CN114660190B - Method for detecting herbicidal ether pesticide residues in soil - Google Patents
Method for detecting herbicidal ether pesticide residues in soil Download PDFInfo
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- CN114660190B CN114660190B CN202111604934.2A CN202111604934A CN114660190B CN 114660190 B CN114660190 B CN 114660190B CN 202111604934 A CN202111604934 A CN 202111604934A CN 114660190 B CN114660190 B CN 114660190B
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000002689 soil Substances 0.000 title claims abstract description 79
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 17
- 238000009333 weeding Methods 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 44
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005259 measurement Methods 0.000 claims abstract description 16
- 238000001819 mass spectrum Methods 0.000 claims abstract description 14
- 238000000638 solvent extraction Methods 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 16
- 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 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000002170 ethers Chemical class 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 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
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 239000000203 mixture Substances 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
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000010586 diagram Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012634 fragment Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000012086 standard solution Substances 0.000 claims description 5
- 239000000126 substance Substances 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
- 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
- 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
- 238000010813 internal standard method Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000005070 sampling Methods 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000004009 herbicide Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 9
- 238000011156 evaluation Methods 0.000 abstract description 4
- 238000011835 investigation Methods 0.000 abstract description 4
- 238000003900 soil pollution Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005527 soil 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
- 230000008859 change Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000012502 risk assessment Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical 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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000010355 oscillation Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011160 research Methods 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
- 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
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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
-
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/86—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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- 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)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a method for detecting herbicide ether pesticide residues in soil, wherein the herbicide ether in the soil is subjected to pressurized extraction on a pressure solvent extraction instrument by using a mixed solvent of dichloromethane and acetone, and an extract is subjected to concentration, purification and solvent conversion, separated by using a gas chromatograph and detected by using a mass spectrum detector. The matrix marking experiment shows that: when the content of the weeding ether in the soil matrix sample is 0.2 mg/kg-2.0 mg/kg, the relative standard deviation (n=6) of the measurement result is 4.0-5.3%; the recovery rate of 6 independent determinations is 93.5% -106%, 94.2% -104% and 95.2% -106% when the scalar of the weeding ether in the soil matrix sample is 2 mug, 5 mug and 10 mug; when the soil sampling amount is 10g and the volume of the fixed volume of the extract is 1.0mL, the detection limit of the weeding ether in the soil is 0.04mg/kg, and the lower measurement limit is 0.16mg/kg. The invention adopts a mass spectrum detector for qualitative, has high resolution and strong anti-interference capability; the soil sample is extracted by adopting a pressure solvent extraction instrument, so that the operation is convenient, and the automation degree is high; can meet the soil pollution investigation, risk evaluation and repair evaluation.
Description
Technical Field
The invention belongs to the technical field of environmental detection, and relates to a detection method of herbicidal ether pesticide residues in soil.
Background
The weeding ether is 2, 4-dichlorophenyl-4-nitrophenyl ether, and is a contact herbicide. The department of agriculture of 6 months 2002 issues a publication No. 199, and the herbicidal ether is a pesticide prohibited by national regulations. The world health organization international cancer research institute, 10 months 2017 published a list of carcinogens and herbicidal ethers were listed in the class 2B list of carcinogens. The herbicidal ether has been used as one of the main varieties of herbicide pesticides and is widely applied to agriculture and forestry weeding. Because the molecular structure of the pesticide is generally relatively stable and difficult to degrade naturally, the pesticide can not degrade and disappear in natural environment quickly after being applied, but is retained and accumulated in soil, underground water, surface water and marine water in different ways, and then finally endangers the health of human bodies through the ways of biological absorption 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 and movement of many old pesticide plants are stopped, and the safety utilization of the pesticide plant plots is becoming more and more popular in the public.
