(C#N)C=NN1C1=NN(CCCC2)C2=C1Cl IHHMUBRVTJMLQO-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XITQUSLLOSKDTB-UHFFFAOYSA-N nitrofen Chemical group C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1Cl XITQUSLLOSKDTB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004856 soil analysis Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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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
- G01N30/02—Column chromatography
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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Abstract
The invention discloses a method for detecting the pesticide residue of weedicide in soil, which comprises the steps of carrying out pressure extraction on the weedicide in the soil by using a mixed solvent of dichloromethane and acetone on a pressure solvent extractor, concentrating, purifying and carrying out solvent conversion on extract liquor, separating in a gas chromatograph and detecting by a mass spectrum detector. The matrix labeling experiment shows that: when the content of the weedicide in the soil matrix sample is 0.2 mg/kg-2.0 mg/kg, the relative standard deviation (n is 6) of the measurement result is 4.0% -5.3%; when the addition amount of the weedicide in the soil matrix sample is 2 mug, 5 mug and 10 mug, the recovery rates of 6 times of independent measurement are 93.5-106%, 94.2-104% and 95.2-106% respectively; when the sampling amount of the soil is 10g and the constant volume of the extract is 1.0mL, the detection limit of the method for the phytocide in the soil is 0.04mg/kg, and the measurement lower limit is 0.16 mg/kg. The invention adopts a mass spectrum detector for qualitative determination, and has high resolution and strong anti-interference capability; the pressure solvent extraction instrument is adopted to extract the soil sample, the operation is convenient, and the automation degree is high; the soil pollution investigation, risk assessment and restoration evaluation can be met.
Description
Technical Field
The invention belongs to the technical field of environmental detection, and relates to a method for detecting the pesticide residue of weedicide in soil.
Background
The chemical name of the herbicidal ether is 2, 4-dichlorophenyl-4-nitrophenyl ether, which is a contact herbicide. The Ministry of agriculture of 6 months 2002 issues No. 199 bulletin, and the aclonifen is a pesticide prohibited by the national regulations. The international cancer research institution of world health organization in 10 months in 2017 publishes a carcinogen list, and the aclonifen is listed in a category 2B carcinogen list. The herbicidal ether is used as one of the main varieties of herbicide pesticides and is widely applied to weeding in agriculture and forestry. The molecular structure of the pesticide is generally relatively stable and difficult to naturally degrade, so that the pesticide cannot be degraded and disappear in the natural environment quickly after being applied, but is retained and accumulated in soil, underground water bodies, surface water bodies and ocean water bodies in different forms and ways, and finally harms human health through the ways of bioabsorption and enrichment, food chain transfer and the like. In addition, with the rapid development of social economy and the continuous expansion of urban built-up areas, the production of old pesticide plants is stopped and the old pesticide plants are moved, and the safe utilization of the pesticide plant plots is more and more concerned by the public in society.
The content detection of the characteristic factors of the pesticides in the soil is a key technical support for evaluating the soil environment quality of the agriculture and forestry land and environmental investigation and risk evaluation before the decommissioning land of a pesticide factory is developed and utilized, no special national standard or industrial standard is established for the determination of the herbicidal ether in the soil at present, the determination method of the herbicidal ether in the soil related to the prior literature report is a method research before 20 years, the method is mainly used for carrying out soaking extraction, vibration extraction or ultrasonic extraction by using an organic solvent and then carrying out gas chromatography, liquid chromatography or thin-layer chromatography analysis, and the determination method uses retention time for qualitative detection and has poor anti-interference performance in a qualitative mode, and a false positive detection result is very easy to appear. At present, the rapid development of sample pretreatment and analysis application technologies and the continuous change of software and hardware of instruments, a method for determining the pesticide residue in the soil with convenient operation, strong qualitative anti-interference capability and high quantitative accuracy is needed to be established.
