CN110196294B - Solid phase extraction detection method for neonicotinoid insecticides in water and conversion products thereof - Google Patents

Solid phase extraction detection method for neonicotinoid insecticides in water and conversion products thereof Download PDF

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CN110196294B
CN110196294B CN201910462706.2A CN201910462706A CN110196294B CN 110196294 B CN110196294 B CN 110196294B CN 201910462706 A CN201910462706 A CN 201910462706A CN 110196294 B CN110196294 B CN 110196294B
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熊晶晶
谭保祥
李慧珍
马雪
游静
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Jinan University
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Abstract

The invention belongs to the technical field of pesticide detection, and discloses a solid-phase extraction detection method for a neonicotinoid pesticide in water and a conversion product thereof. The method specifically comprises the following steps: (1) activating a solid phase extraction column; (2) after adjusting the pH value of the water sample, adding a recovery rate indicator, and then extracting the water sample in a solid phase extraction column; (3) after vacuum drying the solid phase extraction small column, eluting to obtain an eluent, and then adding an internal standard compound; (4) and detecting the concentration of the target compound. The self-filling mixed adsorbent solid phase extraction column is simple and convenient in operation method, can simultaneously analyze the neonicotinoid insecticides and the conversion products thereof in water, has good adsorption performance on the neonicotinoid insecticides and the conversion products thereof, has the detection limit of 0.56-5.43 ng/L in surface water, and has the matrix effect of-7.58% -21.1%.

Description

Solid phase extraction detection method for neonicotinoid insecticides in water and conversion products thereof
Technical Field
The invention belongs to the technical field of pesticide detection, and particularly relates to a solid-phase extraction detection method for a neonicotinoid pesticide in water and a conversion product thereof.
Background
The neonicotinoid insecticides are novel insecticides which are used in a large scale at present after traditional insecticides such as organic chlorine, organic phosphorus, pyrethroid and the like, are used in more than 120 countries in registration, occupy more than 25 percent of the global insecticide market, and mainly comprise acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam. Neonicotinoid insecticides are highly water soluble and can easily enter water environment systems, and the harm to non-target aquatic organisms is gradually recognized and concerned by people. On the other hand, the environmental neonicotinoid insecticide parent compound generates conversion products, and the harm of the conversion products is not ignored. To assess the hazards of neonicotinoid insecticides and their conversion products in an aqueous environment, effective monitoring should first be performed. Among them, solid phase extraction is widely used in monitoring pollutants in water because of its advantages of less solvent consumption, high sensitivity and simple operation. However, the hydrophilic-lipophilic balance (HLB) solid phase extraction columns commonly used do not provide the desired extraction of highly polar neonicotinoid insecticides, especially their conversion products. For example, the sample to be tested may cause target compound loss during the processing, the recovery rate is low, and the accuracy of the test method cannot be ensured; in addition, the neonicotinoid insecticides and the transformation products thereof have more varieties and great differences, and are difficult to detect all compounds simultaneously. In view of the advantages of the solid-phase extraction method in analyzing organic pollutants and in order to effectively perform analysis of neonicotinoid insecticides and their conversion products in water, there is a need for improvement of the current solid-phase extraction method to develop a new solid-phase extraction method suitable for analyzing neonicotinoid insecticides and their conversion products.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a solid-phase extraction detection method for neonicotinoid insecticides and conversion products thereof in water.
The purpose of the invention is realized by the following scheme:
a solid phase extraction detection method of neonicotinoid insecticides in water and conversion products thereof comprises the following steps:
(1) activating the solid phase extraction column filled with the mixed adsorbent by using methanol and water;
(2) after adjusting the pH value of the water sample, adding a recovery rate indicator, and then adding the water sample into the activated mixed adsorbent solid-phase extraction column in the step (1);
(3) after vacuum drying the mixed adsorbent solid phase extraction cartridge loaded with the water sample in the step (2), sequentially eluting with an organic solvent, an organic solvent added with acid and an organic solvent added with alkali to obtain an eluent, and then adding an internal standard compound into the eluent;
(4) and detecting the concentration of the target compound by adopting an ultra-high liquid chromatography tandem mass spectrum.
The neonicotinoid insecticide is at least one of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; the conversion product of the neonicotinoid insecticide is at least one of 6-chloronicotinic acid, demethylacetamiprid, imidacloprid guanidine, imidacloprid olefin, imidacloprid urea, aminothiacloprid and demethylthiamethoxam.