The detection of the content of the pesticide characteristic factors in the soil is a key technical support for evaluating the environmental quality of the soil for agriculture and forestry and for environmental investigation and risk assessment before the retired land block of an agricultural chemical factory is redeveloped and utilized, no special national standard or industry standard is formulated for the detection of the herbicide ether in the soil at present, the detection methods of the herbicide ether in the soil which are related in the prior literature report are all researched by methods before 20 years, and the detection methods are mainly carried out by using gas chromatography, liquid chromatography or thin-layer chromatography after soaking extraction, oscillation extraction or ultrasonic extraction by using organic solvents, and are all detected by using an electronic capture detector, a nitrogen-phosphorus detector and an ultraviolet detector or by adopting a thin-layer chromatography, so that the detection methods are qualitative in retention time, poor in anti-interference performance in a qualitative mode and extremely easy to generate false positive detection results. At present, the sample pretreatment and analysis application technology is rapidly developed, and the software and hardware of the instrument are gradually changed day by day, so that a method for measuring the herbicidal ether pesticide residue in the soil, which is convenient to operate, high in qualitative anti-interference capability and high in quantitative accuracy, is necessary to be established.
Disclosure of Invention
The invention aims to provide a method for measuring herbicide ether pesticide residues in soil, which is convenient to extract soil samples, has strong qualitative anti-interference capability and high quantitative accuracy, wherein a pressure solvent extractor is used for extracting herbicide ether in soil, and extract liquid enters a gas chromatograph for separation after being concentrated, purified and solvent-converted into n-hexane and is detected by a mass spectrum detector, so that the technical defects of the existing detection method in the aspects of qualitative analysis, sample extraction and the like are overcome.
In order to achieve the above object of the present invention, the following technical solutions are adopted:
The method for detecting the herbicidal ether pesticide residue in the soil specifically comprises the following steps:
Step 1, collecting and storing a sample: soil samples are collected according to soil environment monitoring technical Specification (HJ/T166) and are put into a clean brown glass bottle for preservation; the sample is refrigerated, protected from light and sealed in the transportation process, and if the sample cannot be analyzed and measured in time, the sample is refrigerated below 4 ℃ protected from light; when the soil sample is stored for 7 days in a refrigerator environment at 4 ℃, the change of the measurement result is less than 20%; the change of the measured result is less than 5% when the soil sample extract is stored for 7 days in a refrigerator environment at 4 ℃.
Step 2, sample preparation and extraction: removing foreign matters (branches, leaves, stones, etc.) in the soil sample, uniformly mixing the sample, and drying the sample by a freeze dryer if the moisture content of the sample is higher than 30%; simultaneously weighing two about 10g (accurate to 0.01 g) of soil samples, one for measuring the dry matter content and one for extraction by a pressure solvent extractor; the sample for extraction is added with a proper amount of diatomite, ground into a quicksand shape, then is filled into an extraction tank, and the weeding ether in the soil sample is extracted by pressurizing with a mixed solvent of dichloromethane and acetone (volume ratio is 1:1) on a pressure solvent extraction instrument.
Step 3, soil dry matter content determination: the dry matter content of the soil sample was measured according to the method of measuring dry matter and moisture of soil (HJ 613).
Step 4, pressure solvent extraction instrument conditions: the carrier gas (nitrogen) pressure is 1.0MPa, the heating temperature is 100 ℃, the pressure is 1700psi, the preheating balance is 5min, the static extraction time is 5min, the solvent leaching volume is 60% of the pool volume, the extraction nitrogen purging time is 70s, and the static extraction is carried out for 2 times.
Step 5, concentrating and purifying the extract liquid: the extract is dehydrated by anhydrous sodium sulfate, concentrated by a rotary evaporator or a water bath nitrogen blowing instrument, the solvent is converted into n-hexane, the internal standard (phenanthrene-d 10) solution is quantitatively added, and the volume is fixed to 1mL by n-hexane to be measured. 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, a rotary evaporator or a water bath nitrogen blowing instrument is used for concentration, the solvent is converted into n-hexane, and after the internal standard (phenanthrene-d 10) solution is quantitatively added, the n-hexane is used for volume measurement to 1mL to be measured. If the sample contains more sulfur-containing compounds, copper particles can be used for removing during purification. In addition to the use of commercially available special purification columns, gel permeation chromatography can also be used for purification.
Step 6, gas chromatography mass spectrometry instrument conditions: the temperature of the sample inlet is 280 ℃; the 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℃(6min); carrier gas is helium, and the column flow is 1.0mL/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 quaternary rod is 150 ℃; the data acquisition mode is full scanning.