Disclosure of Invention
The invention aims to provide a method for measuring the pesticide residue in the soil, which is convenient for extracting a soil sample, strong in qualitative anti-interference capability and high in quantitative accuracy.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a method for detecting the pesticide residue of the aclonifen in soil specifically comprises the following steps:
And 5, concentrating and purifying the extract: dehydrating the extract by using anhydrous sodium sulfate, concentrating by using a rotary evaporator or a water bath nitrogen blower, converting the solvent into n-hexane, quantitatively adding an internal standard (phenanthrene-d 10) solution, and fixing the volume to 1mL by using the n-hexane to be detected. If the extraction concentrated solution contains obvious impurities or has darker color, a commercial special purification column such as a graphitized carbon black solid phase extraction column and an aminopropyl bonded silica gel solid phase extraction column can be used for purification, then a rotary evaporator or a water bath nitrogen blower is used for concentration, the solvent is converted into n-hexane, an internal standard (phenanthrene-d 10) solution is added quantitatively, and then the n-hexane is used for fixing the volume to 1mL to be detected. If the sample contains more sulfur compounds, the copper particles can be removed during purification. Gel permeation chromatography may be used for purification in addition to commercial dedicated purification columns.
Step 7, standard curve establishment: preparing a standard series of 5 mass concentration points, so that the mass concentration of the aclonifen is respectively 2.0 mug/mL, 4.0 mug/mL, 8.0 mug/mL, 10.0 mug/mL and 20.0 mug/mL, and the mass concentration of the internal standard substance (phenanthrene-d 10) is 2.0 mug/mL; carrying out sample injection analysis in sequence from low concentration to high concentration according to the instrument conditions in the step 6 to obtain a mass spectrum total ion flow graph of the herbicidal ether with different concentrations, and recording the retention time and the peak area of a quantitative ion mass spectrum peak of the herbicidal ether, wherein the quantitative ion of the herbicidal ether is 283, and the qualitative ions are 202 and 253; and establishing a standard curve of the herbicidal ether by taking the mass concentration ratio of the herbicidal ether to the internal standard compound as a horizontal coordinate and taking the quantitative ion response value ratio of the target compound to the internal standard compound as a vertical coordinate.
Step 8, sample determination: and (3) setting conditions of the gas chromatography-mass spectrometer according to the step 6, after the conditions are stable, sending the extraction concentrated solution with constant volume in the step 5 into a gas chromatograph through an automatic sample injector for separation and detecting by a mass spectrum detector, and quantifying by using retention time, fragment ion mass-to-charge ratio and abundance ratio.
Step 9, calculating a result: according to the peak areas of the herbicidal ether and the internal standard substance measured by the gas chromatography-mass spectrometer, the concentration of the herbicidal ether in the extraction liquid is calculated by a standard curve equation, and then according to the sample amount and the dry matter content of the sample, the concentration of the herbicidal ether in the soil sample is calculated. The difference between the relative retention time of the aclonifen in the sample and the relative retention time of the compound in the standard series solution is within +/-0.03 s, and the relative deviation between the abundance ratio of the auxiliary qualitative ions to the quantitative ions of the aclonifen in the sample and the abundance ratio of the auxiliary qualitative ions to the quantitative ions in the standard solution is within +/-30%.
The content W (mg/kg) of the target substance in the soil is rhoi×V÷(m×ωdm)
In the formula: rhoiThe concentration of the target substance (the aclonide or the cyanophos) in the extract is obtained by a standard curve, and the concentration is mg/L.
V is volume of extract to be constant volume, mL.
m is soil sample weighing amount, g.
ωdm-soil sample dry matter content,%.
Compared with the prior art, the invention has the beneficial effects that:
1. the method adopts a mass spectrum detector for qualitative determination, is a brand new qualitative technical route different from the existing literature method, and compared with the literature method, the retention time is qualitative, and the method adopts the mass spectrum detector for qualitative determination by the retention time, the mass-to-charge ratio and the abundance ratio of the characteristic fragment ions, so that the resolution ratio is higher and the anti-interference capability is strong.
2. The method for extracting the pesticide residue in the soil by adopting the pressure solvent extractor is a brand new extraction mode different from the existing literature method, is convenient to operate, has high automation degree, and is an efficient soil analysis pretreatment method.
3. The method for determining the pesticide residue in the soil by adopting the pressure solvent extraction-gas chromatography-mass spectrometry provides a new key technical support for soil pollution condition investigation, risk assessment and restoration effect evaluation for the re-development and safe utilization of retired land blocks of a weedicide production enterprise.
4. The method for measuring the pesticide residue in the soil has the advantages of lower detection limit and higher recovery rate, the detection limit of the method is 0.04mg/kg, the standard addition recovery rate of a soil matrix sample is 93.5-106%, the recovery rate is superior to that of a literature method, and the technical requirements of soil pollution condition investigation, risk evaluation and restoration effect evaluation detection are completely met.
