CN103293267A - GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing pyrethroid pesticide residue in tobacco and tobacco product - Google Patents
GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing pyrethroid pesticide residue in tobacco and tobacco product Download PDFInfo
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Abstract
The invention relates to a GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing pyrethroid pesticide residue in tobacco and a tobacco product, which is characterized by comprising the following steps: drenching a sample with water, and adding acetonitrile and an internal standard substance; performing vortex extraction and salting-out stratification, and performing secondary salting-out and liquid-liquid extraction with a sodium chloride water solution and n-hexane; and taking the n-hexane supernatant, and determining according to a GC-MS/MS method. The method provided by the invention simplifies the existing sample treatment method, provides a cleaner on-machine solution, and reduces the maintenance of instruments in the operating process. The sample pretreatment process of the method provided by the invention employs the step of drenching the sample with water in the existing method to improve the extraction effect of the acetonitrile on a pesticide target substance, and simultaneously omits the step of putting into a refrigerator before adding into a salting-out package. Inspection discovers that most of pyrethroid pesticides are thermostable, so that the pyrethroid pesticides can not be degraded due to heat release caused by the combination of anhydrous magnesium sulfate and water, thus saving the operating time herein.
Description
Technical field
The invention belongs to Detecting Pesticide technical field in tobacco and the tobacco product, relate generally to the pyrethroid pesticide remained determination techniques in tobacco and the tobacco product.
Background technology
Pyrethroid pesticide is a kind of broad spectrum pesticide that can prevent and treat various pests, and its killing ability is stronger than organochlorine, organophosphorus, so its consumption is little, and working concentration is low, and is also less to people and animals' harm.So the use of pyrethroid pesticide is comparatively extensive, its recall rate is also higher but Just because of this.
Residues of pesticides refer to the applications of pesticide after crops, remain in trace pesticide and metabolin and catabolite etc. in environment, crops and the biosome.In the storage process after grow seedlings growth and the harvesting of tobacco, inevitably use herbicide, plant growth regulator, pesticide, acaricide and germifuge etc.And simultaneously tobacco as a kind of product of sucking, its security requirement height, therefore, the residues of pesticides in the tobacco have obtained paying close attention to widely.
In view of harmfulness and the importance of residues of pesticides, a lot of countries and regions have proposed the Pesticide Residue in the multiple kinds of crops and quality control method, as the method simultaneously of Japan, the SANCO/10684/2009 of European Union etc.International tobacco scientific research cooperation center (CORESTA) has proposed guiding residual the limiting the quantity of of 99 kinds of agricultural chemicals in the tobacco (GRLs, Guidance Residue Levels) in Dec, 2003, and revise in June, 2008, now is 118 kinds.
Detection method to pyrethroid pesticide remained analysis in the tobacco mainly contains gas chromatography (GC) and gas chromatography-mass spectrography (GC-MS).Gas chromatography-tandem mass spectrum (GC-MS/MS) does not also have to be used for separately the detection analysis of pyrethroid pesticide.Mass spectrum has improved the reliability of method on qualitative as detecting device, and second order ms (MS/MS) is one-level mass spectrum (MS) relatively, and its antijamming capability is stronger, lower to the requirement of sample pre-treatments.
The high selectivity and the strong anti-interference ability that be to adapt to second order ms, using maximum in the pre-treating method is exactly QuEChERS method simply fast.From 2003, Anastassiades etc. proposed to be applicable to that this method develops rapidly and updates after the QuEChERS method of multi-residue analysis in the fruits and vegetables, and are applied to the mensuration of residues of pesticides in tobacco and the tobacco product.The General Principle of this method is, acetonitrile extraction back purifies with PSA, then or dilution or solvent replace last machine testing.
Summary of the invention:
Purpose of the present invention is intended to further simplify existing method and obtain cleaner last machine solution, provide a kind of sample behind water infiltration, add acetonitrile and internal standard compound, vortex extraction then, the layering of saltouing, carry out with sodium-chloride water solution and normal hexane then that secondary is saltoutd and liquid-liquid extraction, get the normal hexane supernatant, (GC-MS/MS) carries out method for measuring with gas chromatography-tandem mass spectrometry.This method can fast, accurately detect in tobacco and the tobacco product pyrethroid pesticide remained, and measurement result is accurate, good reproducibility.
