CN113311095A - Water body pesticide pretreatment enrichment method and water body pesticide content detection method - Google Patents
Water body pesticide pretreatment enrichment method and water body pesticide content detection method Download PDFInfo
- Publication number
- CN113311095A CN113311095A CN202110499332.9A CN202110499332A CN113311095A CN 113311095 A CN113311095 A CN 113311095A CN 202110499332 A CN202110499332 A CN 202110499332A CN 113311095 A CN113311095 A CN 113311095A
- Authority
- CN
- China
- Prior art keywords
- water body
- pesticide
- phase extraction
- solid phase
- pesticides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000575 pesticide Substances 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000001514 detection method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 42
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims abstract description 40
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 12
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000620 organic polymer Polymers 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229920000779 poly(divinylbenzene) Polymers 0.000 claims abstract description 5
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 claims abstract description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001819 mass spectrum Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 20
- 239000005947 Dimethoate Substances 0.000 abstract description 12
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 abstract description 12
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 abstract description 11
- 238000007689 inspection Methods 0.000 abstract description 8
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000005946 Cypermethrin Substances 0.000 description 9
- 229960005424 cypermethrin Drugs 0.000 description 9
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- RDYMFSUJUZBWLH-AZVNHNRSSA-N qy5y9r7g0e Chemical compound C([C@H]12)OS(=O)OC[C@@H]1[C@]1(Cl)C(Cl)=C(Cl)[C@@]2(Cl)C1(Cl)Cl RDYMFSUJUZBWLH-AZVNHNRSSA-N 0.000 description 8
- XQUXKZZNEFRCAW-UHFFFAOYSA-N fenpropathrin Chemical compound CC1(C)C(C)(C)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 XQUXKZZNEFRCAW-UHFFFAOYSA-N 0.000 description 7
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 7
- 231100000572 poisoning Toxicity 0.000 description 7
- 230000000607 poisoning effect Effects 0.000 description 7
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 241001251200 Agelas Species 0.000 description 2
- 101100189913 Caenorhabditis elegans pept-1 gene Proteins 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010008428 Chemical poisoning Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- -1 carbamate ester Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003993 organochlorine pesticide Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas 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
- G01N2030/062—Preparation extracting sample from raw material
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to the technical field of water body detection, in particular to a pretreatment enrichment method for pesticides in a water body and a detection method for pesticide content in the water body. The invention relates to a method for enriching pesticides in water body by pretreatment, which adopts solid-phase extraction, wherein two organic polymer solid-phase extraction columns are adopted for the solid-phase extraction and are connected in series, and fillers in the organic polymer solid-phase extraction columns are respectively polydivinylbenzene polymer, polyvinyl divinylbenzene with pyrrolidone and trace ureido functional groups bonded on the surfaces, hydrophilic styrene-divinylbenzene polymer and functionalized styrene-divinylbenzene polymer; the pesticide is one or more of organic phosphorus, organic chlorine, carbamate and pyrethrin. Based on the enrichment method, a pesticide GC-MS inspection method is established, and results show that a working curve, detection limit, recovery rate and precision all meet the inspection of pesticides in water toxicity, wherein the detection limit of pentachlorophenol, dimethoate, methamidophos and carbofuran is lower than the requirement of GB 11607-1989 fishery water quality standard.
Description
Technical Field
The invention relates to the technical field of water body detection, in particular to a water body pesticide pretreatment enrichment method and a water body pesticide content detection method.
Background
The common water poisoning cases are mainly fishpond water pesticide poisoning cases. With the vigorous development of the Guangdong provincial aquaculture industry, cases of fish pond theft or repeated poison exposure are increased suddenly, and huge economic losses are caused to farmers. The most important characteristics of the toxicity-throwing case are that the randomness of the pesticide is high, the regionality is strong, the pesticide content in the fishpond water is low, the matrix is complex, and the inspection difficulty is high. The key of detecting the fishpond poisoning case is to effectively enrich and quickly detect the pesticide in the water sample of the fishpond poisoning case.