Drawings
FIG. 1 is a total ion flow diagram for the detection of the pesticide residue in the soil by the method of the present invention;
FIG. 2 is a graph of a standard curve of aclonifen;
FIG. 3 is a total ion flow diagram of the herbicidal ether and interferents.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
Instruments and reagents used in the examples:
gas chromatography-Mass spectrometer, model Agilent 7890B/5977B, with liquid autosampler and HP-5MS column (30 m. times.250. mu. m. times.0.25. mu.m), Agilent technologies, Inc.
Rapid solvent extraction apparatus, model Thermo Scientific ASE 350.
Water bath nitrogen blower, model Organomation N-EVAP.
Electronic balance, model YP502N, shanghai tianmei balance instruments ltd.
Herbicidal Ether, purity of 99.5%, Shanghai' an spectral laboratory science and technology GmbH.
Stock solutions of internal standard (phenanthrene-d 10), ρ 1000mg/L, carbofuran.
Acetone, dichloromethane, methanol, pesticide residue grade, Shanghai' an spectrum experiment science and technology, Inc.
Anhydrous sodium sulfate, super pure, group of Chinese medicine.
The detection method comprises the following steps:
(1) collecting a sample: collected according to soil environmental monitoring technical Specification (HJ/T166), and placed in a clean brown glass bottle to be refrigerated in dark at a temperature of below 4 ℃.
(2) Preparation and extraction of samples: removing foreign matters, branches, leaves, stones and the like in the soil sample, and uniformly mixing the sample; two (to the nearest 0.01g) soil samples of about 10g were weighed simultaneously, one for determination of dry matter content and one for extraction with a pressure solvent extractor; adding a proper amount of diatomite into a sample for extraction, grinding the sample into a quicksand shape, then putting the sample into an extraction cell, and performing pressure extraction on the sample of the soil by using a mixed solvent (volume ratio is 1:1) of dichloromethane and acetone on a pressure solvent extractor.
(3) Setting the conditions of a pressure solvent extractor: the pressure of carrier gas (nitrogen) is 1.0MPa, the heating temperature is 100 ℃, the pressure is 1700psi, the preheating and balancing are carried out for 5min, the static extraction time is 5min, the solvent leaching volume is 60 percent of the cell volume, the extraction nitrogen purging time is 70s, and the static extraction is carried out for 2 times.
(4) And (3) measuring the dry matter content of the soil: the dry matter content of the soil samples was determined according to gravimetric method of determination of dry matter and moisture of soil (HJ 613).
(5) Preparing an internal standard use solution: accurately transferring 200.0 mu L of phenanthrene-d 10 internal standard stock solution into a 10mL volumetric flask by using a micropipette, metering the volume by using methanol, and uniformly mixing to obtain an internal standard use solution with the concentration of 20 mg/L.
(6) Concentrating and purifying the extract: and dehydrating the extract liquor by using anhydrous sodium sulfate, concentrating by using a rotary water bath nitrogen blowing instrument, converting the solvent into normal hexane, quantitatively adding 100 mu L of internal standard use solution, and fixing the volume to 1mL by using the normal hexane to be detected.
(7) Setting conditions of a gas chromatography-mass spectrometer: the sample inlet temperature is 280 ℃; column temperature 40 ℃ (0min) → 15 ℃/min → 70 ℃ (0min) → 20 ℃/min → 90 ℃ (0min) → 7.27 ℃/min → 130 ℃ (0min) → 20 ℃/min → 180 ℃ (0min) → 10 ℃/min → 200 ℃ (0min) → 30 ℃/min → 260 ℃ (0min) → 20 ℃/min → 300 ℃ (6 min); the carrier gas is helium, and the column flow is 1.0 mL/min; the sample injection mode is split sample injection, the split ratio is 10:1, and the sample injection amount is 1.0 mu L; the interface temperature is 280 ℃; the ion source is an EI source, the temperature of the ion source is 230 ℃, the electron energy of the ion source is 70eV, and the temperature of a quadrupole rod is 150 ℃; the data acquisition mode is full scanning.