Step 7, standard curve establishment: preparing a standard series of 5 mass concentration points, wherein the mass concentration of the weeding ether is 2.0 mug/mL, 4.0 mug/mL, 8.0 mug/mL, 10.0 mug/mL and 20.0 mug/mL respectively, and the mass concentration of the internal standard substance (phenanthrene-d 10) is 2.0 mug/mL; sequentially carrying out sample injection analysis from low concentration to high concentration according to the instrument condition in the step 6 to obtain mass spectrum total ion flow diagrams of the herbicidal ethers with different concentrations, recording the retention time of the herbicidal ethers and the peak area of the mass spectrum of quantitative ions, wherein the quantitative ions of the herbicidal ethers are 283, and the qualitative ions are 202 and 253; and establishing a weeding ether standard curve by taking the mass concentration ratio of the weeding ether to the internal standard compound as an abscissa and taking the quantitative ion response value ratio of the target compound to the internal standard compound as an ordinate.
Step 8, sample measurement: setting the conditions of a gas chromatograph-mass spectrometer according to the step 6, after the conditions are stable, sending the extraction concentrated solution subjected to volume fixing in the step 5 into the gas chromatograph through an automatic sampler for separation and detecting by a mass spectrometer detector, and quantifying by an internal standard method according to the retention time, the mass-to-charge ratio of fragment ions and the abundance ratio thereof.
Step 9, calculating results: and according to the peak areas of the weeding ether and the internal standard substance measured by the gas chromatograph-mass spectrometer, the concentration of the weeding ether in the extract liquid is obtained by a standard curve equation, and then the concentration of the weeding ether in the soil sample is obtained according to the sample sampling amount and the dry matter content thereof. The difference between the relative retention time of the weeding ether 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 auxiliary qualitative ions and quantitative ions of the weeding ether in the sample and the abundance ratio of auxiliary qualitative ions and quantitative ions in the standard solution is within +/-30%.
Target content W (mg/kg) =ρ i×V÷(m×ωdm in soil
Wherein: ρ i -the concentration of the target (herbicidal ether or cartap) in the extract, mg/L, as determined by the standard curve.
V-volume of extract, mL.
M-soil sample weight, g.
Omega dm -soil sample dry matter content,%.
Compared with the prior art, the invention has the beneficial effects that:
1. Compared with the retention time qualitative method, the invention adopts the mass spectrum detector to qualify the retention time, the characteristic fragment ion mass-charge ratio and the abundance ratio thereof, and has higher resolution and strong anti-interference capability.
2. The method for extracting the herbicidal ether pesticide residues in the soil by using the pressure solvent extraction instrument is a brand new extraction mode different from the existing literature method, is convenient to operate and high in automation degree, and is an efficient soil analysis pretreatment method.
3. The weeding ether pesticide residue in the soil is measured by adopting a pressure solvent extraction-gas chromatography mass spectrometry method, so that a key technical support required by new soil pollution condition investigation, risk assessment and restoration effect evaluation is provided for the redevelopment and safety utilization of retired plots of weeding ether pesticide production enterprises.
4. The method for determining the herbicidal ether pesticide residue in the soil has the advantages of lower detection limit and higher recovery rate, wherein the detection limit of the method is 0.04mg/kg, the standard adding recovery rate of a soil matrix sample is 93.5-106%, the method is superior to the recovery rate described in the literature method, and the technical requirements of soil pollution condition investigation, risk assessment and restoration effect evaluation detection are completely met.
Drawings
FIG. 1 is a total ion flow diagram of the detection of herbicidal ether pesticide residues in soil by the method of the present invention;
FIG. 2 is a standard graph of herbicidal ethers;
FIG. 3 is a total ion flow diagram of the herbicidal ethers and interferents.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings and examples.
The apparatus and reagents used in the examples:
gas chromatograph-mass spectrometer model Agilent 7890B/5977B with liquid autosampler and HP-5MS chromatography column (30 m.times.250 μm.times.0.25 μm), agilent technologies Co.
Quick solvent extractor, model Thermo SCIENTIFIC ASE.
A water bath nitrogen blower, model Organomation N-EVAP.