If the water body simultaneously contains carbamate, organic phosphorus, pyrethrin and organochlorine pesticides, the detection difficulty can be further increased, effective enrichment needs to be carried out, and the collection, enrichment and detection need to be convenient, quick and stable so as to meet the requirement of quick and accurate determination in the case of detecting and detoxifying.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a water body pesticide pretreatment enrichment method. Based on the enrichment method, a set of pesticide GC-MS detection method is established at the same time so as to detect the pesticide and the content in the water body. Aiming at the characteristics of low pesticide concentration, complex matrix and high inspection difficulty in the case of water poisoning, the invention establishes a method for efficiently enriching and rapidly extracting the on-site pesticide of the large-volume water sample.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for enriching pesticides in water body before treatment adopts solid phase extraction, wherein pesticides in water body are enriched, two organic polymer solid phase extraction columns are adopted for series connection in the solid phase extraction, and fillers in the organic polymer solid phase extraction columns are respectively a polydivinylbenzene polymer, a polyvinyl divinylbenzene with pyrrolidone and trace ureido functional groups bonded on the surface, a hydrophilic styrene-divinylbenzene polymer and a functionalized styrene-divinylbenzene polymer; the pesticide is organic phosphorus and organic chlorine.
Further, the organophosphorus is methamidophos, and the organochlorine is pentachlorophenol.
Further, the pesticide also comprises one or more of carbamate and pyrethrin.
Further, the pesticide is methamidophos, phorate, dimethoate, carbofuran, propoxur, cypermethrin, fenpropathrin, alpha-endosulfan and pentachlorophenol.
Furthermore, solid phase extraction columns, the filler of which is polydivinylbenzene polymer and the surface of which is bonded with pyrrolidone and a trace amount of ureido functional groups, are sequentially connected in series. When the solid-phase extraction of the two fillers is used for separately detecting methamidophos, phorate, dimethoate, carbofuran, propoxur, cypermethrin, fenpropathrin, alpha-endosulfan and pentachlorophenol, the recovery rate of the methamidophos is low when the methamidophos is detected, and the pentachlorophenol cannot be detected when the alpha-endosulfan and the pentachlorophenol are detected, the problem can be effectively solved after the two extraction columns are connected in series, and the enrichment effect of the methamidophos and the pentachlorophenol is improved.
Furthermore, solid phase extraction columns with the filler of hydrophilic styrene-divinylbenzene polymer and functionalized styrene-divinylbenzene polymer are connected in series in sequence. When the solid-phase extraction of the two fillers is used for separately detecting methamidophos, phorate, dimethoate, carbofuran, propoxur, cypermethrin, fenpropathrin, alpha-endosulfan and pentachlorophenol, the recovery rate of the methamidophos detected by the filler is low, and the recovery rate of the pentachlorophenol detected by the filler is low.
Further, the body of water is taken from a body of water in a pond.
Further, the solid phase extraction column was activated with ethanol.
The invention also provides a method for detecting the pesticide content in the water body, which comprises the following steps:
s1: by utilizing the pretreatment enrichment method, a sample is loaded through a solid phase extraction column for enrichment;
s2: eluting and concentrating the enriched pesticide, and carrying out gas chromatography-mass spectrometry detection;
wherein, the chromatographic conditions in step S2 are: the chromatographic column is an HP-5MS column, and the temperature programming condition is as follows: the initial temperature is 60 ℃, the temperature is increased to 180 ℃ at the speed of 10 ℃/min and is kept for 10min, and the temperature is increased to 280 ℃ at the speed of 20 ℃/min and is kept for 10 min; the temperature of a sample inlet is 200 ℃, the split ratio is 5:1, and the flow is 1.0 mL/min;
mass spectrum conditions: EI mode ionization, wherein the standard electron energy is 70 eV; the mass spectrum scanning range is 45-450 amu; scan mode detection; ion source temperature: 230 ℃; interface transmission temperature: 280 ℃.