The objective of the invention is to be achieved through the following technical solutions: the assay method of pyrethroid pesticide remained amount may further comprise the steps in tobacco of the present invention and the tobacco product:
The preparation of a, inner mark solution: preparation TPP(triphenyl) concentration is the acetone soln of 20 μ g/mL;
B, take by weighing sample: take by weighing 2.0 g tobacco samples in 50 mL tool plug centrifuge tubes, be accurate to 0.1 g;
C, add the water infiltration sample: accurately add 10 mL water, soak into 10 min;
D, oscillation extraction: accurately add 10 mL acetonitriles and 100 μ L inner mark solutions, on whirlpool mixing shaker with 2000 rpm vortexs, 1 min;
E, the layering of saltouing: add the pack of saltouing and (contain 4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate), immediately on whirlpool mixing shaker with 2000 rpm, 2 min that vibrate, on supercentrifuge with centrifugal 3 min of 5000 rpm;
F, liquid-liquid extraction: get 1 mL acetonitrile extract in 15 mL centrifuge tubes, and add 1 mL normal hexane and 5 mL, 20% sodium-chloride water solution, on the whirlpool mixer oscillator with speed oscillation 2 min of 2000 rpm, with centrifugal 3 min of 5000 rpm, it is stand-by to get the upper strata hexane solution on supercentrifuge;
G, preparation standard operation solution: take by weighing 0.010 g(respectively and be accurate to 0.1 mg) various standard sample of pesticide, place same 10 mL volumetric flasks, with acetone solution and constant volume, (9:1 v/v) dilutes the standard operation solution that also finally is mixed with the various agricultural chemicals with concentration gradient to use normal hexane-acetone then;
H, prepare matrix and join the mark working solution: after blank tobacco sample is handled by identical pre-treatment mode, after getting 1 mL upper strata hexane solution nitrogen respectively and drying up, redissolve with the pesticide standard working solution of 1 mL variable concentrations gradient;
I, GC-MS/MS measure: the matrix of drawing the variable concentrations for preparing is joined the mark working solution, behind the organic filter membrane of 0.22 μ m, injects GC-MS/MS excessively;
J, pesticide residue determination result's calculating: carry out the quantitative test of agricultural chemicals object with internal standard method, namely select the quasi-molecular ions area to compare its respective concentration with the secondary of agricultural chemicals and interior mark TPP and carry out regretional analysis, obtain typical curve; Sample after extracting is measured, recorded the secondary that detects agricultural chemicals and interior mark TPP and select the ion peak area ratio, the substitution typical curve is tried to achieve the content of pyrethroid pesticide in the sample.
In the present invention, the manner of formulation of standard operation solution is as follows: take by weighing 0.01 g(respectively and be accurate to 0.1 mg) various standard sample of pesticide, place same 10 mL volumetric flasks, with acetone solution and constant volume, being mixed with each pesticide concentration is the mixed standard solution I of 1 mg/mL; Accurately pipette 1 mL mixed standard solution I then, place 100 mL volumetric flasks, with the acetone constant volume, being mixed with each pesticide concentration is the mixed standard solution II of 10 μ g/mL; Accurately pipette 2 mL mixed standard solution II then, place 10 mL volumetric flasks, (being mixed with each pesticide concentration is the mixed standard solution III of 2 μ g/mL for 9:1, v/v) constant volume with normal hexane-acetone; Accurately pipette the mixed standard solution III of 0.01 mL, 0.025 mL, 0.05 mL, 0.1 mL, 0.25 mL, 0.5 mL and 1 mL, place 10 mL volumetric flasks, accurately add 100 μ L inner mark solutions, with normal hexane-acetone (9:1, v/v) constant volume namely gets the series standard working solution.The series standard solution concentration of preparation is: 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL.
