CN101915816B - Method for detecting amide and triazine herbicide residues in water body by utilizing graphene - Google Patents
Method for detecting amide and triazine herbicide residues in water body by utilizing graphene Download PDFInfo
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Abstract
The invention discloses a method for detecting amide and triazine herbicide residues in a water body by utilizing graphene, which belongs to the field of analysis on pesticide residues in water bodies. The method comprises the following steps: adsorbing the amide and the triazine herbicide in the water body by using the graphene, filtering, eluting, concentrating and detecting, thereby realizing detection of the amide and the triazine herbicide in the water body. By using the graphene as an adsorbing material, the invention has the advantages of small use amount, strong adsorptive capacity and low preparation cost; the operation is simple, convenient and quick, and avoids reextraction and pre-activation; the use amount of solvent is small, the graphene and extraction columns can be recycled, thus, the invention has the advantages of environmental protection and cost saving; and the invention has high accuracy, and the recovery rate is 80-110%.
Description
Technical field
The invention belongs to pesticide residue analysis field in the water body, be specifically related to a kind of method of utilizing Graphene to detect acid amides and triazine herbicide residues in the water body.
Background technology
Graphene is a kind of carbonaceous new material of the tightly packed one-tenth individual layer of carbon atom bi-dimensional cellular shape crystalline network; The thickness of this graphite crystal film has only 0.335nm; Be merely 200,000 of hair/; Be the elementary cell that makes up other dimension carbonaceous materials (like zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite), have excellent crystallinity and electricity property.Perfectly Graphene is two-dimentional, includes only hexagonal cellular (isogonism hexagon); If have five jiaos of cellulars and heptangle cellular to exist, can constitute the defective of Graphene; A spot of five jiaos of cellular existence can make the Graphene warpage go into shape; 12 five jiaos of cellulars can form fullerene.The theoretical specific surface area of grapheme material is up to 2600m
2/ g has outstanding heat conductivility (3000W/ (mK)) and mechanical property (1060GPa), and at a high speed electron mobility (15000cm under the room temperature
3/ (Vs)).The Graphene particular structural makes its a series of character such as conductivity that have perfect quantum tunneling effect, half integral quantum Hall effect, never disappear, and has caused the huge interest of scientific circles, and Graphene is just starting the upsurge of one research.The Graphene particular structure makes it have the good performance of each side; And present people's extensive concern is the application of Graphene at aspects such as electricity, calorifics and mechanics; Yet at rare report aspect its characterization of adsorption, the characteristic that especially is used to adsorb the residues of pesticides material as adsorbent is not appeared in the newspapers in the world as the Graphene with huge specific surface area.Yet relevant CNT but has report widely as new adsorbent in the application aspect the absorption organic pollution materials.The basic composition unit of Graphene and CNT is the same; Both all are couplings of carbon hexatomic ring; Structural similar the similar of both physical propertys of causing equally; Therefore, also have to be excavated for the novel carbonaceous nano material Graphene after CNT in the application aspect the pesticide residue analysis.
Herbicide is the one type of agricultural chemicals that water resource safety is had maximum hidden danger, particularly underground water electrode tool is threatened.Acid amides and triazine herbicide are one of common herbicide kind, and it all has characteristics separately in structure with using.All contain amide structure like the amide-type herbiciding agent molecule, majority is a processing soil treatment agent, in water, generally has bigger solubleness and leaching property, compares in soil, and it needs longer degradation time in water, and all there are certain harm in its parent and metabolin.And triazine herbicide is to be basic structure with three pyridines in view of structure, whether is evenly distributed on phenyl ring by the N atom, can be divided into two types of s-triazine and non-s-triazine; Its broad weed-killing spectrum, the scope of application is big, is mainly absorbed by root system of plant; Inhale conduction in having, along with triazine herbicide worldwide is widely used, after this type agricultural chemicals gets into rainwash; Often cause surface water pollution; And human, animals and plants and hydrobiont are caused adverse effect, and caused a series of harm humans health and Agro-ecology problem, caused the tremendous economic loss.Therefore, strengthen the research of the residue detection of two types of herbicides in the water body also ever more important.
For acid amides in the water body and triazine herbicide residues analysis, traditional preprocessing technology is a liquid liquid apportion design, but the method solvent load is big; Both costs of idleness; Can cause harmful effect to environment and operating personnel again, but also will extract repeatedly, operating process is more loaded down with trivial details.Another one tradition and use aspect the herbicide residue analysis in water body very widely that pretreatment technology is a solid phase extraction; The common amount of filler of this method is bigger, as is usually used in adsorbent C18, C8, Florisil, carbon black, PSA of pesticide residue analysis etc., and these adsorbent consumptions are generally all at hundreds of milligram even more; And pillar need be used solvent pre-leaching activation in advance; The waste solvent, pillar is disposable, and cost is than higher.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing Graphene to detect acid amides and triazine herbicide residues in the water body.