Electronic balance, model YP502N, shanghai, tianmei balance instruments limited.
Herbicidal ethers, 99.5% pure, shanghai An Spectrum laboratory technologies Co., ltd.
Internal standard (phenanthrene-d 10) stock solution, ρ=1000 mg/L, carbofuran company.
Acetone, methylene chloride, methanol, pesticide residue grade, shanghai An Spectrum experiment technology Co., ltd.
Anhydrous sodium sulfate, superior purity, national drug group.
The detection method comprises the following steps:
(1) And (3) collecting a sample: collecting according to soil environment monitoring technical Specification (HJ/T166), and placing in clean brown glass bottle, and refrigerating at below 4deg.C in dark place.
(2) Sample preparation and extraction: removing foreign matters, branches, leaves, stones and the like in the soil sample, and uniformly mixing the sample; simultaneously weighing two about 10g (accurate to 0.01 g) of soil samples, one for measuring the dry matter content and one for extraction by a pressure solvent extractor; the sample for extraction is added with a proper amount of diatomite, ground into a quicksand shape, then is filled into an extraction tank, and the weeding ether in the soil sample is extracted by pressurizing with a mixed solvent of dichloromethane and acetone (volume ratio is 1:1) on a pressure solvent extraction instrument.
(3) Pressure solvent extraction instrument condition setting: the carrier gas (nitrogen) pressure is 1.0MPa, the heating temperature is 100 ℃, the pressure is 1700psi, the preheating balance is 5min, the static extraction time is 5min, the solvent leaching volume is 60% of the pool volume, the extraction nitrogen purging time is 70s, and the static extraction is carried out for 2 times.
(4) Soil dry matter content determination: the dry matter content of the soil sample was measured according to the method of measuring dry matter and moisture of soil (HJ 613).
(5) Preparation of 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, fixing the volume by using methanol, and uniformly mixing to obtain an internal standard use solution with the concentration of 20mg/L.
(6) Concentrating and purifying the extract liquid: the extract is dehydrated by anhydrous sodium sulfate, concentrated by a rotary water bath nitrogen blower, the solvent is converted into n-hexane, 100 mu L of internal standard use solution is quantitatively added, and the volume is fixed to 1mL of the internal standard use solution by n-hexane to be measured.
(7) Gas chromatograph mass spectrometer condition settings: the temperature of the sample inlet is 280 ℃; the 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℃(6min); carrier gas is helium, and the column flow is 1.0mL/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 quaternary rod is 150 ℃; the data acquisition mode is full scanning.
(8) Preparing standard herbicide use solution: accurately weighing 12.75mg of the weeding ether in a 25mL volumetric flask, and uniformly mixing after metering the volume by methanol to obtain the standard weeding ether use solution with the concentration of 500mg/L.
(9) Establishing a standard curve: taking 5 volumetric flasks of 5mL, adding 2mL of methanol in advance, adding 20 mu L, 40 mu L, 80 mu L, 100 mu L and 200 mu L of standard use solution of weeding ether respectively, adding 100 mu L of standard use solution of internal standard, fixing the volume by using methanol, and uniformly mixing to prepare a standard series of 5 mass concentration points, so that the mass concentration of weeding ether is 2.0 mu g/mL, 4.0 mu g/mL, 8.0 mu g/mL, 10.0 mu g/mL and 20.0 mu g/mL in sequence, and the mass concentration of internal standard substances is 2.0 mu g/mL. And (3) sequentially carrying out sample injection analysis from low concentration to high concentration according to the instrument condition in the step (7) to obtain mass spectrum total ion flow diagrams of the herbicidal ethers with different concentrations, and recording the retention time of the herbicidal ethers and the quantitative ion mass spectrum peak area. And establishing a calibration curve equation of the weeding ether as Y= 0.02759X-0.002714, wherein the mass concentration ratio of the weeding ether to the internal standard compound is taken as an abscissa, the quantitative ion response value ratio of the weeding ether to the internal standard compound is taken as an ordinate, and the linear correlation coefficient r is 0.998. Fig. 1 is a total ion flow diagram of the detection of herbicidal ether pesticide residues in soil, and fig. 2 is a standard plot of herbicidal ether.
