CN114088685A - Method for rapidly detecting pesticide residues in water body - Google Patents
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- CN114088685A CN114088685A CN202111388950.2A CN202111388950A CN114088685A CN 114088685 A CN114088685 A CN 114088685A CN 202111388950 A CN202111388950 A CN 202111388950A CN 114088685 A CN114088685 A CN 114088685A
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 23
- 238000001514 detection method Methods 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims description 42
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- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 28
- 239000005944 Chlorpyrifos Substances 0.000 claims description 27
- 239000005892 Deltamethrin Substances 0.000 claims description 27
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims description 27
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- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 claims description 27
- 238000011084 recovery Methods 0.000 claims description 19
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- 238000003756 stirring Methods 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
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- Biochemistry (AREA)
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Abstract
The invention relates to the technical field of environmental pollutant detection, in particular to a method for rapidly detecting pesticide residues in a water body, and provides the method for rapidly detecting the pesticide residues in the water body.
Description
Technical Field
The invention relates to the technical field of detection of environmental pollutants, in particular to a method for rapidly detecting pesticide residues in a water body.
Background
Pesticides are essential chemicals in the production of agricultural products. Although the use of pesticides increases crop yields, their residue in agricultural or environmental waters can pose a significant potential hazard to human health and the ecosystem. The three medicines of chlorpyrifos, deltamethrin and atrazine are all pesticides for preventing and treating crop diseases, and are common pollutants in domestic water environment. Indexes of water environment quality to be controlled are specified in a surface water environment quality standard (GB 3838), a drinking water sanitation standard (GB 5749-. The medicine can be absorbed by plant seeds, roots and leaves, has long residual period and certain toxicity to human and livestock. Wherein, the chlorpyrifos is an efficient and widely applied organophosphorus pesticide, can inhibit the activity of acetylcholinesterase in pests, belongs to a toxic pesticide, and has higher toxicity to fishes and aquatic organisms; deltamethrin is one of the pyrethroid insecticides with the highest toxicity to insects, has the effects of contact poisoning and stomach poisoning, no fumigating and systemic effects, stimulation to human skin and eye mucosa and strong toxicity to fish and bees; atrazine belongs to triazine pesticides (herbicides), is widely applied to agriculture, and can damage the health of animals or human bodies due to long-term high-concentration atrazine ingestion, such as tremor, change of organ weight and damage to heart and liver.
In order to reduce potential health threats as much as possible, pesticide pollutant detection in water bodies is rapidly identified, screened and detected, and the method becomes a research hotspot of researchers. Most current pesticide detection methods, such as High Performance Liquid Chromatography (HPLC) and gas chromatography and mass-tandem mass spectrometry (GC/GC-MS), have relatively high sensitivity. However, these methods require professional instrument operation, the detection process consumes a long time, the sample pretreatment is complicated, the cost is high, and the working requirements in the field of rapid online monitoring cannot be met; the spectrum technology is used as a detection means, has the advantages of rapidness and high efficiency, and is widely applied to rapid identification and screening of pollutants; the Surface Enhanced Raman Spectroscopy (SERS) has high sensitivity and less moisture interference, can identify the fingerprint information of pollutants, has remarkable advantage in the aspect of quick detection of pesticide residues, is widely applied to the detection of pesticide residues in water, has the advantage of simultaneously quickly detecting various pesticides, and can identify the fingerprint information of different pesticides. However, the SERS detection technology requires the use of highly active substrates, and how to obtain a low-cost and high-performance enhanced substrate has been a difficult point of research. In view of the current development situation of the SERS detection technology, in order to realize the online detection of three pesticide mixed pollutants including chlorpyrifos, deltamethrin and atrazine in a water body, a cheap and efficient detection substrate is required to be developed, and the detection substrate has the functions of enhancing Raman signals and recycling materials.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to solve the problems, the invention provides a method for rapidly detecting pesticide residues in a water body, which has the advantages of high precision, low cost, simple and convenient operation, short time and recyclable materials.
The technical scheme adopted by the invention is as follows:
a method for rapidly detecting pesticide residues in a water body comprises the following steps:
s1: preparing a filter paper substrate;
the filter paper substrate comprises a filter paper carrier and loading materials AgNPs and ZnONPs loaded on the filter paper carrier;
s2: establishing a detection method for detecting pesticide residues in the water body based on SERS by using the filter paper substrate in S1, determining the linear range and detection limit of the detection method, and verifying the recovery rate of the detection method;
s3: the filter paper substrate is used for carrying out an in-situ photocatalytic degradation experiment of a target object, a target pesticide is loaded on the filter paper substrate by adopting a dropping method, the filter paper substrate is illuminated by using an ultraviolet lamp, and the target pesticide concentration on the filter paper substrate before and after illumination is detected by using a Raman instrument.