Further, the column model was 30 m.times.0.25 mm.times.0.25. mu.m.
Further, the flow rate of the sample (water sample) passing through the solid phase extraction column in the step S1 is 3-9.0 mL/min.
Compared with the prior art, the invention has the beneficial effects that:
the invention overcomes the problems of low pesticide concentration, complex matrix and the like in the case of water poisoning, and brings great inspection difficulty, establishes a method for efficiently enriching and quickly extracting the pesticide on site of the large-volume water sample, establishes a GC-MS inspection method by using the common pesticide in the case of water poisoning, and ensures that the working curve, detection limit, recovery rate and precision of pesticide inspection meet the inspection requirements of the case of water poisoning, wherein the detection limit of pentachlorophenol, dimethoate, methamidophos and carbofuran is lower than the requirements of GB 11607-1989 fishery water quality standard.
Drawings
FIG. 1 is a TIC chart of GC-MS for detecting pesticide standard substance by the detection method of the invention.
Detailed Description
The test methods used in the following experimental examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
1. The information of the solid phase extraction column used in this example is as follows: the technical personnel in the field can select corresponding commercial model according to the requirement of the filler, the model of the manufacturer is not strictly limited, and the specification of the following solid phase extraction column model is 500mg/6 mL.
2. The 9 classes of pesticides mentioned in this example: organic phosphorus: methamidophos, phorate, dimethoate; carbamate ester: carbofuran, propoxur; pyrethrin: cypermethrin, fenpropathrin; organic chlorine: alpha-endosulfan and pentachlorophenol.
3. The detection method adopted in the embodiment is as follows:
(1) treatment of the test sample
Extracting a water sample on site, passing the water sample through a solid phase extraction column (activated by ethanol before use) at the sample flow rate of 7.0mL/min, sending the water sample to a laboratory, dehydrating and drying: blowing nitrogen or vacuum pumping the solid phase extraction column to dryness to remove water; and (3) elution: eluting with 5ml ethyl acetate through solid phase extraction column, and removing water from the eluate through anhydrous sodium sulfate dry column or anhydrous sodium sulfate powder; concentration and volume fixing: the eluate was blown nearly dry at 45 ℃ and room temperature with nitrogen, and then made up to 100. mu.L with methanol for examination.
(2) Instruments and reagents
7890A 5977A gas chromatograph-MS (Agilent Technologies, USA). Chromatographic conditions are as follows: chromatography column HP-5MS column (30 m.times.0.25 mm. times.0.25 μm) Quartz capillary column. Temperature programming: 60 deg.C (0min)10℃/min 180℃(10min)20℃/min280 deg.C (10min), representing an initial temperature of 60 deg.C, heating to 180 deg.C at 10 deg.C/min for 10min, and heating to 280 deg.C at 20 deg.C/min for 10 min; solvent delay time 3 min. The sample injection volume is 1 muL, the sample injection inlet temperature is 200 ℃ (the ultra-inert diversion liner tube), the diversion ratio is 5:1, and the flow is 1.0 mL/min. Mass spectrum conditions: EI mode ionization, wherein the standard electron energy is 70 eV; the mass spectrum scanning range is 45-450 amu; scan mode detection; ion source temperature: 230 ℃; interface transmission temperature: 280 ℃.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Firstly, analyzing a pesticide standard product:
1. 9 pesticide standards (methamidophos, phorate, dimethoate, propoxur, carbofuran, pentachlorophenol, alpha-endosulfan, fenpropathrin, cypermethrin) are prepared into methanol or acetone solutions with the concentration of 1000 mu g/mL (the methanol or the acetone is analytically pure, and other reagents are analytically pure if no special indication exists). Then using methanol to prepare 9 mixed standard solutions with pesticide concentration of 100 mu g/mL, wherein TIC of GC-MS (conditions are as above) is shown in figure 1 (1-methamidophos, 2-propoxur, 3-phorate, 4-dimethoate, 5-carbofuran, 6-pentachlorophenol, 7-alpha-endosulfan, 8-fenpropathrin, 9-cypermethrin), and retention time and characteristic ions of each pesticide are shown in Table 1.