When GC-MS/MS measured, the chromatographic condition of employing was: chromatographic column: TR-Pesticide II elastic quartz capillary tube chromatographic column (30 m * 0.25 mm * 0.25 μ m); Injector temperature: 250 ℃; Temperature programme: 90 ℃ of initial temperatures, keep rising to 180 ℃ with 25 ℃/min behind 5 min, keep 15 min; Rise to 280 ℃ with 5 ℃/min then, keep 6.5 min; Program behind the post: 300 ℃, keep 5 min; Split sampling is not shunted time 1 min; Carrier gas: helium (purity is 99.999%); Constant current mode, flow velocity are 1.2 mL/min; Sample size: 1 μ L.Total run time is 55 min.
The mass spectrum condition that adopts is: EI ionization pattern, ionization energy 70 eV; Filament current: 50 μ A; Ion source temperature: 250 ℃; Transmission line temperature: 280 ℃; Q2 collides gas: argon gas (purity 99.999%), and collision pond pressure is 1.0 mTorr; Solvent delay 5 min; Scan mode: multiple-reaction monitoring (MRM).44 kinds of agricultural chemicals and interior target retention time and mass spectrum parameter see Table 1.
Table 1 pyrethroid pesticide object and interior target retention time and MRM parameter
Method of the present invention has been simplified existing sample treatment, and cleaner last machine solution is provided, and has reduced instrument maintenance in use.Compared with prior art the inventive method has following excellent results:
⑴ used for reference the step of " with the water infiltration sample " in the existing method in the inventive method sample pretreatment process to improve acetonitrile to the effect of extracting of agricultural chemicals object; Saved the step of " adding saltout bag before put into refrigerator " simultaneously, found that through investigating pyrethroid pesticide is mostly thermally-stabilised, not can because of anhydrous magnesium sulfate and water cause degraded in conjunction with heat release, so locate and can save the running time.
⑵ save matrix in the inventive method sample pretreatment process and disperse the purifying step of Solid-Phase Extraction (d-SPE), but get the acetonitrile extract, carry out liquid-liquid extraction and secondary is saltoutd with normal hexane and sodium-chloride water solution, guaranteed nonpolar and the recovery low pole object.Simultaneously, because normal hexane is nonpolar strong, so the polarity coextraction matrix in the supernatant liquor also significantly reduces, last machine solution is cleaner, has reduced instrument maintenance in use.
⑶ the inventive method has adopted the GC-MS/MS of high sensitivity and strong anti-interference ability to detect, and therefore has the advantage of operating accurate, highly sensitive and good reproducibility.
1. the detectability of the inventive method:
The matrix of variable concentrations agricultural chemicals is joined the mark working solution inject GC-MS/MS, calculate detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), detectability is between 0.24 ng/g～4.55 ng/g.
2. the repeatability of the inventive method and recovery of standard addition:
The standard solution (concentration is 50 ng/mL) that adds pyrethroid pesticide in blank tobacco sample carries out pre-treatment and GC-MS/MS then respectively and analyzes, and calculates its recovery according to adding the scalar sum measured value, the results are shown in Table 2.As can be seen from Table 2, the recovery of agricultural chemicals is between 89.94%～102.78%, and relative standard deviation (RSD) illustrates the recovery height of the inventive method, good reproducibility between 1.85%～10.49%.
Description of drawings
Fig. 1 is assay method process flow diagram of the present invention (this figure is as Figure of abstract).
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Example 1:
1. instrument and reagent:
Pyrethroid pesticide: Biphenthrin, cyfloxylate, lambda-cyhalothrin, cypermethrin, decis, fenvalerate, flucythrinate, Permethrin (suitable), Permethrin (instead), Tefluthrin, interior mark: TPP is standard items; Acetonitrile, acetone, normal hexane are chromatographic grade reagent; Distilled water meets the requirement of one-level water among the GB/T 6682.
U.S. Thermo Fisher TSQ Quantum GC gas chromatography-triple level Four bar tandem mass spectrometers; Switzerland Mettler AE 163 electronic balance (sensibility reciprocals: 0.0001g); U.S. Labnet VtexMixer VX200 oscillator; Germany Sigma high speed freezing centrifuge.