A kind of method of utilizing Graphene to detect acid amides and triazine herbicide residues in the water body, the concrete operations step is following:
(1) extraction: the Graphene of getting 10～50mg joins 20～1000mL and contains in the water sample of target herbicide, and wherein, the concentration of target herbicide is 0.1～100 μ g/L in the water sample, regulates PH to 3～11 then, stirs and leaves standstill 5～60 minutes;
(2) filter: the water sample of step (1) is passed through filtrator fast, and water is drained;
(3) wash-out: get 3～15mL eluting solvent directly on the filtrator with the target herbicide wash-out of enrichment to the Graphene, elution speed is controlled at 0.4～8mL/min, then with eluent again through 2～5g anhydrous magnesium sulfate or anhydrous sodium sulfate;
(4) concentrate: the eluent of step (3) is steamed near doing at 30～60 ℃ of underspins,, use 1～2mL solvent constant volume then again with nitrogen or air blow drying;
(5) detect: the sample behind the constant volume is carried out gas chromatography or liquid chromatographic detection;
(6) reclaim: used Graphene and extraction pillar are washed recycling successively with organic solvent and distilled water.
The said target herbicide of step (1) is selected from one or more in the following material: Stam F-34, alachlor, Acetochlor, the third careless amine, butachlor, isopropyl methoxalamine, naphthalene propionyl grass amine, benfluralin, Diflufenican, suffer, Simanex, atrazine, prometryn, cyanazine, propazine, trietazine, chlorazine, ametryn, terbutryn, atraton, prometon, metribuzin, desmetryn, dipropetryn, methoxy third are clean;
Eluting solvent described in the step (3) is to be selected from a kind of in the following solvent: normal hexane, acetone, methyl alcohol, ethanol; Acetonitrile, ethyl acetate, benzene, methylene chloride; Cyclohexane, ethyl acetate: acetone (V: V=2: 1), ethyl acetate: acetone (V: V=1: 1), methyl alcohol: ethyl acetate (V: V=1: 1); Acetone: normal hexane (V: V=3: 1), acetone: normal hexane (V: V=2: 1), acetone: normal hexane (V: V=1: 1); Acetone: normal hexane (V: V=1: 2), methyl alcohol: normal hexane (V: V=1: 1), methyl alcohol: normal hexane (V: V=1: 2);
Solvent described in the step (4) is to be selected from a kind of in the following solvent: normal hexane, ethyl acetate, acetone, methyl alcohol, methylene chloride, acetonitrile;
Organic solvent described in the step (6) is to be selected from the following organic solvent one or both: normal hexane, sherwood oil, acetone, ethanol, acetonitrile, ethyl acetate, benzene, methylene chloride, cyclohexane.
Said Graphene is commercially available.
Beneficial effect of the present invention: as sorbing material, consumption is few with Graphene in (1) the present invention, high adsorption capacity, and preparation cost is low; (2) the present invention is easy and simple to handle fast, has not only avoided extraction repeatedly but also avoided the pre-leaching activation; (3) solvent load of the present invention is few, and Graphene can reuse with the extraction pillar, not only environmental protection but also practice thrift cost; (4) accuracy of the present invention is high, and the recovery is between 80～110%.
Description of drawings
Fig. 1 is the SIM chromatogram of five kinds of amide herbicide standard specimens of GC-MS and internal standard compound;
Fig. 2 is the SIM chromatogram that five kinds of amide herbicides of GC-MS add sample and internal standard compound;
Fig. 3 is the Scan mass spectrogram of GC-MS Acetochlor standard specimen;
Fig. 4 is the Scan mass spectrogram of GC-MS alachlor standard specimen;
Fig. 5 is the Scan mass spectrogram of GC-MS isopropyl methoxalamine standard specimen;
Fig. 6 is the Scan mass spectrogram of GC-MS butachlor standard specimen;
Fig. 7 is the Scan mass spectrogram of the GC-MS third careless amine standard specimen.