Furthermore, AgNPs in S1 are nano particle suspension prepared by a reduction method, and are uniformly loaded on a filter paper carrier by adopting a soaking method.
Furthermore, ZnONPs in S1 are dispersed nano particle suspension and are uniformly loaded on a filter paper carrier by adopting a soaking method.
Further, the preparation of the filter paper substrate in S1 includes the following steps:
s11: adding 10-20 mg of HONH2Dissolving Cl and 10-20 mg NaOH in 10-100mL of deionized water, and dropwise adding 10-100mL of 10mM AgNO while continuously stirring2Stirring the solution for 10 minutes to prepare AgNPs suspension;
s12: respectively dissolving 0.1-1 g of zinc acetate and 0.1-1 g of potassium hydroxide in 10-100mL of ethanol, heating the zinc acetate solution to 50-70 ℃ under stirring, dripping the potassium hydroxide solution after 20-40min, continuously stirring for 8-15min until the solution is clarified to become an emulsion, and centrifuging the obtained emulsion for multiple times and washing with deionized water to obtain ZnO nanoparticles;
s13: cutting the filter paper into 1-5 cm2And soaking the paper sheets with the sizes into the ZnO nano particle dispersion liquid for 3-8 minutes, drying, soaking the dried filter paper into the AgNPs suspension liquid for 3-8 minutes, taking out, washing with deionized water for several times, and naturally drying to obtain the filter paper substrate.
Further, the establishment of the detection method in S2 includes the following steps:
s21: collecting Raman spectra of mixed pesticides of chlorpyrifos, deltamethrin and atrazine with low concentration to high concentration, and establishing a linear relation between the corresponding Raman spectrum characteristic peak intensity and the target concentration;
s22: selecting an ultraviolet lamp with the wavelength of 254nm, irradiating for 10 minutes, repeating the recovery process for 5 times, and testing the reusability of the filter paper substrate;
s23: and (4) testing the recovery rates of the chlorpyrifos, the deltamethrin and the atrazine in the actual water sample by adding a label, and verifying the recovery rate of the detection method.
Furthermore, in S21, the concentration range of chlorpyrifos is 5000ug/L, the concentration range of deltamethrin is 100 ug/L and 10000ug/L, and the concentration range of atrazine is 10 ug/L to 10000 ug/L.
Further, in S21, the characteristic peak of chlorpyrifos was 348cm-1The characteristic peak of deltamethrin is 736cm-1The characteristic peak of atrazine is 1029cm-1。
Further, in S21, characteristicsThe peak intensity is in direct proportion to the concentration of three pesticide targets in the mixed pesticide, and R of chlorpyrifos, deltamethrin and atrazine in the mixed sample2Respectively 0.990, 0.992 and 0.994, and the lowest detection limits of chlorpyrifos, deltamethrin and atrazine in the mixed sample are respectively 33.7 mug/L, 66.4 mug/L and 25.0 mug/L.
Further, in S22, the same filter paper substrate is used, the recovery process is repeated, the signal intensity of chlorpyrifos, deltamethrin and atrazine is reduced to below 20% in each recovery process, and the signal intensity of the characteristic peak is restored to the original level after the filter paper substrate is reloaded with the chlorpyrifos, deltamethrin and atrazine solution.
Further, in S22, the average recovery of the three pesticide targets ranges from 87.03 to 117.3 with RSD < 17.6%.
The invention has the following beneficial effects:
according to the method for rapidly detecting the pesticide residue in the water body, the filter paper SERS detection substrate with AgNPs and ZnO nanoparticles is prepared, the loaded ZnONPs can enable the detection substrate to have the function of degrading pesticide pollutants under ultraviolet illumination, the functional SRES substrate can sensitively realize the recovery detection of chlorpyrifos, deltamethrin and atrazine pesticides, the filter paper substrate can complete the degradation of the pollutants within 10 minutes under the irradiation of ultraviolet light, and various pesticides in a mixed sample can still be detected after the process is repeated for 5 times.
Drawings
Fig. 1 is a detection flowchart in the embodiment of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. The various starting materials used in the examples are, unless otherwise indicated, conventional commercial products.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The numerical values set forth in the examples of the present invention are approximations, not necessarily values. All values within the error range may be included without being limited to the specific values disclosed in the embodiments of the present invention where the error or experimental conditions allow.