2. sample preparation:
Take by weighing about 2 g samples, be accurate to 0.01 g, in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate and after sample is fully soaked into by water, leave standstill 10 min.Pipette 10 mL acetonitriles to centrifuge tube, add mark working fluid in the 100 μ L, and place on the whirlpool mixing shaker with 2000 r/min velocity fluctuations, 1 min.In centrifuge tube, add 4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate, immediately on whirlpool mixing shaker with 2000 rpm, 2 min that vibrate, on supercentrifuge with centrifugal 3 min of 5000 rpm;
Get 1 mL acetonitrile extract in 15 mL centrifuge tubes, include 1 mL normal hexane and 5 mL, 20% sodium-chloride water solution, with speed oscillation 2 min of 2000 rpm, with centrifugal 3 min of 5000 rpm, it is stand-by to get the upper strata hexane solution on supercentrifuge on the whirlpool mixer oscillator;
3. prepare standard operation solution:
Take by weighing 0.01 g(respectively and be accurate to 0.1 mg) various standard sample of pesticide, place same 10 mL volumetric flasks, with acetone solution and constant volume, being mixed with each pesticide concentration is the mixed standard solution I of 1 mg/mL; Accurately pipette 1 mL mixed standard solution I then, place 100 mL volumetric flasks, with the acetone constant volume, being mixed with each pesticide concentration is the mixed standard solution II of 10 μ g/mL; Accurately pipette 2 mL mixed standard solution II then, place 10 mL volumetric flasks, (being mixed with each pesticide concentration is the mixed standard solution III of 2 μ g/mL for 9:1, v/v) constant volume with normal hexane-acetone; Accurately pipette the mixed standard solution III of 0.01 mL, 0.025 mL, 0.05 mL, 0.1 mL, 0.25 mL, 0.5 mL and 1 mL, place 10 mL volumetric flasks, accurately add 100 μ L inner mark solutions, with normal hexane-acetone (9:1, v/v) constant volume namely gets the series standard working solution.The series standard solution concentration of preparation is: 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL.
4. prepare matrix and join the mark working solution:
After blank tobacco sample handled (with reference to step 2. sample preparation ") by identical pre-treatment mode, after getting 1 mL upper strata hexane solution nitrogen respectively and drying up, redissolve with the pesticide standard working solution of 1 mL variable concentrations gradient;
5. assay method:
The agricultural chemicals matrix of the variable concentrations for preparing is joined the mark working solution inject GC-MS/MS, carry out the quantitative test of agricultural chemicals with internal standard method, namely compare its respective concentration with agricultural chemicals with the secondary selection quasi-molecular ions area of interior mark TPP and carry out regretional analysis, obtain typical curve; Sample after extracting is measured, recorded the secondary that detects agricultural chemicals and interior mark TPP and select the ion peak area ratio, the substitution typical curve, the content of trying to achieve the pyrethroid pesticide in the sample sees Table 3.
Table 3The testing result of agricultural chemicals object among the sample A
| Sequence number | The Chinese adopted name | The content of agricultural chemicals object in the sample (μ g/g) |
| 1 | Biphenthrin | —— |
| 2 | Cyfloxylate | —— |
| 3 | Lambda-cyhalothrin | —— |
| 4 | Cypermethrin | —— |
| 5 | Decis | —— |
| 6 | Fenvalerate | 0.04 |
| 7 | Flucythrinate | —— |
| 8 | Permethrin (suitable) | —— |
| 9 | Permethrin (instead) | —— |
| 10 | Tefluthrin | —— |
Annotate: "-" expression does not detect
When GC-MS/MS measured, the chromatographic condition of employing was: chromatographic column: TR-Pesticide II elastic quartz capillary tube chromatographic column (30 m * 0.25 mm * 0.25 μ m); Injector temperature: 250 ℃; Temperature programme: 90 ℃ of initial temperatures, keep rising to 180 ℃ with 25 ℃/min behind 5 min, keep 15 min; Rise to 280 ℃ with 5 ℃/min then, keep 6.5 min; Program behind the post: 300 ℃, keep 5 min; Split sampling is not shunted time 1 min; Carrier gas: helium (purity is 99.999%); Constant current mode, flow velocity are 1.2 mL/min; Sample size: 1 μ L.Total run time is 55 min.
The mass spectrum condition that adopts is: EI ionization pattern, ionization energy 70 eV; Filament current: 50 μ A; Ion source temperature: 250 ℃; Transmission line temperature: 280 ℃; Q2 collides gas: argon gas (purity 99.999%), and collision pond pressure is 1.0 mTorr; Solvent delay 5 min; Scan mode: multiple-reaction monitoring (MRM).Pyrethroid pesticide and interior target retention time and mass spectrum parameter see Table 1.
Example 2:
As described in embodiment 1, select another tobacco sample B, the content that records pyrethroid pesticide object in the sample sees Table 4.
Table 4The testing result of agricultural chemicals object among the sample B
| Sequence number | The Chinese adopted name | The content of agricultural chemicals object in the sample (μ g/g) |
| 1 | Biphenthrin | —— |
| 2 | Cyfloxylate | —— |
| 3 | Lambda-cyhalothrin | —— |
| 4 | Cypermethrin | —— |
| 5 | Decis | —— |
| 6 | Fenvalerate | 0.02 |
| 7 | Flucythrinate | —— |
| 8 | Permethrin (suitable) | —— |
| 9 | Permethrin (instead) | —— |
| 10 | Tefluthrin | —— |
Annotate: "-" expression does not detect
Example 3:
As described in embodiment 1, select another tobacco sample C, the content that records pyrethroid pesticide object in the sample sees Table 5.
Table 5The testing result of agricultural chemicals object among the sample C
| Sequence number | The Chinese adopted name | The content of agricultural chemicals object in the sample (μ g/g) |
| 1 | Biphenthrin | —— |
| 2 | Cyfloxylate | —— |
| 3 | Lambda-cyhalothrin | 0.03 |
| 4 | Cypermethrin | —— |
| 5 | Decis | —— |
| 6 | Fenvalerate | 1.32 |
| 7 | Flucythrinate | —— |
| 8 | Permethrin (suitable) | —— |
| 9 | Permethrin (instead) | —— |
| 10 | Tefluthrin | —— |
Annotate: "-" expression does not detect
Example 4:
As described in embodiment 1, select another tobacco sample D, the content that records pyrethroid pesticide object in the sample sees Table 6.
Table 6The testing result of agricultural chemicals object among the sample D
| Sequence number | The Chinese adopted name | The content of agricultural chemicals object in the sample (μ g/g) |
| 1 | Biphenthrin | 0.05 |
| 2 | Cyfloxylate | —— |
| 3 | Lambda-cyhalothrin | —— |
| 4 | Cypermethrin | —— |
| 5 | Decis | —— |
| 6 | Fenvalerate | —— |
| 7 | Flucythrinate | —— |
| 8 | Permethrin (suitable) | —— |
| 9 | Permethrin (instead) | —— |
| 10 | Tefluthrin | —— |
Annotate: "-" expression does not detect
Claims (4)
1. analyze GC-MS/MS method pyrethroid pesticide remained in tobacco and the tobacco product for one kind, it is characterized in that: be with sample behind water infiltration, add acetonitrile and internal standard compound, vortex extraction then, the layering of saltouing, carry out with sodium-chloride water solution and normal hexane afterwards that secondary is saltoutd and liquid-liquid extraction, get the normal hexane supernatant, (GC-MS/MS) carries out method for measuring with gas chromatography-tandem mass spectrometry, and concrete grammar is as follows:
The preparation of a, inner mark solution: preparation TPP(triphenyl) concentration is the acetone soln of 20 μ g/mL;
B, take by weighing sample: take by weighing 2.0 g tobacco samples in 50 mL tool plug centrifuge tubes, be accurate to 0.1 g;
C, add the water infiltration sample: accurately add 10 mL water, soak into 10 min;
D, oscillation extraction: accurately add 10 mL acetonitriles and 100 μ L inner mark solutions, on whirlpool mixing shaker with 2000 rpm vortexs, 1 min;
E, the layering of saltouing: add the pack of saltouing and (contain 4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate), immediately on whirlpool mixing shaker with 2000 rpm, 2 min that vibrate, on supercentrifuge with centrifugal 3 min of 5000 rpm;
