CN110146559B - Soil pollution detection method - Google Patents
Soil pollution detection method Download PDFInfo
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- CN110146559B CN110146559B CN201910368283.8A CN201910368283A CN110146559B CN 110146559 B CN110146559 B CN 110146559B CN 201910368283 A CN201910368283 A CN 201910368283A CN 110146559 B CN110146559 B CN 110146559B
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- 238000001514 detection method Methods 0.000 title claims abstract description 44
- 238000003900 soil pollution Methods 0.000 title claims abstract description 13
- 239000002689 soil Substances 0.000 claims abstract description 119
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000000706 filtrate Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000000909 electrodialysis Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 95
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 70
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 63
- 239000000047 product Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 238000005070 sampling Methods 0.000 claims description 28
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000003480 eluent Substances 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000502 dialysis Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
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- 238000000576 coating method Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 239000000693 micelle Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 230000010494 opalescence Effects 0.000 claims description 7
- 239000008055 phosphate buffer solution Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229920000767 polyaniline Polymers 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 206010028980 Neoplasm Diseases 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 102000003839 Human Proteins Human genes 0.000 description 1
- 108090000144 Human Proteins Proteins 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
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- 201000011510 cancer Diseases 0.000 description 1
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- 238000010828 elution Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- AXFBAIOSECPASO-UHFFFAOYSA-N pentacyclo[6.6.2.02,7.04,16.011,15]hexadeca-1(14),2(7),3,5,8(16),9,11(15),12-octaene Chemical compound C1=C(C=C23)C4=C5C3=CC=CC5=CC=C4C2=C1 AXFBAIOSECPASO-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000003802 soil pollutant Substances 0.000 description 1
- 238000005527 soil sampling Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
Abstract
The invention relates to the technical field of soil detection, in particular to a soil pollution detection method, which comprises the following steps: s1, soil collection: s2, drying soil; s3, grinding and sieving soil; s4: centrifugal filtration; s5: electrodialysis of the filtrate; s6: adjusting the pH value of the filtrate, soaking and drying by an electrochemical sensor; s7: measuring peak current of an electrochemical sensor; the method can realize rapid and accurate determination of the benzopyrene content in the soil, improves the detection efficiency of the benzopyrene in the soil, has a large application prospect, and is suitable for further popularization and application.
Description
Technical Field
The invention relates to the technical field of soil detection, in particular to a soil pollution detection method.
Background
Soil pollutants can be broadly divided into two general categories, inorganic and organic. The inorganic pollutants mainly comprise acid, alkali, heavy metal, salts, compounds of radioactive elements cesium and strontium, compounds containing arsenic, selenium and fluorine, and the like. The organic pollutants mainly comprise organic pesticides, phenols, cyanide, petroleum, synthetic detergents, 3, 4-benzopyrene, harmful microorganisms caused by municipal sewage, sludge and stable manure, and the like. When the soil contains too much harmful substances and exceeds the self-cleaning capacity of the soil, the composition, structure and function of the soil are changed, the microbial activity is inhibited, and the harmful substances or decomposition products thereof gradually accumulate in the soil and pass through the soil, plants and human bodies, or are indirectly absorbed by the human bodies through the soil, water and human bodies, so that the degree of harming the health of the human bodies is achieved, namely the soil pollution.
Benzopyrene is also called benzo (alpha) pyrene, and is a common high-activity indirect carcinogen. It is easy to combine with human DNA after being breathed or eaten, and the synthetic procedure of human protein is disturbed. It plays a role of a "trigger" in the action of DNA: the structure, direction and function of the DNA can be changed only by extremely micro-nanogram-level benzopyrene; the DNA combined with benzopyrene, the synthesized cells are not normal cells, but tumors, and thus cancer is caused. It is easy to remain in water, soil and crops.
Many countries are now also conducting surveys of the benzopyrene content in the soil. The current method for detecting the benzopyrene content is high in cost and long in detection time.