(10) Sample measurement: setting the condition of a gas chromatograph-mass spectrometer according to the step (7), after the condition is stable, sending the extraction concentrated solution subjected to volume fixing in the step (6) into the gas chromatograph through an automatic sampler for separation and detecting by a mass spectrometer detector, and quantifying by an internal standard method according to the retention time, the mass-to-charge ratio of fragment ions and the abundance ratio thereof.
(11) And (3) calculating results: and according to the peak areas of the weeding ether and the internal standard substance measured by the gas chromatograph-mass spectrometer, the concentration of the weeding ether in the extract liquid is obtained by a standard curve equation, and then the concentration of the weeding ether in the soil sample is obtained according to the sample sampling amount and the dry matter content thereof. The difference between the relative retention time of the weeding ether 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 auxiliary qualitative ions and quantitative ions of the weeding ether in the sample and the abundance ratio of auxiliary qualitative ions and quantitative ions in the standard solution is within +/-30%.
Target content W (mg/kg) =ρ i×V÷(m×ωdm in soil
Wherein: ρ i -the concentration of the target (herbicidal ether or cartap) in the extract, mg/L, as determined by the standard curve.
V-volume of extract, mL.
M-soil sample weight, g.
Omega dm -soil sample dry matter content,%.
Example 1
(1) Method detection limit: diluting the standard use solution of the weeding ether by 10 times to obtain the standard use solution of the weeding ether, accurately transferring 20 mu L of the standard use solution of the weeding ether into an extraction tank filled with 10g of quartz sand by using a micropipette according to the technical guidelines of environmental monitoring analysis method standard (HJ 168), performing pressurized extraction on a pressure solvent extraction instrument by using methylene dichloride and acetone (1:1) according to the instrument condition in the step (3), performing nitrogen blowing concentration on the extraction liquid according to the step (6), converting the solvent into n-hexane, quantitatively adding 100 mu L of the standard use solution, then using n-hexane to fix the volume to 1mL, sending the mixture into a gas chromatograph by using an automatic sampler according to the instrument condition in the step (7), separating the mixture, detecting the mixture by using a mass spectrum detector, and determining the weeding ether content. The whole process is repeated for 6 times, the minimum detection limit MDL of the weeding ether is calculated to be 0.04mg/kg according to the following formula, and the detection limit of the weeding ether is measured to be 0.16mg/kg by taking the 4-time minimum detection limit as the lower limit.
MDL＝t(n-1,0.99)×S
Wherein: n—number of replicates of the sample, method n=7;
t—t distribution value when the degree of freedom is n-1 and the confidence is 99% (t= 3.143 when n=7);
S-standard deviation of n replicates.
(2) The detection limit of the thin layer chromatography of the comparison document 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 of the invention is 0.04mg/kg, which is superior to the detection limit of the comparison document method.
Example 2
The precision of the method is as follows: accurately transferring different volumes of standard use liquid of the weeding ether into an extraction tank filled with 10g of soil matrix sample by using a micropipette, performing pressurized extraction on a pressure solvent extraction instrument by using methylene dichloride and acetone (1:1) according to the instrument conditions in the step (3), performing nitrogen blowing concentration on the extraction liquid according to the step (6), converting the solvent into n-hexane, quantitatively adding 100 mu L of internal standard use liquid, metering the volume to 1mL by using n-hexane, sending the internal standard use liquid into a gas chromatograph by using an automatic sampler according to the instrument conditions in the step (7), separating the mixture, detecting the mixture by using a mass spectrum detector, and determining the weeding ether content in the soil matrix sample. The above operation was repeated 5 times in the whole procedure, and the precision measurement was performed, wherein the precision measurement data are shown in Table 1, and the relative standard deviation RSD (n=6) of the measurement results was 4.0% to 5.3% when the content of the herbicidal ether in the soil matrix sample was 0.2mg/kg to 2.0 mg/kg.