The numerical ranges disclosed in the examples of the present invention are intended to indicate the relative amounts of the components in the mixture and the ranges of temperatures or other parameters recited in the other method examples.
The method for rapidly detecting the pesticide residue in the water body specifically comprises the following steps:
(1) respectively dissolving 1g of zinc acetate and 1g of potassium hydroxide in 100mL of ethanol, heating the zinc acetate solution to 60 ℃ under stirring, dripping the potassium hydroxide solution after 30min, continuously stirring for 10min until the solution becomes opaque from clarification, and centrifuging the obtained emulsion for 5 times and washing the solution with deionized water to obtain ZnO nanoparticles;
(2) 20mg of HONH2Cl and 20mg NaOH were dissolved in 90mL deionized water and 90mL 10mM AgNO was added dropwise with continued stirring2Stirring the solution for 10 minutes to prepare AgNPs suspension;
(3) cutting filter paper into the size of 1 x 1cm, immersing the filter paper sheet in ZnONPs dispersion liquid for 5 minutes, drying, immersing the dried filter paper in AgNPs suspension liquid for 5 minutes, taking out the filter paper sheet for further purification, washing the filter paper substrate loaded with ZnO by deionized water for 6 times, and naturally drying to obtain a filter paper SERS substrate;
(4) evaluating the SERS detection performance of the filter paper substrate, collecting 50-500ug/L chlorpyrifos, 100-1000ug/L deltamethrin and 100-1000ug/L attritorEstablishing the relationship between the Raman spectrum intensity and concentration of the target object by Raman spectrum of the mixed pesticide of the Lazine, and selecting 348cm-1Selecting 736cm as the characteristic peak of chlorpyrifos-1Selecting 1029cm as characteristic peak of deltamethrin-1Is a characteristic peak of atrazine, the strength of the characteristic peak is in direct proportion to the concentration of three pesticide targets in the mixed pesticide, R of chlorpyrifos, deltamethrin and atrazine in the mixed sample20.990, 0.992, and 0.994, respectively;
(5) and further evaluating the SERS detection performance of the paper filter paper substrate, and performing a labeling experiment to test the recovery rates of chlorpyrifos, deltamethrin and atrazine in an actual water sample, wherein the average recovery rate range of the three pesticide target objects in the labeling process is 81.9-117.3, and the RSD is less than 17.6%.
(6) And (3) testing the cyclic usability of the filter paper substrate for detecting the three pesticides, selecting an ultraviolet lamp with the wavelength of 254nm, irradiating for 10 minutes, repeating the recovery process for 5 times, reducing the intensity of the chlorpyrifos, the deltamethrin and the atrazine to be below 20% in each recovery process, and recovering the signal intensity of the characteristic peak to the original level after reloading the chlorpyrifos, the deltamethrin and the atrazine.
Referring to the above embodiments, according to the method for rapidly detecting pesticide residues in water provided by the present application, by preparing the filter paper SERS detection substrate with AgNPs and ZnO nanoparticles, the supported ZnONPs can make the detection substrate have a function of degrading pesticide pollutants under ultraviolet irradiation, the functional SRES substrate can sensitively realize the recoverable detection of chlorpyrifos, deltamethrin and atrazine pesticides, the filter paper substrate can complete the degradation of pollutants within 10 minutes under ultraviolet irradiation, after repeating for 5 times, various pesticides in a mixed sample can still be detected, the detection process is convenient and rapid, no pretreatment is needed, the detection cost is low, and meanwhile, due to the photocatalyst supported on the surface, the filter paper substrate can degrade the pesticide pollutants adsorbed on the surface in situ under ultraviolet irradiation, thereby realizing self-cleaning, repeating the injection and illumination processes and enabling the material to be reused, the material can degrade pollutants by photocatalysis after being used, and does not need to worry about secondary pollution to the environment, meanwhile, the lowest detection limits of the detection method are 33.7 mu g/L of chlorpyrifos, 66.4 mu g/L of deltamethrin and 25.0 mu g/L of atrazine, and the detection requirement can be met.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for rapidly detecting pesticide residues in a water body is characterized by comprising the following steps:
s1: preparing a filter paper substrate;
the filter paper substrate comprises a filter paper carrier and loading materials AgNPs and ZnONPs loaded on the filter paper carrier;
s2: establishing a detection method for detecting pesticide residues in the water body based on SERS by using the filter paper substrate in S1, determining the linear range and detection limit of the detection method, and verifying the recovery rate of the detection method;
s3: the filter paper substrate is used for carrying out an in-situ photocatalytic degradation experiment of a target object, a target pesticide is loaded on the filter paper substrate by adopting a dropping method, the filter paper substrate is illuminated by using an ultraviolet lamp, and the target pesticide concentration on the filter paper substrate before and after illumination is detected by using a Raman instrument.