Disclosure of Invention
Aiming at the problems, the invention provides a soil pollution detection method, which can realize the rapid and accurate determination of the benzopyrene content in soil, improves the detection efficiency of the benzopyrene in the soil and has a larger application prospect.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a soil contamination detection method comprising the steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: the peak current value of the dried electrochemical sensor was measured using an electrochemical analyzer.
Preferably, the soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
Preferably, the moisture content in the soil after drying in S2 should be less than 4%.
Preferably, the preparation method of the electrochemical sensor in S6 includes the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12 hours, cooling and introducing air, and precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5 days, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
Preferably, the molar ratio of p-styrenesulfonic acid to styrene in step 1) is 1:2.4-2.5, wherein the azodiisobutyronitrile is 1 percent of the total molar amount of the reaction monomers.
Preferably, the molar ratio of the aniline in the step 3) to the para-styrenesulfonic acid segment in the solution is 1:0.5-10; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:3-5:1.
Preferably, the eluent in the step 4) is formed by mixing methanol and acetic acid according to a volume ratio of 8:2.
Preferably, the coating thickness of the Au electrode surface cleaning product in the step 4) is 30-80 μm.
The beneficial effects are that:
1. according to the invention, the misleading of soil detection in a specific area can be effectively avoided by a specific soil sampling method, the accuracy of soil detection is ensured, the analysis time of soil is reduced, and the soil detection efficiency is effectively improved.
2. The electrochemical sensor is constructed by polyaniline nano particles, benzopyrene wrapped in the polyaniline nano particles is eluted in the preparation process, so that holes with complementarity to the shape, the size and the charge distribution of the benzopyrene molecules are left on the polyaniline nano particles, the holes can have better specific identification and sensitivity to the benzopyrene, and in addition, the polyaniline with a nano structure has a large specific surface area, so that the electrochemical sensor can have higher sensitivity and quicker response speed to the benzopyrene; when benzopyrene is combined with holes on polyaniline nanoparticles, interaction exists between the benzopyrene and molecular chains in the polyaniline nanoparticles, so that the electron transport capacity of polyaniline is improved, and the strength of an electric signal is enhanced; the peak current detected by the electrochemical sensor can be corresponding to the concentration of benzopyrene by utilizing the characteristic, so that the concentration of benzopyrene can be conveniently detected.
3. The electrochemical sensor can be repeatedly used after being subjected to elution treatment after detection, so that the detection cost of benzopyrene in soil is reduced, and the electrochemical sensor has a great application prospect and a great commercial value.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
a soil contamination detection method comprising the steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: the peak current value of the dried electrochemical sensor was measured using an electrochemical analyzer.
The soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
And S2, the water content in the soil after drying is less than 4%.
The preparation method of the electrochemical sensor in S6 comprises the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12 hours, cooling and introducing air, and precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5 days, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
The mol ratio of the p-styrenesulfonic acid to the styrene in the step 1) is 1:2.4 the addition was made, with azobisisobutyronitrile being 1% of the total molar amount of the reaction monomers.
The molar ratio of the aniline in the step 3) to the p-styrenesulfonic acid chain segment in the solution is 1:0.5; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:3:1.
The eluent in the step 4) is formed by mixing methanol and acetic acid according to the volume ratio of 8:2.
The smearing thickness of the Au electrode surface cleaning product in the step 4) is 30-80 mu m.
Example 2:
a soil contamination detection method comprising the steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: the peak current value of the dried electrochemical sensor was measured using an electrochemical analyzer.
The soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
And S2, the water content in the soil after drying is less than 4%.
The preparation method of the electrochemical sensor in S6 comprises the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12 hours, cooling and introducing air, and precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5 days, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
The mol ratio of the p-styrenesulfonic acid to the styrene in the step 1) is 1:2.5 the addition was made, with azobisisobutyronitrile being 1% of the total molar amount of the reaction monomers.