Table 1: retention time and characteristic ion of each pesticide in GC-MS
| Serial number | Pesticide | Retention time/min | Characteristic ion | Quantitative extraction of |
| 1 | Methamidophos | 7.958 | 94,141,47,64 | 94 |
| 2 | Killing drug | 12.955 | 110,152,81,58 | 110 |
| 3 | Phorate | 14.251 | 75,121,97,260 | 75 |
| 4 | Leguo (fruit of musical instruments) | 14.923 | 87,93,125.79 | 87 |
| 5 | Carbofuran | 15.179 | 164,149,131,122 | 164 |
| 6 | Pentachlorophenol | 15.466 | 266,165,130,95 | 266 |
| 7 | Alpha-endosulfan | 24.936 | 195,237,170.265 | 195 |
| 8 | Fenpropathrin | 27.767 | 97,181,265,125 | 97 |
| 9 | Cypermethrin | 30.362,30.492,30.653 | 163,181,91,127 | 163 |
Secondly, the invention simultaneously analyzes 9 pesticides to be detected, and the physicochemical parameters are shown in Table 2.
Table 2: physical and chemical parameters of 9 kinds of pesticide
Note that: "-" indicates no data
Kow ratio of the equilibrium concentration of the organic compound in both octanol and water phases, reflecting the lipophilic/hydrophilic size of the organic compound. The value is generally 10-4 to 10-8, and is generally represented by lgKow for convenience. The lgKow is less than 1 and belongs to a polar compound, the lgKow is more than 3 and belongs to a non-polar compound, and the lgKow is 1-3 and belongs to a medium polar compound.
As can be seen from Table 2, the water solubility or polarity of the 9 pesticides varied widely, with hydrophobic constants ranging from-0.8 for methamidophos to 6.6 for cypermethrin. Therefore, in selecting a solid phase extraction column, its water solubility or polarity must be considered. For the organophosphorus pesticide with high water solubility of methamidophos, solid phase extraction from polar matrix water is difficult, a column cannot be found to simultaneously achieve high recovery rate extraction of the 9 pesticides, and the extraction of the 9 pesticides can only be relatively achieved under the condition that certain detection limit is met.
And thirdly, adding pesticide mixed standard products into the blank fishpond water to prepare 9 water samples to be detected, wherein the pesticide concentrations of the water samples are all 0.1 mu g/mL. The solid phase extraction and GC-MS detection methods were used to extract with different solid phase extraction columns, and the results of obtaining the recovery rate were found in table 3.
Table 3 recovery rates in units of (n 6, RSD 3-15%) for different solid phase extraction columns
As can be seen from Table 3, the isolation of pentachlorophenol from Agela Cleanert PEP-2 alone resulted in lower recovery of methamidophos from the GDX403 extraction column and pentachlorophenol from the Agilent Bond Elut PPL extraction column, and therefore, it was considered that the two solid phase extraction columns were connected in series and the recovery data are shown in Table 4.
Table 4 recovery rate of the series solid phase extraction column, unit% (n ═ 6, RSD ═ 3-15%)
As can be seen from Table 4, the recovery rate of the substance to be detected is affected by different serial connection sequences of the two solid phase extraction columns, namely, the Agela Cleanert PEP-2 is serially connected with the upper part of the GDX403, and the recovery rate of the pentachlorophenol is 0. The Agilent Bond Elut Plexa and the Agilent Bond Elut PPL solid phase extraction columns are sequentially connected in series, and the extraction effect on pesticides is optimal.