2. The method for rapidly detecting pesticide residues in water bodies according to claim 1, wherein AgNPs in S1 is a nanoparticle suspension prepared by a reduction method, and is uniformly loaded on a filter paper carrier by adopting a soaking method.
3. The method for rapidly detecting pesticide residues in the water body according to claim 1, wherein ZnONPs in S1 are dispersed nano particle suspensions and are uniformly loaded on a filter paper carrier by a soaking method.
4. The method for rapidly detecting pesticide residues in water bodies according to claim 1, wherein the preparation of the filter paper substrate in S1 comprises the following steps:
s11: adding 10-20 mg of HONH2Dissolving Cl and 10-20 mg NaOH in 10-100mL of deionized water, and dropwise adding 10-100mL of 10mM AgNO while continuously stirring2Stirring the solution for 10 minutes to prepare AgNPs suspension;
s12: respectively dissolving 0.1-1 g of zinc acetate and 0.1-1 g of potassium hydroxide in 10-100mL of ethanol, heating the zinc acetate solution to 50-70 ℃ under stirring, dripping the potassium hydroxide solution after 20-40min, continuously stirring for 8-15min until the solution is clarified to become an emulsion, and centrifuging the obtained emulsion for multiple times and washing with deionized water to obtain ZnO nanoparticles;
s13: cutting the filter paper into 1-5 cm2And soaking the paper sheets with the sizes into the ZnO nano particle dispersion liquid for 3-8 minutes, drying, soaking the dried filter paper into the AgNPs suspension liquid for 3-8 minutes, taking out, washing with deionized water for several times, and naturally drying to obtain the filter paper substrate.
5. The method for rapidly detecting pesticide residues in a water body according to claim 1, wherein the establishment of the detection method in S2 comprises the following steps:
s21: collecting Raman spectra of mixed pesticides of chlorpyrifos, deltamethrin and atrazine with low concentration to high concentration, and establishing a linear relation between the corresponding Raman spectrum characteristic peak intensity and the target concentration;
s22: selecting an ultraviolet lamp with the wavelength of 254nm, irradiating for 10 minutes, repeating the recovery process for 5 times, and testing the reusability of the filter paper substrate;
s23: and (4) testing the recovery rates of the chlorpyrifos, the deltamethrin and the atrazine in the actual water sample by adding a label, and verifying the recovery rate of the detection method.
6. The method as claimed in claim 5, wherein in S21, the concentration range of chlorpyrifos is 100-5000ug/L, the concentration range of deltamethrin is 100-10000ug/L, and the concentration range of atrazine is 10-10000 ug/L.
7. The method for rapidly detecting pesticide residues in water bodies according to claim 5, wherein the characteristic peak of chlorpyrifos in S21 is 348cm-1The characteristic peak of deltamethrin is 736cm-1The characteristic peak of atrazine is 1029cm-1。
8. The method for rapidly detecting pesticide residues in water bodies according to claim 5, wherein in S21, the intensity of the characteristic peak is in direct proportion to the concentration of three pesticide targets in the mixed pesticide, and R of chlorpyrifos, deltamethrin and atrazine in the mixed sample2Respectively 0.990, 0.992 and 0.994, and the lowest detection limits of chlorpyrifos, deltamethrin and atrazine in the mixed sample are respectively 33.7 mug/L, 66.4 mug/L and 25.0 mug/L.
9. The method for rapidly detecting pesticide residues in a water body according to claim 5, wherein in S22, the same filter paper substrate is used, the recovery process is repeated, the signal intensity of chlorpyrifos, deltamethrin and atrazine in each recovery process is reduced to be below 20%, and the signal intensity of characteristic peaks is restored to the original level after the filter paper substrate is reloaded with chlorpyrifos, deltamethrin and atrazine solution.
10. The method for rapidly detecting pesticide residues in water bodies as claimed in claim 5, wherein in S22, the average recovery rate of three pesticide targets ranges from 87.03 to 117.3, and the RSD is less than 17.6%.
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| CN115308180A (en) * | 2022-08-08 | 2022-11-08 | 青岛农业大学 | Fluorescent zinc oxide quantum dot, and preparation method and application thereof |
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