The molar ratio of the aniline in the step 3) to the p-styrenesulfonic acid chain segment in the solution is 1:10; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:4:1.
The eluent in the step 4) is formed by mixing methanol and acetic acid according to the volume ratio of 8:2.
The smearing thickness of the Au electrode surface cleaning product in the step 4) is 30-80 mu m.
Example 3:
a soil contamination detection method comprising the steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: the peak current value of the dried electrochemical sensor was measured using an electrochemical analyzer.
The soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
And S2, the water content in the soil after drying is less than 4%.
The preparation method of the electrochemical sensor in S6 comprises the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12 hours, cooling and introducing air, and precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5 days, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
The mol ratio of the p-styrenesulfonic acid to the styrene in the step 1) is 1:2.4 the addition was made, with azobisisobutyronitrile being 1% of the total molar amount of the reaction monomers.
The molar ratio of the aniline in the step 3) to the p-styrenesulfonic acid chain segment in the solution is 1:3.5; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:5:1.
The eluent in the step 4) is formed by mixing methanol and acetic acid according to the volume ratio of 8:2.
The smearing thickness of the Au electrode surface cleaning product in the step 4) is 30-80 mu m.
Example 4:
a soil contamination detection method comprising the steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: the peak current value of the dried electrochemical sensor was measured using an electrochemical analyzer.
The soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
And S2, the water content in the soil after drying is less than 4%.
The preparation method of the electrochemical sensor in S6 comprises the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12 hours, cooling and introducing air, and precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5 days, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
The mol ratio of the p-styrenesulfonic acid to the styrene in the step 1) is 1:2.5 the addition was made, with azobisisobutyronitrile being 1% of the total molar amount of the reaction monomers.
The molar ratio of the aniline in the step 3) to the p-styrenesulfonic acid chain segment in the solution is 1:6.5; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:5:1.
The eluent in the step 4) is formed by mixing methanol and acetic acid according to the volume ratio of 8:2.
The smearing thickness of the Au electrode surface cleaning product in the step 4) is 30-80 mu m.
Example 5:
a soil contamination detection method comprising the steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: the peak current value of the dried electrochemical sensor was measured using an electrochemical analyzer.
The soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
And S2, the water content in the soil after drying is less than 4%.
The preparation method of the electrochemical sensor in S6 comprises the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12 hours, cooling and introducing air, and precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5 days, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
The mol ratio of the p-styrenesulfonic acid to the styrene in the step 1) is 1:2.4 the addition was made, with azobisisobutyronitrile being 1% of the total molar amount of the reaction monomers.
The molar ratio of the aniline in the step 3) to the p-styrenesulfonic acid chain segment in the solution is 1:8.5; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:3:1.
The eluent in the step 4) is formed by mixing methanol and acetic acid according to the volume ratio of 8:2.
The smearing thickness of the Au electrode surface cleaning product in the step 4) is 30-80 mu m.
And (3) data detection:
the electrochemical sensors prepared using each example were each run at 0.0004mM;0.015mM;0.035mM;0.080mM;0.5mM;0.8mM;1.5mM; the peak current value was measured with 2mM benzopyrene, and the measurement results were shown in the following table:
wherein the peak current and benzopyrene concentration conform to a linear equation: ip (μa) =15.82×c+4.462, wherein C: benzopyrene concentration (mM).