Embodiment
Embodiment 1:
In the deionized water of 20mL, add alachlor, Acetochlor, the third careless amine, butachlor, isopropyl methoxalamine standard solution; Make its interpolation concentration in water be 100 μ g/L; With watery hydrochloric acid the PH of water sample is transferred to 3, in water sample, add Graphene 30mg then, left standstill after the stirring 60 minutes.Then with water sample fast through filtration unit, after draining, with the ethyl acetate of 10mL: acetone (V: V=1: 1) wash-out; Flow speed control is at 1mL/min, and eluting solvent is crossed the 2g anhydrous sodium sulfate and inserted in the heart bottle, steams near doing at 30 ℃ of underspins then; Dry up with nitrogen again, use the normal hexane constant volume of 2mL at last, detect with Agilent GC-MS after pouring the sample introduction bottle into; The HP-5MS post, injector temperature: 290 ℃; Column temperature: 120 ℃ keep 1min, rise to 200 ℃ with the speed of 20 ℃/min, keep 3min, rise to 230 ℃ with the speed of 10 ℃/min, keep 1min, and the speed with 30 ℃/min rises to 260 ℃ at last, keeps 2min; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Transmission line temperature: 280 ℃; Quota ion: alachlor (160), Acetochlor (146), the third careless amine (162), butachlor (176), isopropyl methoxalamine (162).Used Graphene and pillar are with the washing with acetone twice of 30mL, again with 3 recyclings of 50mL distilled water washing.The interpolation recovery of five kinds of herbicides is followed successively by 97.2%, 98.3%, 95.5%; 93.0%, 98.1%, relative standard deviation (RSD) is respectively 3.33%; 4.85%, 2.80%, 6.54%; 2.97%, minimum detection limit (LOD) is 0.015 μ g/L, and the chromatogram of five kinds of herbicide standard specimens is seen Fig. 1; The recovery chromatogram that five kinds of herbicides add in the water sample is seen Fig. 2; Peak sequence is followed successively by: Acetochlor, alachlor, isopropyl methoxalamine, butachlor, the third careless amine, tricresyl phosphate propyl ester TPP (internal standard compound).The Scan mass spectrogram of five kinds of herbicide standard specimens is seen Fig. 3～7.
Embodiment 2:
In the deionized water of 200mL, add atrazine, Simanex, chlorazine standard solution respectively; Make its interpolation concentration in water for being 50 μ g/L; With weak aqua ammonia the PH of water sample is transferred to 11, in water sample, add Graphene 10mg then, left standstill after the stirring 5 minutes.Then with water sample fast through filtration unit, take out in after, with the normal hexane wash-out of 3mL, flow speed control is at 0.4mL/min; Eluting solvent is crossed the 3g anhydrous sodium sulfate and is inserted in the heart bottle, steams near doing at 50 ℃ of underspins then, dries up with nitrogen again, uses the methanol constant volume of 2mL at last; Detect Tianjin, island C18 reverse-phase chromatographic column, moving phase: A pure water, B acetonitrile with Tianjin, island HPLC-UVD after pouring the sample introduction bottle into; Condition of gradient elution: 5%B keeps 2min, and B becomes 25% behind the 8min, becomes 70% behind the 8min, becomes 100% behind the 7min; Flow velocity 1mL/min, sampling volume: 20 μ L, detect wavelength: 215nm.Used Graphene and pillar are used 10mL washing with alcohol twice again with the ethyl acetate washed twice of 10mL, again with 3 recyclings of 50mL distilled water washing.It is 90.3%, 88.7%, 92.0% that the interpolation recovery of three kinds of herbicides is respectively, and relative standard deviation (RSD) is respectively 9.28%, 5.65%, 7.70%, and minimum detection limit (LOD) is respectively 0.14 μ g/L, 0.12 μ g/L, 0.08 μ g/L.
Embodiment 3:
In the deionized water of 1000mL, add prometryn, propazine, trietazine, terbutryn, prometon, dipropetryn, the methoxy third clean standard solution; Make its interpolation concentration in water be 0.1 μ g/L; PH transfers to 7, in water sample, adds Graphene 50mg then, leaves standstill after the stirring 30 minutes.Then water sample is passed through filtration unit fast, after draining, with the methylene chloride wash-out of 15mL, flow speed control is at 8mL/min; Eluting solvent is crossed the 5g anhydrous sodium sulfate and is inserted in the heart bottle, steams near doing at 60 ℃ of underspins then, dries up with nitrogen again; Use 1mL ethyl acetate constant volume at last, pour into behind the sample introduction bottle and detect, the HP-5 post with Agilent GC-NPD; Injector temperature: 230 ℃, detecting device: 300 ℃, column temperature: 60 ℃ keep 2min; Speed with 15 ℃/min rises to 150 ℃, and the speed with 15 ℃/min rises to 260 ℃ again, keeps 10min; Input mode: split sampling not, sample size: 1 μ L.Used Graphene is used the washing with acetone twice of 10mL again with the normal hexane washed twice of 10mL, again with 3 recyclings of 30mL distilled water washing.It is 95.7%, 91.3%, 88.6%, 90.8%, 101.2% that the interpolation recovery of seven kinds of herbicides is respectively; 87.9%, 93.1%, relative standard deviation (RSD) is respectively 10.20%, 8.55%, 3.40%; 9.67%, 8.67%, 5.62%, 11.30% minimum detection limit (LOD) is respectively 0.01mg/L, 0.02mg/L; 0.02mg/L, 0.04mg/L, 0.02mg/L, 0.01mg/L, 0.03mg/L.