(8) Preparation of standard use solution of the herbicidal ether: accurately weighing 12.75mg of the herbicidal ether in a 25mL volumetric flask, diluting to constant volume with methanol, and uniformly mixing to obtain the standard use solution of the herbicidal ether with the concentration of 500 mg/L.
(9) Establishing a standard curve: taking 5mL volumetric flasks, adding 2mL of methanol in advance, adding 20, 40, 80, 100 and 200 μ L of the standard use solution of the aclonifen respectively, adding 100 μ L of the internal standard use solution, diluting to constant volume with methanol, mixing uniformly to prepare a standard series of 5 mass concentration points, and enabling the mass concentrations of the aclonifen to be 2.0 μ g/mL, 4.0 μ g/mL, 8.0 μ g/mL, 10.0 μ g/mL and 20.0 μ g/mL in sequence, wherein the mass concentrations of the internal standard substances are all 2.0 μ g/mL. And (4) carrying out sample injection analysis in sequence from low concentration to high concentration according to the instrument condition in the step (7), obtaining a mass spectrum total ion flow graph of the herbicidal ether with different concentrations, and recording the retention time of the herbicidal ether and the peak area of a quantitative ion mass spectrum peak. And establishing a calibration curve equation of the herbicidal ether as Y (0.02759X-0.002714) and a linear correlation coefficient r as 0.998 by taking the mass concentration ratio of the herbicidal ether to the internal standard compound as an abscissa and taking the quantitative ion response value ratio of the herbicidal ether to the internal standard compound as an ordinate. Fig. 1 is a total ion flow diagram of the detection of the pesticide residue of the aclonifen in the soil, and fig. 2 is a standard curve diagram of the aclonifen.
(10) And (3) sample determination: and (3) setting conditions of a gas chromatography-mass spectrometer according to the step (7), after the conditions are stable, sending the extraction concentrated solution with constant volume in the step (6) into a gas chromatograph through an automatic sample injector for separation, detecting the separation by a mass spectrum detector, and quantifying by retention time, fragment ion mass-to-charge ratio and abundance ratio, and an internal standard method.
(11) And (4) calculating a result: according to the peak areas of the herbicidal ether and the internal standard substance measured by the gas chromatography-mass spectrometer, the concentration of the herbicidal ether in the extraction liquid is calculated by a standard curve equation, and then according to the sample amount and the dry matter content of the sample, the concentration of the herbicidal ether in the soil sample is calculated. The difference between the relative retention time of the aclonifen in the sample and the relative retention time of the compound in the standard series solution is within +/-0.03 s, and the relative deviation between the abundance ratio of the auxiliary qualitative ions to the quantitative ions of the aclonifen in the sample and the abundance ratio of the auxiliary qualitative ions to the quantitative ions in the standard solution is within +/-30%.
The content W (mg/kg) of the target substance in the soil is rhoi×V÷(m×ωdm)
In the formula: rhoiThe concentration of the target substance (the pyraclonil or the cyanophos) in the extract is obtained by a standard curve, and the concentration is mg/L.
V is volume of extract to be constant volume, mL.
m-soil sample weighing, g.
ωdm-soil sample dry matter content,%.
Example 1
(1) The method comprises the following steps: diluting the standard use solution of the aclonifen by 10 times to obtain an aclonifen labeling solution, accurately transferring 20 mu L of the aclonifen labeling solution into an extraction pool filled with 10g of quartz sand by using a micropipette according to the technical guide rule of environmental monitoring and analysis method standard formulation (HJ 168), performing pressure extraction on a pressure solvent extraction instrument by using dichloromethane and acetone (1:1) according to the instrument conditions in the step (3), performing nitrogen blowing concentration on the extract according to the step (6) to convert the solvent into normal hexane, quantitatively adding 100 mu L of the internal standard use solution, performing constant volume to 1mL by using the normal hexane, sending the normal hexane into a gas chromatograph according to the instrument conditions in the step (7) for separation by using an automatic sampler, detecting by using a mass spectrometer, and determining the content of the aclonifen. The above operation was repeated 6 times in the whole flow, and the minimum method detection limit MDL of the herbicidal ether was calculated as 0.04mg/kg according to the following formula, and when 4 times the minimum detection limit was used as the method measurement lower limit, the method measurement lower limit of the herbicidal ether was 0.16 mg/kg.