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The soil pollution detection method is characterized by comprising the following steps of:
s1: selecting a soil detection area, and collecting soil in the area;
s2: taking out a proper amount of soil, and placing the soil in a drying oven for drying;
s3, placing the dried soil sample into a ball mill for grinding treatment, and sieving with a 150-200 mesh sieve after grinding;
s4: adding 20-30 times of deionized water solution into the ground soil sample, ultrasonically mixing for 30-45min, centrifuging and filtering the suspension to obtain clear filtrate;
s5: electrodialysis is carried out on the obtained clear filtrate to remove ions in the filtrate;
s6: adding 0.1M phosphate buffer solution into the deionized filtrate to adjust the pH to 7.0, soaking the electrochemical sensor in the solution for 10-15min, taking out and drying;
s7: measuring a peak current value of the dried electrochemical sensor by using an electrochemical analyzer;
the preparation method of the electrochemical sensor in the step S6 comprises the following steps:
1) Sequentially adding p-styrenesulfonic acid, styrene and azodiisobutyronitrile into a flask at room temperature, then adding a proper amount of dimethylformamide, stirring and dissolving, introducing nitrogen into the flask to remove air, sealing, then reacting in an oil bath at 85 ℃ for 12h, cooling and introducing air, and then precipitating the product by taking petroleum ether as a precipitating agent for three times; dissolving the obtained product continuously, dialyzing in deionized water, and freeze-drying to obtain a product A;
2) Adding dimethylformamide into the product A at room temperature, stirring and dissolving to prepare a polymer solution with the concentration of 50mg/ml, dropwise adding deionized water into the polymer solution at the speed of 1-2ml/s under the condition of continuous stirring, stopping dropwise adding and continuing stirring for 5-8 hours after blue opalescence appears in the solution, gradually dropwise adding a large amount of water into the solution to fix micelles, continuing stirring for 3-5 hours, then loading the solution into a dialysis bag for dialysis for 3-5d, removing the dimethylformamide in the solution, and then fixing the volume of the dialyzed solution to 5mg/ml for later use;
3) Adding the solution with the concentration of 5mg/ml into a flask, introducing nitrogen into the flask to discharge air, then adding benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline into the solution, stirring and dissolving, adding ammonium sulfate into the solution after the benzopyrene, 2-acrylamide-2-methylpropanesulfonic acid and aniline are fully dissolved to initiate aniline to polymerize, reacting the mixed solution in an ice water bath for 15-18h, then taking out a reaction product, and respectively carrying out methanol precipitation and centrifugal separation for three times to obtain a product B;
4) Adding eluent into the product B, stirring, standing for 24 hours at normal temperature, then washing for 3-5 times by using the eluent, eluting benzopyrene wrapped in long-chain molecules, uniformly coating the washed product on an Au electrode, and then carrying out normal-temperature ventilation drying on the Au electrode to obtain the electrochemical sensor.
2. The method for detecting soil pollution according to claim 1, wherein: the soil collection method in S1 is as follows:
a) Selecting a plurality of sampling points in the soil detection area;
b) Collecting soil samples at a plurality of sampling points by using a serpentine point distribution method, and taking a mixed sample of surface soil with the thickness of 0-25cm during collection;
c) And (3) taking the soil of one group of sampling points for independent detection, and detecting the mixed sample after the soil of the rest sampling points is uniformly mixed.
3. The method for detecting soil pollution according to claim 1, wherein: and S2, the water content in the soil after drying is less than 4%.
4. The method for detecting soil pollution according to claim 1, wherein: the mol ratio of the p-styrenesulfonic acid to the styrene in the step 1) is 1:2.4-2.5, wherein the azodiisobutyronitrile is 1 percent of the total molar amount of the reaction monomers.
5. The method for detecting soil pollution according to claim 1, wherein: the molar ratio of the aniline in the step 3) to the p-styrenesulfonic acid chain segment in the solution is 1:0.5-10; the molar ratio of the aniline to the benzopyrene to the 2-acrylamide-2-methylpropanesulfonic acid is 1:3-5:1.
6. The method for detecting soil pollution according to claim 1, wherein: the eluent in the step 4) is formed by mixing methanol and acetic acid according to the volume ratio of 8:2.
7. The method for detecting soil pollution according to claim 1, wherein: the smearing thickness of the Au electrode surface cleaning product in the step 4) is 30-80 mu m.
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