Table 1 precision measurement data (n=6)
Example 3
(1) Accuracy of the method: the standard solution is respectively and accurately taken by a micropipette at 40 mu L, 100 mu L and 200 mu L, and the standard solution is added into an extraction tank filled with 10g of soil matrix sample, the pressure extraction is carried out on a pressure solvent extraction instrument by using methylene dichloride and acetone (1:1) according to the instrument condition of step (3), the solvent is converted into normal hexane by the nitrogen blowing concentration of step (6), 100 mu L of internal standard use solution is quantitatively added, the normal hexane is used for constant volume to 1mL, the mixture is sent into a gas chromatograph by an automatic sampler according to the instrument condition of step (7) for separation and detected by a mass spectrum detector, and the content of the weeding ether in the soil matrix sample is measured, and the measurement result is shown in table 2.
TABLE 2 data for determining recovery rate by adding standard
(2) The recovery rate of the thin layer chromatography of the comparison document 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 is 93.5-106%, which is superior to the recovery rate of the comparison document method.
Interference test: according to the method disclosed by the reference, the determination of the easily-interfered weeding ether such as the organic chlorine pesticide DDT, DDE, DDD is carried out by using the gas chromatography mass spectrometry method disclosed by the invention to simultaneously determine the weeding ether and the organic chlorine pesticide, wherein the mass spectrum detector is characterized by retention time, characteristic fragment ion mass-charge ratio and abundance ratio, and the qualitative identification of the weeding ether is not interfered by the organic chlorine pesticide DDT, DDE, DDD.
Example 4
Sample storage stability: the collected soil samples of the retired plots of the pesticide factories are taken back to the laboratory and stored in a refrigerator environment at 4 ℃, wherein the No. 1 sample is the soil sample containing the higher concentration of the herbicidal ether, and the No. 2 sample is the soil sample containing the lower concentration of the herbicidal ether. And (3) performing stability test on the soil sample according to the pressure solvent extraction condition in the step (3), the concentration constant volume step in the step (6) and the gas chromatography-mass spectrometry analysis condition in the step (7), wherein the measurement result is shown in table 4, and the change of the measurement result is less than 20% when the soil sample is stored for 7 days in a refrigerator environment at 4 ℃.
Table 4 soil sample stability assay data
Example 5
Storage stability of the extract: and (3) carrying out soil sample extraction, concentration and volume fixing according to the step (2) and the step (6) after taking the collected soil samples of the retired plots of the pesticide factories back to a laboratory, and storing the extract liquid in a refrigerator environment at the temperature of 4 ℃, wherein a No. 1 sample is a soil sample extract liquid containing the higher concentration of the herbicidal ether, and a No. 2 sample is a soil sample extract liquid containing the lower concentration of the herbicidal ether. And (3) performing a stability test on the soil sample extract according to the gas chromatography-mass spectrometry analysis condition 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 extract is stored for 7 days in a refrigerator environment at 4 ℃.
TABLE 5 sample extract stability assay data
The above embodiments are merely for illustrating the technical aspects of the present invention, and although the present invention has been described in detail with reference to the above 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 detection method of herbicidal ether pesticide residue in soil is characterized in that: the method comprises the following steps:
Step 1, collecting and storing a sample: collecting soil samples, storing in clean dark glass bottles, refrigerating, keeping away from light, sealing in the sample transportation process, and refrigerating the samples at a temperature below 4 ℃ in the dark if the samples cannot be analyzed and measured in time;
step 2, sample preparation and extraction: removing foreign matters in a soil sample, uniformly mixing the sample, and when the moisture content of the sample is higher than 30%, firstly drying the sample by a freeze dryer until the moisture content is lower than 30%; simultaneously weighing two parts of 10g soil samples, one part of the soil samples is used for measuring the dry matter content, and the other part of the soil samples is used for extraction by a pressure solvent extraction instrument; adding diatomite into a sample for extraction, grinding the sample to form a quicksand shape, then loading the mixture into an extraction tank, and performing pressurized extraction on the herbicidal ether in the soil sample on a pressure solvent extractor;
step 3, measuring the dry matter content of the soil;
Step4, extracting by a pressure solvent extractor: pressure solvent extractor conditions: the carrier gas pressure is 1.0MPa, the heating temperature is 100 ℃, the pressure is 1700psi, the preheating balance is 5min, the static extraction time is 5min, the solvent leaching volume is 60% of the pool volume, the extraction nitrogen purging time is 70s, the static extraction is carried out for 2 times, and the liquid after the static extraction is mixed to obtain an extract;
Step 5, concentrating and purifying the extract liquid: dewatering the extract, concentrating by using a rotary evaporator or a water bath nitrogen blowing instrument, converting the solvent, quantitatively adding an internal standard phenanthrene-d 10 solution, and fixing the volume to 1mL by using n-hexane to be measured;
when the extraction concentrated solution contains obvious impurities or has 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, the purification is carried out, a rotary evaporator or a water bath nitrogen blowing instrument is used for concentrating and converting the solvent into n-hexane, and after the internal standard phenanthrene-d 10 solution is quantitatively added, the n-hexane is used for volume fixing to 1mL to be detected;
removing copper particles when the sample contains sulfur-containing compounds and is purified; also include purification using commercially available dedicated purification columns or purification using gel permeation chromatography;
Step 6, gas chromatography mass spectrometry instrument conditions: the temperature of the sample inlet is 280 ℃; the column temperature is 40 ℃ to 15 ℃ to 70 ℃ to 20 ℃ to 90 ℃ to 7.27 ℃ to 130 ℃ to 20 ℃ to 180 ℃ to 10 ℃ to 200 ℃ to 30 ℃ to 260 ℃ to 20 ℃ to 300 ℃ and is maintained for 6min; the carrier gas is helium, and the flow rate of the column is 1.0mL/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 quaternary rod is 150 ℃; the data acquisition mode is full scanning;
Step 7, standard curve establishment: preparing a standard series of 5 mass concentration points, wherein the mass concentration of the weeding ether is 2.0 mug/mL, 4.0 mug/mL, 8.0 mug/mL, 10.0 mug/mL and 20.0 mug/mL respectively, and the mass concentration of the internal standard phenanthrene-d 10 is 2.0 mug/mL; sequentially carrying out sample injection analysis from low concentration to high concentration according to the instrument condition in the step 6 to obtain mass spectrum total ion flow diagrams of the herbicidal ethers with different concentrations, recording the retention time of the herbicidal ethers and the peak area of the mass spectrum of quantitative ions, wherein the quantitative ions of the herbicidal ethers are 283, and the qualitative ions are 202 and 253; establishing a weeding ether standard curve by taking the mass concentration ratio of the weeding ether to the internal standard compound as an abscissa and taking the quantitative ion response value ratio of the target compound to the internal standard compound as an ordinate;
Step 8, sample measurement: setting gas chromatograph-mass spectrometer conditions according to the step 6, after the conditions are stable, sending the extraction concentrated solution subjected to volume fixation in the step 5 into the gas chromatograph through an automatic sampler for separation and detecting by a mass spectrometer detector, and quantifying by an internal standard method according to retention time, fragment ion mass-charge ratio and abundance ratio;
Step 9, calculating results: according to the peak areas of the weeding ether and the internal standard substance measured by a gas chromatograph-mass spectrometer, the concentration of the weeding ether in the extract is obtained by a standard curve equation, and then the concentration of the weeding ether in the soil sample is calculated according to the sample sampling amount and the dry matter content thereof; the difference between the relative retention time of the weeding ether 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 auxiliary qualitative ions and quantitative ions of the weeding ether in the sample and the abundance ratio of auxiliary qualitative ions and quantitative ions in the standard solution is within +/-30%.
2. The method for detecting herbicidal ether pesticide residues in soil according to claim 1, wherein the method comprises the following steps: the extraction method of the herbicidal ether pesticide residue in the soil sample in the step 2 is pressure solvent extraction, and the extraction solvent is a mixed solvent of dichloromethane and acetone, and the volume ratio is 1:1.
3. The method for detecting herbicidal ether pesticide residues in soil according to claim 1, wherein the method comprises the following steps: and (3) dehydrating the extract in the step (5) by using anhydrous sodium sulfate, and converting the solvent of the extract into n-hexane.
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| CN102539559A (en) * | 2011-12-24 | 2012-07-04 | 浙江大学 | Method for quantitatively detecting residual sulfonylurea herbicide trace amount in soil |
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