MDL＝t(n-1,0.99)×S
In the formula: n is the number of parallel measurements of the sample, and n is 7;
t is a t distribution value when the degree of freedom is n-1 and the confidence coefficient is 99% (t is 3.143 when n is 7);
s-standard deviation of n replicates.
(2) The detection limit of the thin layer chromatography of the reference is 1.25mg/kg, the detection limit of the liquid chromatography is 0.11mg/kg, and the detection limit of the gas chromatography-mass spectrometry method of the invention is 0.04mg/kg, which is superior to the detection limit of the method of the reference.
Example 2
The method has the following precision: accurately transferring the standard use solution of the weedicide with different volumes into an extraction pool containing 10g of a soil matrix sample by using a micropipette, performing pressure extraction on a pressure solvent extraction instrument by using dichloromethane and acetone (1:1) according to the instrument conditions in the step (3), performing nitrogen-blown concentration on the extract according to the step (6) to convert the solvent into normal hexane, quantitatively adding 100 mu L of the internal standard use solution, performing constant volume to 1mL by using the normal hexane, feeding the internal standard use solution into a gas chromatograph by using an automatic sample feeder according to the instrument conditions in the step (7), separating and detecting by using a mass spectrum detector to determine the content of the weedicide in the soil matrix sample. The precision measurement is carried out by repeating the operation for 5 times in the whole process, the precision measurement data are shown in table 1, and when the content of the aclonifen in the soil matrix sample is 0.2 mg/kg-2.0 mg/kg, the relative standard deviation RSD (n is 6) of the measurement result is 4.0% -5.3%.
Table 1 precision measurement data (n ═ 6)
Example 3
(1) The method has the following accuracy: accurately taking 40 mu L, 100 mu L and 200 mu L of the herbicidal ether standard solution by using a micropipette respectively into an extraction pool filled with 10g of a soil matrix sample, performing pressure extraction on a pressure solvent extractor by using dichloromethane and acetone (1:1) according to the instrument condition of the step (3), converting the solvent into n-hexane by performing nitrogen blowing concentration on an extract according to the step (6), quantitatively adding 100 mu L of the internal standard solution, performing constant volume to 1mL by using the n-hexane, sending the internal standard solution into a gas chromatograph by using an automatic sampler according to the instrument condition of the step (7), separating and detecting by using a mass spectrometer, and determining the content of the herbicidal ether in the soil matrix sample, wherein the determination result is shown in Table 2.
TABLE 2 measurement of recovery with addition of standard
(2) The recovery rate of the thin layer chromatography of the reference is 80-95%, the recovery rate of the liquid chromatography is 84.7-100.2%, the recovery rate of the gas chromatography is 77.9-94%, and the recovery rate of the gas chromatography-mass spectrometry of the invention is 93.5-106%, which is superior to the recovery rate of the method of the reference.
Interference test: according to the method of the reference, the method simultaneously determines the weedicide DDT, DDE, DDD and other easily interfered weedicide, the gas chromatography-mass spectrometry is used for simultaneously determining the weedicide DDT and the organic chlorine pesticide, the mass spectrometry detector is used for determining the weedicide by retention time, characteristic fragment ion mass-to-charge ratio and abundance ratio, the qualitative identification of the weedicide is completely not interfered by the organic chlorine pesticide DDT, DDE, DDD and the like, and the method simultaneously determines the total ions of the weedicide DDT, DDE, DDD and the like as shown in figure 3.
Example 4
Storage stability of the sample: and (3) bringing collected soil samples of retired plots of the pesticide factories back to a laboratory and storing the samples in a refrigerator environment at 4 ℃, wherein the sample No. 1 is a soil sample containing high-concentration weedicide, and the sample No. 2 is a soil sample containing low-concentration weedicide. And (4) performing a stability test on the soil sample according to the pressure solvent extraction condition in the step (3), the concentration and volume determination step in the step (6) and the gas chromatography-mass spectrometry analysis condition in the step (7), wherein the measurement result is shown in a table 4, and when the soil sample is stored in a refrigerator environment at 4 ℃ for 7 days, the change of the measurement result is less than 20%.