Four, linear equation, detection limit
Adding mixed standard solutions (9 pesticide standard substance mixed solutions) with series concentrations into blank fishpond water to prepare water samples (9 water samples to be detected with the pesticide concentrations of above concentrations) with concentrations of 0.1, 0.5, 1, 2, 5, 10, 20, 50, 100, 200 and 500ng/mL, carrying out solid-phase extraction after field collection, wherein the conditions of the solid-phase extraction are as above (solid-phase extraction columns are connected in series by Plexa + ppl), and the chromatographic conditions are as above. The concentration of the pesticide to be detected is taken as the abscissa, the chromatographic peak area of the extracted base peak ion fragment is taken as the ordinate to establish a standard curve, and the linear equation, the correlation coefficient and the detection limit of the 9 pesticides are obtained, and the result is shown in table 5. All pesticides have correlation coefficient of above 0.99, good linearity, and detection limit of 0.5-10ng/mL (S/N is 3). The detection limit of pentachlorophenol, dimethoate, methamidophos and carbofuran is lower than GB 11607-1989 fishery water quality standard (sodium pentachlorophenol is less than or equal to 10ng/mL, dimethoate is less than or equal to 100ng/mL, methamidophos is less than or equal to 1000ng/mL, carbofuran is less than or equal to 10ng/mL)
TABLE 59 Linear Range, regression equation, detection limits for pesticides
Fifthly, precision and recovery rate
Respectively adding 6 samples of low, medium and high concentration level mixed standard solutions into blank fishpond water, simulating field enrichment extraction and laboratory determination, adopting a solid phase extraction column of Plexa + ppl series connection, and obtaining the results shown in Table 6 under the conditions of solid phase extraction and chromatography. The recovery rates of dimethoate, propoxur and carbofuran are between 91.7% and 107.2%, the recovery rates of phorate, pentachlorophenol, alpha endosulfan and fenpropathrin are between 42.6% and 60.7%, the recovery rate of cypermethrin is between 29.3% and 36.6%, and the recovery rate of methamidophos is between 14.6% and 16.9%. The Relative Standard Deviation (RSD) is 3.8% -13.7%.
TABLE 69 recovery and precision of the pesticides on standard (n ═ 6)
As can be seen from tables 5 and 6, the working curve, detection limit, recovery rate and precision of pesticide detection meet the detection of pesticides in water toxicity cases, wherein the detection limit of pentachlorophenol, dimethoate, methamidophos and carbofuran is lower than the requirement of GB 11607-1989 fishery water quality standard.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A method for enriching pesticides in water body before treatment is characterized in that solid phase extraction is adopted to enrich pesticides in water body, two organic polymer solid phase extraction columns are adopted in the solid phase extraction to be connected in series, and fillers in the organic polymer solid phase extraction columns are polydivinylbenzene polymers, polyvinyl divinylbenzene with pyrrolidone and trace ureido functional groups bonded on the surfaces, hydrophilic styrene-divinylbenzene polymers and functionalized styrene-divinylbenzene polymers respectively; the pesticide comprises organic phosphorus and organic chlorine.
2. The water body pesticide pretreatment enrichment method as claimed in claim 1, wherein the organophosphorus is methamidophos and the organochlorine is pentachlorophenol.
3. The water body pesticide pretreatment enrichment method as claimed in claim 1 or 2, wherein the pesticide further comprises one or more of carbamate and pyrethrin.
4. The water body pesticide pretreatment enrichment method as claimed in claim 1, wherein the solid phase extraction columns with the filler being polydivinylbenzene polymer and the surface bonded with pyrrolidone and trace ureido functional groups are connected in series in sequence.
5. The water body pesticide pretreatment enrichment method as claimed in claim 1, wherein solid phase extraction columns with fillers of hydrophilic styrene-divinylbenzene polymer and functionalized styrene-divinylbenzene polymer are connected in series in sequence.
6. The method for enriching the water body before pesticide treatment according to claim 1, wherein the water body is taken from a pond water body.
7. The water body pesticide pretreatment enrichment method as claimed in claim 1, wherein the solid phase extraction column is activated by ethanol.