Claims (4)
1. a method of utilizing Graphene to detect acid amides and triazine herbicide residues in the water body is characterized in that, carries out according to following operation steps:
(1) extraction: the Graphene of getting 10～50mg joins 20～1000mL and contains in the water sample of target herbicide, and wherein, the concentration of target herbicide is 0.1～100 μ g/L in the water sample, regulates PH to 3～11 then, stirs and leaves standstill 5～60 minutes;
(2) filter: the water sample after the stirring of step (1) is left standstill passes through filtrator fast, and water is drained;
(3) wash-out: get 3～15mL eluting solvent directly on the filtrator with the target herbicide wash-out of enrichment to the Graphene, elution speed is controlled at 0.4～8mL/min, then with eluent again through 2～5g anhydrous magnesium sulfate or anhydrous sodium sulfate;
(4) concentrate: step (3) is near dried 30～60 ℃ of underspins steamings through the eluent of 2～5g anhydrous magnesium sulfate or anhydrous sodium sulfate, again with nitrogen or air blow drying, use 1～2mL solvent constant volume then;
(5) detect: the sample behind the constant volume is carried out gas chromatography or liquid chromatographic detection;
(6) reclaim: used Graphene and extraction pillar are washed recycling successively with organic solvent and distilled water.
2. the method for utilizing Graphene to detect acid amides and triazine herbicide residues in the water body according to claim 1 is characterized in that, eluting solvent described in the step (3) is to be selected from a kind of in the following solvent: normal hexane; Acetone, methyl alcohol, ethanol; Acetonitrile, ethyl acetate, benzene; Methylene chloride, cyclohexane, volume ratio is 2: 1 the ethyl acetate and the potpourri of acetone; Volume ratio is 1: 1 the ethyl acetate and the potpourri of acetone, and volume ratio is 1: 1 the methyl alcohol and the potpourri of ethyl acetate, and volume ratio is 3: 1 the acetone and the potpourri of normal hexane; Volume ratio is 2: 1 the acetone and the potpourri of normal hexane, and volume ratio is 1: 1 the acetone and the potpourri of normal hexane, and volume ratio is 1: 2 the acetone and the potpourri of normal hexane; Volume ratio is 1: 1 the methyl alcohol and the potpourri of normal hexane, and volume ratio is 1: 2 the methyl alcohol and the potpourri of normal hexane.
3. the method for utilizing Graphene to detect acid amides and triazine herbicide residues in the water body according to claim 1 is characterized in that, solvent described in the step (4) is to be selected from a kind of in the following solvent: normal hexane; Ethyl acetate, acetone, methyl alcohol; Methylene chloride, acetonitrile.
4. the method for utilizing Graphene to detect acid amides and triazine herbicide residues in the water body according to claim 1 is characterized in that, organic solvent described in the step (6) is to be selected from the following organic solvent one or both: normal hexane; Sherwood oil, acetone, ethanol; Acetonitrile, ethyl acetate, benzene; Methylene chloride, cyclohexane.
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| CN104458939B (en) * | 2014-11-26 | 2016-05-18 | 嘉应学院医学院 | A kind of Camellia nitidissima oils volatile ingredient detection method |
| CN105277645B (en) * | 2015-11-23 | 2017-08-22 | 王欣 | A kind of method for determining Pesticide Residues in Tea amount |
| CN110404519A (en) * | 2019-09-04 | 2019-11-05 | 安徽省聚科石墨烯科技股份公司 | A kind of graphene aerogel adsorbent detected for phenylurea analog herbicide in water |
| CN115090277A (en) * | 2022-06-08 | 2022-09-23 | 台州学院 | Preparation of magnetic graphene oxide and adsorption application of magnetic graphene oxide to amide compounds |
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