TABLE 4 soil sample stability determination data
Example 5
The storage stability of the extract: and (3) bringing collected soil samples of retired plots of the pesticide factories back to a laboratory, extracting, concentrating and fixing the volume of the soil samples according to the step (2) and the step (6), and storing the extract liquor in a refrigerator environment at 4 ℃, wherein the sample No. 1 is the soil sample extract liquor containing the high-concentration weedicide, and the sample No. 2 is the soil sample extract liquor containing the low-concentration weedicide. And (3) performing a soil sample extraction liquid stability test according to the gas chromatography-mass spectrometry analysis conditions in the step (7), wherein the measurement result is shown in Table 5, and the change of the measurement result is less than 5% when the soil sample extraction liquid is stored in a refrigerator environment at 4 ℃ for 7 days.
TABLE 5 stability measurement data for sample extracts
The above embodiments are merely to illustrate the technical solutions of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, various changes or modifications may be made by those skilled in the art without departing from the scope of the present invention.
Claims (3)
1. A method for detecting the pesticide residue of the aclonifen in soil is characterized by comprising the following steps: the method comprises the following steps:
step 1, collecting and storing samples: collecting soil sample, storing in clean dark glass bottle, refrigerating, protecting from light, sealing during transportation, and refrigerating at below 4 deg.C in the dark if analysis and determination cannot be performed in time;
step 2, preparation and extraction of samples: removing foreign matters in a soil sample, uniformly mixing the soil sample, and drying the soil sample by using a freeze dryer until the water content of the soil sample is lower than 30% when the water content of the soil sample is higher than 30%; simultaneously weighing two 10g soil samples, wherein one part is used for measuring the dry matter content, and the other part is used for extracting by a pressure solvent extractor; adding diatomite into a sample for extraction, grinding the sample into a quicksand shape, then putting the sample into an extraction tank, and carrying out pressure extraction on the weedicide in the soil sample on a pressure solvent extraction instrument;
step 3, measuring the dry matter content of the soil;
and 4, extracting by a pressure solvent extractor: conditions of the pressure solvent extractor: carrying gas pressure of 1.0MPa, heating temperature of 100 ℃, pressure of 1700psi, preheating and balancing for 5min, static extraction time of 5min, leaching 60% of the cell volume by solvent, purging by extraction nitrogen for 70s, static extraction for 2 times, and mixing the liquid after the static extraction to obtain extraction liquid;
and 5, concentrating and purifying the extract: dehydrating the extract, concentrating by using a rotary evaporator or a water bath nitrogen blower, converting the solvent, quantitatively adding an internal standard phenanthrene-d 10 solution, and performing constant volume to 1mL by using normal hexane to be detected;
when the extracted concentrated solution contains obvious impurities or has a darker color, a commercial special purification column is used, wherein the purification column comprises a graphitized carbon black solid-phase extraction column or an aminopropyl bonded silica gel solid-phase extraction column for purification, a rotary evaporator or a water bath nitrogen blower is used for concentration, the solvent is converted into n-hexane, and after the internal phenanthrene-d 10 solution is quantitatively added, the volume is fixed to 1mL by using the n-hexane to be detected;
when the sample contains sulfur-containing compounds, copper particles are used for removing during purification; also comprises using a commercial special purifying column or using gel permeation chromatography for purification;
step 6, gas chromatography mass spectrometer conditions: the sample inlet temperature is 280 ℃; column temperature 40 ℃ → 15 ℃/min → 70 ℃ → 20 ℃/min → 90 ℃ → 7.27 ℃/min → 130 ℃ → 20 ℃/min → 180 ℃ → 10 ℃/min → 200 ℃ → 30 ℃/min → 260 ℃ → 20 ℃/min → 300 ℃, maintaining for 6 min; the carrier gas is helium, and the column flow is 1.0 mL/min; the sample injection mode is split sample injection, the split ratio is 10:1, and the sample injection amount is 1.0 mu L; the interface temperature is 280 ℃; the ion source is an EI source, the temperature of the ion source is 230 ℃, the electron energy of the ion source is 70eV, and the temperature of a quadrupole rod is 150 ℃; the data acquisition mode is full scanning;
step 7, standard curve establishment: preparing a standard series of 5 mass concentration points, so that the mass concentrations of the aclonifen are respectively 2.0 mug/mL, 4.0 mug/mL, 8.0 mug/mL, 10.0 mug/mL and 20.0 mug/mL, and the mass concentration of the internal standard phenanthrene-d 10 is 2.0 mug/mL; carrying out sample injection analysis in sequence from low concentration to high concentration according to the instrument conditions in the step 6 to obtain a mass spectrum total ion flow graph of the herbicidal ether with different concentrations, and recording the retention time and the peak area of a quantitative ion mass spectrum peak of the herbicidal ether, wherein the quantitative ion of the herbicidal ether is 283, and the qualitative ions are 202 and 253; establishing a standard curve of the herbicidal ether by taking the mass concentration ratio of the herbicidal ether to the internal standard compound as a horizontal coordinate and taking the quantitative ion response value ratio of the target compound to the internal standard compound as a vertical coordinate;
step 8, sample determination: setting the conditions of the gas chromatography-mass spectrometer according to the step 6, after the conditions are stable, sending the extraction concentrated solution with constant volume in the step 5 into a gas chromatograph through an automatic sample injector for separation and detecting by a mass spectrum detector, and quantifying by retention time, fragment ion mass-to-charge ratio and abundance ratio, and an internal standard method;
step 9, calculating a result: according to the peak areas of the herbicidal ether and the internal standard substance measured by a gas chromatography-mass spectrometer, the concentration of the herbicidal ether in the extraction liquid is obtained by a standard curve equation, and then according to the sample amount and the dry matter content of the sample, the concentration of the herbicidal ether in the soil sample is calculated; the difference between the relative retention time of the aclonifen in the sample and the relative retention time of the compound in the standard series solution is within +/-0.03 s, and the relative deviation between the abundance ratio of the auxiliary qualitative ions to the quantitative ions of the aclonifen in the sample and the abundance ratio of the auxiliary qualitative ions to the quantitative ions in the standard solution is within +/-30%.
2. The method for detecting the pesticide residue of the aclonifen in the soil as claimed in claim 1, wherein the method comprises the following steps: the method for extracting the pesticide residue of the aclonifen in the soil sample in the step 2 is pressure solvent extraction, wherein the extraction solvent is a mixed solvent of dichloromethane and acetone, and the volume ratio is 1: 1.
3. The method for detecting the pesticide residue of the aclonifen in the soil as claimed in claim 1, wherein the method comprises the following steps: and 5, dehydrating the extract liquor in the step 5 by using anhydrous sodium sulfate, and converting the solvent of the extract liquor into n-hexane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101718756A (en) * | 2009-11-24 | 2010-06-02 | 湖南省烟草公司郴州市公司 | Method for simultaneously measuring residual quantity of three types of herbicide in vega soil |
| CN102539559A (en) * | 2011-12-24 | 2012-07-04 | 浙江大学 | Method for quantitatively detecting residual sulfonylurea herbicide trace amount in soil |
| CN108362786A (en) * | 2018-01-10 | 2018-08-03 | 杭州中检测研究院有限公司 | The Accelerate solvent extraction analysis method of N,N-dimethylformamide in a kind of soil |
| WO2020232970A1 (en) * | 2019-05-17 | 2020-11-26 | 江南大学 | Method for determining short chain fatty acid content in intestinal contents or excrement |
-
2021
- 2021-12-24 CN CN202111604934.2A patent/CN114660190B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101718756A (en) * | 2009-11-24 | 2010-06-02 | 湖南省烟草公司郴州市公司 | Method for simultaneously measuring residual quantity of three types of herbicide in vega soil |
| CN102539559A (en) * | 2011-12-24 | 2012-07-04 | 浙江大学 | Method for quantitatively detecting residual sulfonylurea herbicide trace amount in soil |
| CN108362786A (en) * | 2018-01-10 | 2018-08-03 | 杭州中检测研究院有限公司 | The Accelerate solvent extraction analysis method of N,N-dimethylformamide in a kind of soil |
| WO2020232970A1 (en) * | 2019-05-17 | 2020-11-26 | 江南大学 | Method for determining short chain fatty acid content in intestinal contents or excrement |
Non-Patent Citations (1)
| Title |
|---|
| 胡恩宇;杨丽莉;王美飞;吴丽娟;: "加速溶剂萃取-气相色谱/串联质谱法测定土壤中20种有机氯农药", 环境监控与预警, no. 06, 15 December 2013 (2013-12-15) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115656395A (en) * | 2022-08-17 | 2023-01-31 | 山东省产品质量检验研究院 | Method for measuring multiple pesticide residues in soil by using dispersed solid phase extraction |
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