8. A method for detecting the content of pesticides in a water body is characterized by comprising the following steps:
s1: enriching a sample by a solid phase extraction column by using the pretreatment enrichment method of claim 1;
s2: eluting and concentrating the enriched pesticide, and carrying out gas chromatography-mass spectrometry detection;
wherein, the chromatographic conditions in step S2 are: the chromatographic column is an HP-5MS column, and the temperature programming condition is as follows: the initial temperature is 60 ℃, the temperature is increased to 180 ℃ at the speed of 10 ℃/min and is kept for 10min, and the temperature is increased to 280 ℃ at the speed of 20 ℃/min and is kept for 10 min; the temperature of a sample inlet is 200 ℃, the split ratio is 5:1, and the flow is 1.0 mL/min;
mass spectrum conditions: EI mode ionization, wherein the standard electron energy is 70 eV; the mass spectrum scanning range is 45-450 amu; scan mode detection; ion source temperature: 230 ℃; interface transmission temperature: 280 ℃.
9. The method for detecting the content of the pesticide in the water body according to claim 8, wherein the type of the chromatographic column is 30m x 0.25mm x 0.25 μm.
10. The method for detecting the content of the pesticide in the water body according to claim 8, wherein the flow rate of the sample loading in the step S1 is 3-9.0 mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110499332.9A CN113311095B (en) | 2021-05-08 | 2021-05-08 | Water body pesticide pretreatment enrichment method and water body pesticide content detection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110499332.9A CN113311095B (en) | 2021-05-08 | 2021-05-08 | Water body pesticide pretreatment enrichment method and water body pesticide content detection method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113311095A true CN113311095A (en) | 2021-08-27 |
| CN113311095B CN113311095B (en) | 2022-11-08 |
Family
ID=77371524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110499332.9A Expired - Fee Related CN113311095B (en) | 2021-05-08 | 2021-05-08 | Water body pesticide pretreatment enrichment method and water body pesticide content detection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113311095B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489249A (en) * | 2011-11-25 | 2012-06-13 | 中国检验检疫科学研究院 | Composite solid-phase extraction column used in vegetable pesticide removing, and preparation method thereof |
| CN104324521A (en) * | 2014-10-17 | 2015-02-04 | 天津博纳艾杰尔科技有限公司 | Chinese herbal medicine solid-phase extraction column and sample pretreatment method for detecting pesticide residues in Chinese herbal medicines |
| CN205199042U (en) * | 2015-12-22 | 2016-05-04 | 广州甘蔗糖业研究所 | Series connection solid phase extraction device |
| CN105572239A (en) * | 2014-10-16 | 2016-05-11 | 无锡市寰创环境科技发展有限公司 | Method for simultaneously and rapidly determining contents of various organic chlorine pesticides in water |
| US20180001229A1 (en) * | 2014-12-17 | 2018-01-04 | Waters Technologies Corporation | Device for solid phase extraction and method for use thereof |
| CN110354816A (en) * | 2019-05-31 | 2019-10-22 | 中国农业科学院茶叶研究所 | A kind of chitosan/oxidized graphene/silicon diatomaceous earth composite material and preparation method, application |
-
2021
- 2021-05-08 CN CN202110499332.9A patent/CN113311095B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489249A (en) * | 2011-11-25 | 2012-06-13 | 中国检验检疫科学研究院 | Composite solid-phase extraction column used in vegetable pesticide removing, and preparation method thereof |
| CN105572239A (en) * | 2014-10-16 | 2016-05-11 | 无锡市寰创环境科技发展有限公司 | Method for simultaneously and rapidly determining contents of various organic chlorine pesticides in water |
| CN104324521A (en) * | 2014-10-17 | 2015-02-04 | 天津博纳艾杰尔科技有限公司 | Chinese herbal medicine solid-phase extraction column and sample pretreatment method for detecting pesticide residues in Chinese herbal medicines |
| US20180001229A1 (en) * | 2014-12-17 | 2018-01-04 | Waters Technologies Corporation | Device for solid phase extraction and method for use thereof |