F, liquid-liquid extraction: get 1 mL acetonitrile extract in 15 mL centrifuge tubes, and add 1 mL normal hexane and 5 mL, 20% sodium-chloride water solution, on the whirlpool mixer oscillator with speed oscillation 2 min of 2000 rpm, with centrifugal 3 min of 5000 rpm, it is stand-by to get the upper strata hexane solution on supercentrifuge;
G, preparation standard operation solution: take by weighing 0.010 g(respectively and be accurate to 0.1 mg) various standard sample of pesticide, place same 10 mL volumetric flasks, with acetone solution and constant volume, (9:1 v/v) dilutes the series standard working solution that also finally is mixed with the various agricultural chemicals with concentration gradient to use normal hexane-acetone then;
H, prepare matrix and join the mark working solution: after blank tobacco sample is handled by identical pre-treatment mode, after getting 1 mL upper strata hexane solution nitrogen respectively and drying up, redissolve with the pesticide standard working solution of 1 mL variable concentrations gradient;
I, GC-MS/MS measure: the matrix of drawing the variable concentrations for preparing is joined the mark working solution, behind the organic filter membrane of 0.22 μ m, injects GC-MS/MS excessively;
J, pesticide residue determination result's calculating: carry out the quantitative test of agricultural chemicals object with internal standard method, namely select the quasi-molecular ions area to compare its respective concentration with the secondary of agricultural chemicals and interior mark TPP and carry out regretional analysis, obtain typical curve; Sample after extracting is measured, recorded the secondary that detects agricultural chemicals and interior mark TPP and select the ion peak area ratio, the substitution typical curve is tried to achieve the content of pyrethroid pesticide in the sample.
2. pyrethroid pesticide remained GC-MS/MS method in analysis tobacco according to claim 1 and the tobacco product, it is characterized in that: pyrethroid pesticide refers to following 10 kinds: Biphenthrin, cyfloxylate, lambda-cyhalothrin, cypermethrin, decis, fenvalerate, flucythrinate, Permethrin (suitable), Permethrin (instead), Tefluthrin.
3. pyrethroid pesticide remained GC-MS/MS method in analysis tobacco according to claim 1 and the tobacco product, it is characterized in that: the series standard working solution concentration with various agricultural chemicals of concentration gradient is: 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL.
4. pyrethroid pesticide remained GC-MS/MS method in analysis tobacco according to claim 1 and the tobacco product is characterized in that:
When GC-MS/MS measured, the chromatographic condition of employing was: chromatographic column: TR-Pesticide II elastic quartz capillary tube chromatographic column (30 m * 0.25 mm * 0.25 μ m); Injector temperature: 250 ℃; Temperature programme: 90 ℃ of initial temperatures, keep rising to 180 ℃ with 25 ℃/min behind 5 min, keep 15 min; Rise to 280 ℃ with 5 ℃/min then, keep 6.5 min; Program behind the post: 300 ℃, keep 5 min; Split sampling is not shunted time 1 min; Carrier gas: helium (purity is 99.999%); Constant current mode, flow velocity are 1.2 mL/min; Sample size: 1 μ L, total run time are 55 min;
The mass spectrum condition that adopts is: EI ionization pattern, ionization energy 70 eV; Filament current: 50 μ A; Ion source temperature: 250 ℃; Transmission line temperature: 280 ℃; Q2 collides gas: argon gas (purity 99.999%), and collision pond pressure is 1.0 mTorr; Solvent delay 5 min; Scan mode: multiple-reaction monitoring (MRM) 2.
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| CN113933446A (en) * | 2021-10-27 | 2022-01-14 | 上海市农产品质量安全中心 | Method for rapidly detecting 10 pyrethroid pesticide residues in situ and kit thereof |
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