Further, the solid phase extraction column filled with the mixed adsorbent in the step (1) is obtained by the following method: the mixed adsorbent is filled into a hollow tube solid phase extraction column by a dry method under the vacuum condition, and the upper end and the lower end of the mixed adsorbent are fixed by a sieve plate, so that the mixed adsorbent solid phase extraction column is obtained; the hollow tube solid phase extraction column is made of polypropylene.
Further, the mass ratio of each adsorbent in the mixed adsorbent in the step (1) is HLB: weak anion exchange (WAX) adsorbents: weak cation exchange (WCX) adsorbents 1-4: 1-10: 1 to 2, further 1 to 4: 1-2: 1-2, most preferably 2:1: 1.
further, the mass of the mixed adsorbent in the solid phase extraction column filled with the mixed adsorbent in the step (1) is 100-400 mg, preferably 200 mg; the specification of the solid phase extraction column is 3-6 mL.
Further, the pH value of the water sample after adjustment in the step (2) is 2-7, and further is 4;
further, when the mass of the mixed adsorbent in the solid phase extraction column filled with the mixed adsorbent in the step (1) is 200-400 mg, the mass ratio of each adsorbent is HLB: WAX: WCX is 1-4: 1-10: 1-2, wherein the pH value of the water sample after adjustment in the step (2) is 4-7; further, when the mass of the mixed adsorbent in the solid phase extraction column packed with the mixed adsorbent in step (1) is 200mg, the mass ratio of each adsorbent is HLB: WAX: WCX ═ 2:1: and (1) adjusting the pH value of the water sample obtained in the step (2) to be 4-7.
Further, the method also comprises a step of removing impurities before adjusting the pH value of the water sample in the step (2), and specifically comprises the steps of sequentially passing the water sample through a 0.7-micrometer glass fiber filter membrane and a 0.22-0.45-micrometer nylon membrane; further, the pore diameter of the nylon membrane is 0.45 μm.
Further, the adding amount of the water sample in the step (2) is 200-1000 mL.
Further, the adding speed of the water sample in the step (2) is 2-3 mL/min.
Further, the recovery rate indicator in the step (2) is acetamiprid-d3The standard adding concentration of the water sample is 10-100 ng/L.
Further, the organic solvent in step (3) is at least one of methanol, acetone and acetonitrile, preferably methanol.
Further, the organic solvent after the acid is added in the step (3) is an organic solvent containing acetic acid with the volume ratio of 0.2-1.0%.
Further, the organic solvent after the alkali is added in the step (3) is an organic solvent containing 0.2-2.5% of ammonia water by volume.
Further, the amount of the organic solvent, the organic solvent after the acid is added and the amount of the organic solvent after the alkali is added in the step (3) are independently 2-8 mL; preferably 5 mL.
Further, when the quality of the single neonicotinoid insecticide in the water sample added in the step (1) is low, carrying out nitrogen-blowing concentration on the eluent obtained in the step (3); furthermore, the nitrogen blowing concentration is to blow and concentrate the elution liquid nitrogen to 0.2-1.0 mL.
Further, the internal standard compound in the step (3) is imidacloprid-d4The concentration of the eluent is 5-100 mug/L; further 10. mu.g/L.
Further, the detection in the step (4) is specifically as follows:
the method is characterized by comprising the steps of (1) performing ultra-high liquid chromatography tandem mass spectrometry on Shimadzu LC-30-AD and AB Sciex QTRAP 5500, wherein a chromatographic column is an Agilent eclipse plus C18 column with the specification of 100mm multiplied by 2.1mm multiplied by 1.8 mu m, and is connected with a zorbax eclipse plus-C18 protective column with the specification of 12.5mm multiplied by 2.1mm multiplied by 5 mu m and the column temperature is 40 ℃; the mobile phase A is: 0.1% (V/V) aqueous formic acid, mobile phase B: acetonitrile, gradient elution;
the gradient elution procedure was as follows: 0-0.5 min, 10% (V/V) B; 3.0min, 90% (V/V) B; 11.0min, 90% (V/V) B; 11.1min, 10% (V/V) B; 11.1-15.0 min, 10% (V/V) B; the sample introduction volume is 2 mu L, the electrospray ion source is adopted, the positive mode is adopted, the multi-reaction monitoring is carried out for quantification, the atomization gas is nitrogen, the rolling curtain gas is 45Psi, the collision gas is 8Psi, the ion spray voltage is 5500V, the ion source temperature is 550 ℃, the ion source gas circuit 1 is 55Psi, the ion source gas circuit 2 is 55Psi, and the inlet voltage and the collision cell outlet voltage are respectively 10.0V and 16.0V.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the method for operating the self-filled mixed adsorbent solid phase extraction column is simple, convenient and accurate, and can simultaneously analyze the neonicotinoid insecticides and the conversion products thereof in the water.
2) The self-filled mixed adsorbent solid-phase extraction column has good adsorption performance on the neonicotinoid insecticides and the conversion products thereof, and the detection limit in surface water is 0.56-5.43 ng/L.
3) The invention has low matrix effect of anabasine insecticides and conversion products thereof in water, and the matrix effect is-7.58-21.1%.
Drawings
FIG. 1 is a graph showing the recovery of neonicotinoid insecticide (a) and its conversion product (b) by the mixed adsorbent, HLB, WAX and WCX adsorbent solid phase extraction column of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
In all examples of the invention, the use of Shimadzu LC-30-AD and AB Sciex QTRAP 5500 ultra high liquid chromatography tandem mass spectrometry determination. The chromatographic column is an Agilent eclipse plus C18 column with the specification of 100mm multiplied by 2.1mm multiplied by 1.8 mu m, a zorbax eclipse plus-C18 protective column with the specification of 12.5mm multiplied by 2.1mm multiplied by 5 mu m is connected, and the column temperature is 40 ℃. The mobile phase A is: 0.1% (V/V) aqueous formic acid, mobile phase B: acetonitrile, gradient elution. The gradient elution procedure was as follows: 0-0.5 min, 10% (V/V) B; 3.0min, 90% (V/V) B; 11.0min, 90% (V/V) B; 11.1min, 10% (V/V) B; 11.1-15.0 min, 10% (V/V) B. The injection volume was 2. mu.L. Electrospray ion source, positive mode, multiple reaction monitoring for quantification, and nitrogen as the atomizing gas. The curtain gas is 45Psi, the collision gas is 8Psi, the ion spray voltage is 5500V, the ion source temperature is 550 ℃, the ion source gas circuit 1 is 55Psi, the ion source gas circuit 2 is 55Psi, and the inlet voltage and the collision cell outlet voltage are 10.0V and 16.0V respectively. The ion pair information and other mass spectrum parameters of each neonicotinoid insecticide and its conversion product are shown in table 1.
TABLE 1 neonicotinoid insecticides and their conversion products ion-pair information and Mass Spectrometry parameters
Figure BDA0002078521660000051
aQuantitative ion pair
Example 1
Comparison of adsorption Effect of Mixed adsorbent solid-phase extraction column and HLB, WAX and WCX solid-phase extraction columns
The new method for solid-phase extraction of the mixed adsorbent is compared with the adsorption effect of the conventional HLB, WAX and WCX solid-phase extraction on the neonicotinoid insecticides and the conversion products thereof.
1) Respectively and dry-filling 200mg of mixed adsorbent with the mass ratio of HLB to WAX to WCX being 2 to 1, HLB, WAX and WCX solid-phase extraction filler into hollow-tube solid-phase extraction small columns made of 6mL polypropylene materials under the condition of vacuumizing on a solid-phase extraction system, and fixing the upper end and the lower end of the mixed filler through sieve plates to obtain the solid-phase extraction small columns with different fillers.
2) And (3) activation: each of the solid-phase extraction cartridges was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: and (2) loading a mixed aqueous solution containing 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with the theoretical standard concentration of 100ng/L at the flow rate of 2-3 mL/min through a loading tube and passing through an activated solid phase extraction column, wherein the loading volume is 1000mL, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) 1.0mL of eluent is taken and added with imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
The recovery rates of the neonicotinoid insecticide (a) and its conversion product (b) by the mixed adsorbent, HLB, WAX and WCX adsorbent solid phase extraction column of example 1 are shown in fig. 1. As can be seen from fig. 1, under the same test conditions, the mixed adsorbent solid-phase extraction method has significantly better extraction effect on neonicotinoid insecticides and their transformed products than the solid-phase extraction method using any HLB, WAX, or WCX adsorbent alone, which indicates that the detection method of the present invention has better detection effect on 14 neonicotinoid insecticides and their transformed products. For example, the commonly used HLB adsorbent solid phase extraction column has a poor extraction effect on dinotefuran (23.6% + -4.4%) and 6-chloronicotinic acid (15.9% + -0.2%), while the WCX adsorbent solid phase extraction column has a good extraction effect on dinotefuran (93.8% + -15.6%), and the WAX adsorbent solid phase extraction column has a good extraction effect on 6-chloronicotinic acid (122% + -27%), so that the solid phase extraction efficiency of the neonicotinoid insecticide and the conversion product thereof in the water body can be obviously improved by using the mixed adsorbent consisting of the HLB adsorbent, the WAX adsorbent and the WCX adsorbent. The solid phase extraction recovery rates (recovery rate measured/actual plus quantity multiplied by 100%) for neonicotinoid insecticides and their conversion products in table 1 were 55.9% ± 1.0% (dinotefuran) to 150% ± 7% (imidacloprid guanidine), 15.9% ± 0.2% (6-chloronicotinic acid) to 150% ± 7% (imidacloprid guanidine), 13.1% ± 2.3% (dinotefuran) to 131% ± 22% (aminothiacloprid), 16.2% ± 0.3% (6-chloronicotinic acid) to 137% ± 8% (aminothiacloprid), respectively, for the mixed adsorbent, the HLB, WAX, WCX adsorbent (recovery rates for other neonicotinoid insecticides and their conversion products were within the ranges described above).
Example 2 extraction effect of mixed adsorbents of different ratios
1) And (2) filling 200mg of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance), WAX (WAX-WAX) and WCX (WCX-WAX ratio) of 4:1:1 into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and fixing the upper end and the lower end of the mixed filler through sieve plates to obtain the mixed adsorbent solid-phase extraction column.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after the pH value of a 200mL mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentrations of 1000ng/L is adjusted to 4 by using dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) 1.0mL of eluent is taken and added with imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
Test results show that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 66.1% +/-6.1% -126% +/-17%.
Example 3 extraction effect of mixed adsorbents of different ratios
1) And (2) filling 200mg of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance) to WAX (WAX-particle balance) to WCX (WCX) to 1:2:2 into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and fixing the upper end and the lower end of the mixed adsorbent through sieve plates to obtain the mixed adsorbent solid-phase extraction column.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after the pH value of a 200mL mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentrations of 1000ng/L is adjusted to 4 by using dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) 1.0mL of eluent is taken and added with imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
Test results show that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 70.1% +/-4.3% -111% +/-11%.
Example 4 extraction effect of mixed adsorbents with different ratios
1) And (2) filling 200mg of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance), WAX (WAX-WAX) and WCX (WCX) being 1:10:1 into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and fixing the upper end and the lower end of the mixed filler through sieve plates to obtain the mixed adsorbent solid-phase extraction column.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after the pH value of a 200mL mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentrations of 1000ng/L is adjusted to 4 by using dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) 1.0mL of eluent is taken and added with imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
Test results show that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 53.2% +/-2.7% -139% +/-7%.
EXAMPLE 5 recovery of spiked in pure Water
1) And (2) filling 200mg of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance), WAX (WAX-WAX) and WCX (WCX-WAX ratio) of 2:1:1 into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and fixing the upper end and the lower end of the mixed filler through sieve plates to obtain the mixed adsorbent solid-phase extraction column.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after 200mL of mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentration of 100ng/L is adjusted to pH value of 2 by dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 8mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) Concentration: blowing and concentrating the elution liquid nitrogen obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
The pure water standard adding test result shows that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 41.7% +/-3.1% -121% +/-16%, except that the recovery rate of the aminothiacloprid is 5.6 +/-1.7%.
EXAMPLE 6 recovery of spiked in pure Water
1) 400mg of filler of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance), WAX (WAX-WAX) and WCX (WCX) being 2:1:1 is filled into a hollow-tube solid-phase extraction small column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and the upper end and the lower end of the mixed filler are fixed through sieve plates, so that the mixed adsorbent solid-phase extraction small column is obtained.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after the pH value of a 200mL mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentrations of 100ng/L is adjusted to 4 by using dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) Concentration: blowing and concentrating the elution liquid nitrogen obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
The results of pure water labeling tests show that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 39.8% +/-1.8% -113% +/-6%, except that imidacloprid guanidine is 14.6 + -9.2%.
Example 7 recovery of spiked in pure Water
1) 400mg of filler of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance), WAX (WAX-WAX) and WCX (WCX) being 2:1:1 is filled into a hollow-tube solid-phase extraction small column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and the upper end and the lower end of the mixed filler are fixed through sieve plates, so that the mixed adsorbent solid-phase extraction small column is obtained.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after adjusting the pH value of a mixed aqueous solution of 1000mL of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentrations of 100ng/L to 7 by using a 0.1M sodium hydroxide solution, loading the mixed aqueous solution through a sample loading tube at a flow rate of 2-3 mL/min and passing the mixed aqueous solution through an activated solid phase extraction cartridge, and performing three parallel samples.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 2.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) 1.0mL of eluent is taken and added with imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
Test results show that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 52.1% +/-5.1% -124% +/-15%.
EXAMPLE 8 recovery of spiked in pure Water
1) 200mg of filler of a mixed adsorbent with HLB (HLB: PWAX: PWCX: 2:1: 1) is loaded into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and the upper end and the lower end of the mixed filler are fixed through sieve plates, so that the mixed adsorbent solid-phase extraction column is obtained.
The filled mixed adsorbent solid phase extraction column is applied to the determination of the standard recovery rate of the neonicotinoid insecticides and the conversion products thereof in the pure water. The standard concentrations of 14 neonicotinoid insecticides and their conversion products (Dr. Ehrenstonifer Gmbh, Augussburg, Germany) in pure water are all 50ng/L, and the pH value of the aqueous solution is adjusted to 4 by dilute hydrochloric acid, three parallel samples are prepared by the following specific operation steps:
2) and (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: loading the aqueous solution containing the insecticide obtained in the step 1) through a loading tube at a flow rate of 2-3 mL/min, and loading the aqueous solution into an activated mixed solid phase extraction cartridge, wherein the loading volume is 200 mL.
4) And (3) elution: and drying the solid phase extraction column loaded with the water sample for at least 15min under the vacuum-pumping condition, eluting the target substance by using methanol, a methanol solution of 0.5% (V/V) acetic acid and a methanol solution of 0.5% (V/V) ammonia water which are 5mL in volume in sequence, and collecting the eluent.
5) Concentration: blowing and concentrating the elution liquid nitrogen obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: after passing through a 0.22 μm organic system pinhole filter, the concentration of the compound was determined using Shimadzu LC-30-AD and AB Sciex QTRAP 5500 ultra-high liquid chromatography mass spectrometer.
The results of pure water labeling tests show that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 88.5% + -9.4% -156% + -12%, except that the recovery rates of nitenpyram and dinotefuran are 49.2% + -7.5% and 56.3 + -5.0%, respectively.
Example 9 comparison of recovery rates of target Compounds eluted Using different elution solvents
The elution effect of the neonicotinoid insecticides and the conversion products thereof on the mixed adsorbent solid phase extraction column is compared by taking common organic solvents of methanol, acetone and acetonitrile as elution solvents.
1) 200mg of filler of a mixed adsorbent with the mass ratio of HLB to WAX to WCX being 2 to 1 is loaded into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and the upper end and the lower end of the mixed filler are fixed through sieve plates, thus obtaining the mixed adsorbent solid-phase extraction column.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after the pH value of a 200mL mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentrations of 100ng/L is adjusted to 4 by using dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: after the solid phase extraction small column loaded with the water sample is dried for at least 15min under the vacuum pumping condition, 5mL of methanol, 0.5% (V/V) of acetic acid methanol solution and 0.5% (V/V) of ammonia water methanol solution are respectively used; 5mL of acetone, 0.5% (V/V) of acetic acid in acetone solution, and 0.5% (V/V) of ammonia in acetone solution; eluting the target substance by using 5mL of acetonitrile, 0.5% (V/V) of acetic acid solution in acetonitrile and 0.5% (V/V) of ammonia water solution in acetonitrile, and collecting the eluent.
5) Concentration: respectively carrying out nitrogen-blown concentration on different eluents obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
Test results show that the recovery rate of the neonicotinoid insecticides and the conversion products thereof with methanol as an elution solvent is 71.7% + -6.2% -112% + -1%, the recovery rate of the neonicotinoid insecticides and the conversion products thereof with acetone as an elution solvent is 89.7% + -3.9% -112% + -4%, except that imidacloprid guanidine is 13.4% + -0.7%, the recovery rate of the neonicotinoid insecticides and the conversion products thereof with acetonitrile as an elution solvent is 51.8% + -8.2% -112% + -12%, except that imidacloprid guanidine and 6-chloronicotinic acid are 13.3 +/-1.2% and 24.1% + -5.0% respectively.
Example 10 limits of detection of pure Water and surface Water methods
1) 200mg of filler of a mixed adsorbent with HLB (HLB: PWAX: PWCX: 2:1: 1) is loaded into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and the upper end and the lower end of the mixed filler are fixed through sieve plates, so that the mixed adsorbent solid-phase extraction column is obtained.
The filled mixed adsorbent solid phase extraction column is applied to the detection limit determination of the neonicotinoid insecticides and the conversion products thereof in pure water by a method. The method comprises the following steps of adding a standard concentration of 0.1-20 ng/L to 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstonerfer Gmbh, Augussburg, Germany) in pure water and surface water, adjusting the pH value of the aqueous solution to be 4 by using dilute hydrochloric acid, and carrying out seven parallel sampling, wherein the specific operation steps are as follows:
2) and (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: and (3) loading the aqueous solution through a sample loading pipe at the flow rate of 2-3 mL/min, and enabling the aqueous solution to pass through the activated mixed solid phase extraction cartridge, wherein the sample loading volume is 200 mL.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under the vacuum-pumping condition, eluting the target substance by using 5mL of methanol, 0.5% (V/V) of acetic acid methanol and 0.5% (V/V) of ammonia water methanol in turn, and collecting the eluent.
5) Concentration: blowing and concentrating the elution liquid nitrogen obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined using Shimadzu LC-30-AD and AB Sciex QTRAP 5500 ultra-high liquid chromatography mass spectrometer.
7) The Method Detection Limit (MDL) of each compound under conditions to obtain a pure water matrix was calculated by formula (1).
MDL＝3.14×SD (1)
SD is the Standard Deviation (SD) of the detected concentration of each target compound in 7 replicates.
The calculation result shows that the method detection limit of the neonicotinoid insecticide and the conversion product thereof in the pure water is lower and is 0.077-2.03 ng/L. The detection limit of the method for the neonicotinoid insecticides and the conversion products thereof in the surface water is 0.56-5.43 ng/L, which shows that the method can be better applied to the concentration monitoring of the neonicotinoid insecticides and the conversion products thereof in the field actual water sample.
Example 11 matrix Effect
1) 14 neonicotinoid insecticides and a series of standard solutions of which the concentration of a conversion product (Dr. Ehrenstonifer Gmbh, Augustburg, Germany) is 0.01-100 mu g/L are prepared by taking pure methanol as a solvent, and an internal standard compound is imidacloprid-d4The concentration was 10. mu.g/L.
2) After solid-phase extraction is carried out on a methanol solvent containing a blank water matrix (1000 mL of mineral water without detecting a target compound in steps (1) to (4) in example 1, eluent obtained by elution of 5mL of methanol, 0.5% (V/V) of acetic acid methanol and 0.5% (V/V) of ammonia water methanol in volume is used for preparing 14 neonicotinoid insecticides and a series of standard solutions of which the concentration of a conversion product (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) is 0.01-100 mu g/L, and an internal standard compound is imidacloprid-d4(10μg/L)。
3) The Shimadzu LC-30-AD and AB Sciex QTRAP 5500 ultra-high liquid chromatography mass spectrometer are used for obtaining the standard curve of each target compound of the two series of standard solutions.
4) The Matrix Effect (ME) of each target compound was calculated by the formula (2).
ME＝(Km-Ks)/Ks (2)
KmThe slope of a standard curve of a target compound in a methanol solvent containing a blank water matrix is shown; ksThe slope of the standard curve of the target compound in methanol solvent is shown.
As a result: the linear range and the matrix effect value of each neonicotinoid insecticide and the conversion product thereof are shown in table 2. As can be seen from Table 2, most of the compounds exhibited matrix-enhancing effects, and only desmethylacetamiprid, imidacloprid olefin, and desmethylthiamethoxam exhibited matrix-attenuating effects. The matrix effect range of all the compounds is-7.58% (imidacloprid alkene) to 21.1% (acetamiprid), which indicates that the matrix effect of each compound in the method is low, and the deviation of quantitative results caused by the matrix effect can be effectively avoided.
Table 2 linear range and matrix effect values for each neonicotinoid insecticide and its conversion products.
Figure BDA0002078521660000151
Example 12 results of field actual sample detection
1) 200mg of filler of a mixed adsorbent with HLB (HLB: PWAX: PWCX: 2:1: 1) is loaded into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and the upper end and the lower end of the mixed filler are fixed through sieve plates, so that the mixed adsorbent solid-phase extraction column is obtained.
The packed mixed adsorbent solid phase extraction column is applied to the measurement of neonicotinoid insecticides and their conversion products in paddy field side drains (N28 degrees 54 '04', E115 degrees 42 '20'), rivers (N28 degrees 50 '20', E115 degrees 32 '58'), ground water (N28 degrees 53 '52', E115 degrees 42 '05'), tap water (N28 degrees 50 '29', E115 degrees 33 '05'), sewage treatment plant inlets (N23 degrees 07 '32', E113 degrees 12 '51')/outlets (N23 degrees 07 '23', E113 degrees 12 '40'). Filtering water sample with 0.7 μm glass fiber filter membrane and 0.45 μm nylon membrane to remove particulate impurities (underground water and tap water do not need to pass through the membrane to remove particulate impurities), adjusting pH to 4 with dilute hydrochloric acid, adding acetamiprid-d3(12.5ng/L) is taken as a recovery indicator, and the specific operation steps are as follows:
2) and (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: and (3) loading the water sample through a sample loading pipe at the flow rate of 2-3 mL/min and passing the water sample through the activated mixed solid phase extraction cartridge, wherein the sample loading volume is 200 mL.
4) And (3) elution: and drying the solid phase extraction column loaded with the water sample for at least 15min under the vacuum-pumping condition, then eluting the target object by using 5mL of methanol, 0.5% (V/V) of acetic acid methanol solution and 0.5% (V/V) of ammonia water methanol solution in sequence, and collecting the eluent.
5) Concentration: blowing and concentrating the elution liquid nitrogen obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(concentration 10. mu.g/L).
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined using Shimadzu LC-30-AD and AB Sciex QTRAP 5500 ultra-high liquid chromatography mass spectrometer.
As a result: and (3) after sample pretreatment and analysis, the collected water sample is used for determining the concentration of each neonicotinoid insecticide and the concentration of the conversion product thereof. As a result, as shown in Table 3, the detection rate of 14 neonicotinoid insecticides and their conversion products was 100%. The detected concentration of the neonicotinoid insecticide is not detected to be 59.9 +/-3.1 ng/L, and the detected concentration of the neonicotinoid insecticide conversion product is not detected to be 44.2 +/-4.5 ng/L.
TABLE 3 field test results (ng/L, n is 3)
Figure BDA0002078521660000161
Figure BDA0002078521660000171
aND: not detected out
b<RL: below the reporting limit
Comparative example 1 recovery rate of added standard in pure water
1) And (2) filling 60mg of a mixed adsorbent with the mass ratio of HLB (hydrophile-lipophile balance), WAX (WAX-WAX) and WCX (WCX-WAX ratio) of 2:1:1 into a hollow-tube solid-phase extraction column made of 6mL polypropylene material by a dry method under the condition of vacuumizing on a solid-phase extraction system, and fixing the upper end and the lower end of the mixed adsorbent through sieve plates to obtain the mixed adsorbent solid-phase extraction column.
2) And (3) activation: the mixed solid phase extraction cartridge was activated with 5mL of methanol and 5mL of pure water in this order.
3) Loading: after 200mL of mixed aqueous solution of 14 neonicotinoid insecticides and conversion products thereof (Dr. Ehrenstontorfer Gmbh, Augusberg, Germany) with theoretical standard concentration of 100ng/L is adjusted to pH 6 by dilute hydrochloric acid, the mixed aqueous solution is loaded through a sample loading tube at the flow rate of 2-3 mL/min and passes through an activated solid phase extraction small column, and three samples are paralleled.
4) And (3) elution: and (3) drying the solid-phase extraction column loaded with the water sample for at least 15min under a vacuum-pumping condition, eluting the target substance by using methanol with the volume of 5mL, 0.5% (V/V) acetic acid methanol and 0.5% (V/V) ammonia water methanol in sequence, and collecting the eluent.
5) Concentration: blowing and concentrating the elution liquid nitrogen obtained in the step 4), fixing the volume to 0.5mL, and adding imidacloprid-d4(10μg/L)。
6) And (3) concentration determination: the mixture was filtered through a 0.22 μm organic pinhole filter and the concentration of the compound was determined by HPLC tandem mass spectrometry using Shimadzu LC-30-AD and AB Sciex QTRAP 5500.
The pure water standard adding test result shows that the recovery rate of each neonicotinoid insecticide and the conversion product thereof is 27.4% +/-6.3% -109% +/-17%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A solid phase extraction detection method for neonicotinoid insecticides in water and their conversion products is characterized by comprising the following steps:
(1) activating the solid phase extraction column filled with the mixed adsorbent by using methanol and water;
(2) after adjusting the pH value of the water sample, adding a recovery rate indicator, and then adding the water sample into the activated mixed adsorbent solid-phase extraction column in the step (1);
(3) after vacuum drying the mixed adsorbent solid phase extraction cartridge loaded with the water sample in the step (2), sequentially eluting with an organic solvent, an organic solvent added with acid and an organic solvent added with alkali to obtain an eluent, and then adding an internal standard compound into the eluent;
(4) detecting the concentration of a target compound by adopting an ultra-high liquid chromatography tandem mass spectrum;
the mass ratio of each adsorbent in the mixed adsorbent in the step (1) is HLB: WAX: WCX is 1-4: 1-10: 1-2;
the mass of the mixed adsorbent in the solid phase extraction column filled with the mixed adsorbent in the step (1) is 100-400 mg;
the pH value of the water sample after adjustment in the step (2) is 2-7;
the organic solvent in the step (3) is methanol; the organic solvent after the acid is added in the step (3) is an organic solvent containing acetic acid with the volume ratio of 0.2-1.0%;
the organic solvent after the alkali is added in the step (3) is an organic solvent with the volume ratio of ammonia water of 0.2-2.5%;
the dosage of the organic solvent, the organic solvent after the acid is added and the organic solvent after the alkali is added in the step (3) is independently 2-8 mL.
2. The method for detecting the solid-phase extraction of the neonicotinoid insecticides in water and the transformed products thereof according to claim 1, wherein the method comprises the following steps:
the specification of the solid phase extraction small column filled with the mixed adsorbent in the step (1) is 3-6 mL;
the adding amount of the water sample in the step (2) is 200-1000 mL;
and (3) adding the water sample in the step (2) at the speed of 2-3 mL/min.
3. The method for detecting the solid-phase extraction of the neonicotinoid insecticides in water and the transformed products thereof according to claim 1, wherein the method comprises the following steps:
when the mass of the mixed adsorbent in the solid phase extraction column filled with the mixed adsorbent in the step (1) is 200-400 mg, the mass ratio of the adsorbents is HLB: WAX: WCX is 1-4: 1-10: 1-2, wherein the pH value of the water sample after the adjustment in the step (2) is 4-7.
4. The method for detecting the solid-phase extraction of the neonicotinoid insecticides in water and the transformed products thereof according to claim 1, wherein the method comprises the following steps:
the solid phase extraction column filled with the mixed adsorbent in the step (1) is obtained by the following method:
the mixed adsorbent is filled into a hollow tube solid phase extraction column by a dry method under the vacuum condition, and the upper end and the lower end of the mixed adsorbent are fixed by a sieve plate, so that the mixed adsorbent solid phase extraction column is obtained;
and (3) before adjusting the pH value of the water sample, removing impurities, namely sequentially passing the water sample through a 0.7-micron glass fiber filter membrane and a 0.22-0.45-micron nylon membrane.
5. The method for detecting the solid-phase extraction of the neonicotinoid insecticides in water and the transformed products thereof according to claim 1, wherein the method comprises the following steps:
the recovery rate indicator in the step (2) is acetamiprid-d3The standard adding concentration of the water sample is 10-100 ng/L.
6. The method for detecting the solid-phase extraction of the neonicotinoid insecticides in water and the transformed products thereof according to claim 1, wherein the method comprises the following steps:
the internal standard compound in the step (3) is imidacloprid-d4The concentration of the eluent is 5-100 mug/L.
7. The method for detecting the solid-phase extraction of the neonicotinoid insecticides in water and the transformed products thereof according to claim 1, wherein the method comprises the following steps:
and (4) carrying out nitrogen blowing concentration on the eluent obtained in the step (3), wherein the nitrogen blowing concentration is to blow and concentrate the elution liquid nitrogen to 0.2-1.0 mL.
8. The method for detecting the solid-phase extraction of the anabasine insecticides in water and the conversion products thereof according to claim 1, wherein the detection in the step (4) is specifically as follows:
the method is characterized by comprising the steps of (1) performing ultra-high liquid chromatography tandem mass spectrometry on Shimadzu LC-30-AD and AB Sciex QTRAP 5500, wherein a chromatographic column is an Agilent eclipse plus C18 column with the specification of 100mm multiplied by 2.1mm multiplied by 1.8 mu m, and is connected with a zorbax eclipse plus-C18 protective column with the specification of 12.5mm multiplied by 2.1mm multiplied by 5 mu m and the column temperature is 40 ℃; the mobile phase A is: 0.1% by volume of aqueous formic acid, and the mobile phase B is: acetonitrile, gradient elution;
the gradient elution procedure was as follows: 0-0.5 min, wherein the volume fraction of the mobile phase B is 10%; 3.0min, the volume fraction of the mobile phase B is 90 percent; 11.0min, the volume fraction of the mobile phase B is 90 percent; 11.1min, the volume fraction of the mobile phase B is 10 percent; 11.1-15.0 min, wherein the volume fraction of the mobile phase B is 10%; the sample introduction volume is 2 mu L, the electrospray ion source is adopted, the positive mode is adopted, the multi-reaction monitoring is carried out for quantification, the atomization gas is nitrogen, the rolling curtain gas is 45Psi, the collision gas is 8Psi, the ion spray voltage is 5500V, the ion source temperature is 550 ℃, the ion source gas circuit 1 is 55Psi, the ion source gas circuit 2 is 55Psi, and the inlet voltage and the collision cell outlet voltage are respectively 10.0V and 16.0V.
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