| CN205199042U (en) * | 2015-12-22 | 2016-05-04 | 广州甘蔗糖业研究所 | Series connection solid phase extraction device |
| CN110354816A (en) * | 2019-05-31 | 2019-10-22 | 中国农业科学院茶叶研究所 | A kind of chitosan/oxidized graphene/silicon diatomaceous earth composite material and preparation method, application |
Non-Patent Citations (5)
| Title |
|---|
| ZHANG P 等: "Mixed-mode solid-phase extraction coupled with liquid chromatography tandem mass spectrometry to determine phenoxy acid, sulfonylurea, triazine and other selected herbicides at nanogram per litre levels in environmental waters", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 刘民 等: "新型吸附剂-固相萃取-超高效液相色谱-串联质谱法测定鱼塘水中21种常见农药", 《理化检验(化学分册)》 * |
| 朱治国 等: "大体积水系中微量农药的固相萃取柱选择", 《中国法医学杂志》 * |
| 胡兴娟: "动物源性食品中药物多残留检测研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 苗水 等: "农药残留测定用新型混合型固相萃取小柱的开发", 《中国卫生检验杂志》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113311095B (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fox et al. | Preparation of alditol acetates and their analysis by gas chromatography (GC) and mass spectrometry (MS) | |
| Prieto et al. | Stir-bar sorptive extraction: A view on method optimisation, novel applications, limitations and potential solutions | |
| Tumlinson et al. | Application of chemical ionization mass spectrometry of epoxides to the determination of olefin position in aliphatic chains | |
| CN110988193B (en) | Method for detecting advanced glycosylation end products in aquatic products | |
| CN105758946A (en) | Method for determining residual quantity of 15 kinds of triazole type pesticides in fruit | |
| CN113376305A (en) | Solid-phase membrane extraction gas chromatography-mass spectrometry detection method for carbazole and polyhalogen carbazole in water body | |
| CN112526050A (en) | Method for measuring polycyclic aromatic hydrocarbon in atmospheric dry and wet sediment through GC-MS | |
| Cartoni et al. | Capillary gas chromatographic—mass spectrometric detection of anabolic steroids | |
| CN111220722B (en) | Method for simultaneously determining 8 p-hydroxybenzoate compounds in soil | |
| CN113311095B (en) | Water body pesticide pretreatment enrichment method and water body pesticide content detection method | |
| Obata et al. | Determination of 9α, 11β-prostaglandin F2 in human urine and plasma by gas chromatography—mass spectrometry | |
| CN106770722A (en) | A kind of method of HBCD chiral isomer in detection animal muscle based on MSPD methods | |
| CN108663464B (en) | Method for detecting fenhexamid in fruits, vegetables or soil | |
| King et al. | Derivatization reactions of carbamate pesticides in supercritical carbon dioxide | |
| CN113713781A (en) | High-selectivity enrichment solid phase microextraction probe for zymotic acid and preparation method and application thereof | |
| CN111198235B (en) | Method for detecting content of isosinensetin in plasma | |
| CN114544800A (en) | Method for detecting methoxy acrylate bactericide by molecular sieve series solid phase extraction | |
| Ito et al. | Sensitive determination of methomyl in blood using gas chromatography–mass spectrometry as its oxime tert.-butyldimethylsilyl derivative | |
| CN114295742A (en) | Method for testing transfer amounts of chloropropanol and fatty acid ester in packaging material | |
| CN110736792A (en) | Application of polypyrrole nano fibers in extraction of bisphenol F, extraction device based on application and detection method | |
| Namera et al. | Monolithic spin column: a new extraction device for analysis of drugs in urine and serum by GC/MS and HPLC/MS | |
| CN112305110A (en) | Detection method suitable for ethyl ester type and glyceride type fish oil product plasticizers | |
| CN112255323A (en) | Novel chlorine-enhanced ionization reagent for liquid chromatography-mass spectrometry detection and application thereof | |
| US5445966A (en) | Extractive hydrogenation for chemical analyses | |
| CN115326995B (en) | Quantitative analysis method of soyaketone in soy sauce |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20221108 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |