CN103913528A - Quantitative detection method for pyrethriods pesticides in fresh tea - Google Patents
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Abstract
The invention discloses a quantitative detection method for pyrethriods pesticides in fresh tea. The quantitative detection method is characterized by comprising the following steps: ultrasonically extracting a fresh tea sample by an acetonitrile solution containing 1% of acetic acid in percentage by volume, then purifying by using an appropriate amount of mixed filler of PSA (Prostate Specific Antigen), C18 and GCB, carrying out nitrogen blowing to concentrate liquid supernatant to be nearly dry, dissolving with normal hexane and making up to volume, increasing programmed temperature and separating by using an HP-5 quartz capillary column, carrying out GC/muECD, and finally quantifying by using a matrix external standard method. Through confirmation by test, the method is wide in linear range; the technical indexes such as detection sensitivity, accuracy and precision meet the requirements of analysis of residues; the pretreatment operation is simple, convenient and quick; through the method, a reliable manner is provided for analysis and research for detecting the residues of the pyrethriods pesticides in the fresh tea.
Description
Technical field
The present invention relates to the detection method field of persticide residue, be specifically related to the quantitative detecting method of pyrethroid pesticide in the fresh leaf of a kind of tea, this quantitative detecting method is to adopt improved QuEChERS method that the fresh leaf of tea is extracted, purified, by vapor-phase chromatography, pyrethroid pesticide is detected again, to reach quick, easy, reliable object.
Background technology
Tealeaves is one of the world's three large plant beverages, because of its unique mouthfeel and there is anticancer, anti-sudden change, remove free radical, favor that the health-care efficacy such as delay senility is more and more subject to people.China is Ye Shi big export country of Tea Production big country, applying pesticides is to ensure tea yield, control and in its growth course, avoid the most effective means that disease and pest threatens, pyrethroid pesticide (English name: Pyrethroid pesticides) is because of wide spectrum, the preventing and controlling that efficient, cost is low, consumption is widely used in tealeaves disease and pest less.But existing studies confirm that this class agricultural chemicals can produce toxic action to the nervous system of human body, that part kind has is carcinogenic, teratogenesis, mutagenesis and certain property accumulated, and excessive use is likely accumulated in human body, causes chronic accumulate poisoning.Therefore, about pyrethroid pesticide, residual in tealeaves is the focal issue that people pay close attention to always.
Many countries, particularly European Union and Japan have formulated harsh Pesticide Residue regulation in the world, to limit the maximum residue limit (MRL) of Pesticides in Tea medicine.China standard GB/T 2763-2012 " Pesticide maximum residue limit " has specified the MRL of 25 kinds of agricultural chemicals in tealeaves, and " The Ministry of Agriculture of the People's Republic of China, MOA bulletin No. 199 " specified that 21 kinds of agricultural chemicals forbid or be limited in tealeaves using.European Union has issued new Pesticide Residue Standard andRegulation (EC) No149/2008 on March 1st, 2008, upgrade the MRL of Pesticide Residues in Tea, new legislation relates to 221 of the existing limit standards of Pesticide Residues in Tea, 171 of provisional limit standards, totally 392, and more than 90% pesticide recovery method detection limit is as MRL.Japan is agricultural chemicals " Positive List System " in formal enforcement on May 29th, 2006 food, in this system, the Pesticide Residue standard relevant with tealeaves reaches 251, and the MRL of most of agricultural chemicals requires to be not more than 0.1mg/kg, the agricultural chemicals of not setting limit standard is all carried out to " uniform limit ", be that content must not exceed 0.01mg/kg, and all adopt " dry tea method " to detect.This has limited the outlet of China's tealeaves to a great extent, the detection of Pesticide Residues in Tea is also had higher requirement simultaneously.
In recent years, about the existing many research reports of the analytical approach of Pesticide Residues in Tea, but mainly concentrate on on tea few to the residual research in the fresh leaf of tea.The fresh leaf of tea, as the raw material of Tea Processing, is the material base that determines tea leaf quality, and its quality is directly connected to the quality of tea leaf quality.Therefore, the persticide residue of directly measuring in the fresh leaf of tea has important practical significance, and not only can realize the source of tealeaves agricultural chemicals and control, and effectively guides peasant correctly to tea place medication, improve the security of drinking tea, and can reduce agricultural chemicals and use unreasonably tea garden soil environment.
Contain the interfering materials such as more moisture, pigment, water-soluble ass, Tea Polyphenols to tea because the fresh leaf of tea likens, more easily cause extraction and cleaning difficulty, the therefore detection method of pyrethrin pesticide in existing mensuration tealeaves, is not suitable for the mensuration of the fresh phyllopodium matter of tea.There are some though domestic about the residual research work report of the fresh leaf agriculture of tea, but only relate to the detection of the organo-chlorine pesticide such as benzene hexachloride, D.D.T. (dichloro-diphenyl-trichloroethane) and a few pyrethrin pesticide, the detection method research of 7 kinds of pyrethrin pesticides such as gamma cyhalothrin, fenvalerate in the fresh leaf of tea is had no to report simultaneously.And in the fresh leaf residues of pesticides of tea leaching process, existing report mainly uses the methods such as traditional mechanical shaking extraction, homogeneous extraction, liquid-liquid extraction, purification means adopt concentrated acid sulfonation method and column chromatography purification method for different target agricultural chemicals more.These pre-treating methods consume that organic solvents are many, sample flux is little, are of limited application, complex operation, expend time in, cost is high, how residual for multiclass is not simply or effective method.
Summary of the invention
The invention provides the quantitative detecting method of pyrethroid pesticide in the fresh leaf of a kind of tea, the detection method length consuming time, complex operation, consumption organic solvent that its object is to solve pyrethrin pesticide in existing mensuration tealeaves mainly with and the reliable and stable not problem of testing result.
For achieving the above object, the technical solution used in the present invention is: the quantitative detecting method of pyrethroid pesticide in the fresh leaf of a kind of tea, and described quantitative detecting method is made up of two parts:
Part I, sets up respectively the typical curve of the tested pyrethroid pesticide of known gradient concentration by vapor-phase chromatography; The foundation of described typical curve is made up of following steps:
The first step, prepares blank matrix extract, and preparation method is made up of following steps:
(1) take the fresh leaf sample of blank tea that 5.0g does not contain tested pyrethroid pesticide after measured, be placed in 50mL centrifuge tube, in centrifuge tube, add 10mL to contain the acetonitrile solution that volume fraction is 1% acetic acid again, mix, ultrasonic extraction 10～15min, then add 2g anhydrous sodium acetate and 1g anhydrous magnesium sulfate, vortex 1.5min～2.5min, then,, with the centrifugal 3.5min～4.5min of rotating speed of 9000r/min, get supernatant and be blank matrix extract to be clean;
(2) separately get a 10mL centrifuge tube, add 0.15g C18,0.15g N-propyl group ethylenediamine, 0.12g ketjenblack EC and 0.3g anhydrous magnesium sulfate, add blank matrix extract to be clean described in 4mL, vortex 1.5min～2.5min, with the centrifugal 4.5min～5.5min of rotating speed of 9000r/min; After centrifugal, pipette 2.0mL supernatant to scale test tube, then under 50～60 DEG C of water-baths, supernatant is slowly blown to 50～70 μ L with nitrogen; In supernatant, add again normal hexane to be settled to 1.0mL, cross after organic system filter membrane, obtain the blank matrix extract of pyrethroid pesticide;
Second step, the matrix hybrid standard working solution of preparation pyrethroid pesticide taking the blank matrix extract that obtains in the described first step as solvent, wherein, described pyrethroid pesticide refers to Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis; In the matrix hybrid standard working solution of described pyrethroid pesticide, the concentration range of each pyrethroid pesticide is:
The 3rd step, with chromatographic peak retention time and the chromatographic peak area of each pesticide composition in the matrix hybrid standard working solution of pyrethroid pesticide described in gas chromatography determination, qualitative with chromatographic peak retention time, then taking mass concentration as horizontal ordinate, draw out the typical curve of pyrethroid pesticide taking chromatographic peak area as ordinate;
Wherein, the chromatographic condition of mensuration pyrethroid pesticide is:
Chromatographic column: the capillary chromatographic column that model is HP-5, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 DEG C, dottle pin purges 3mL/min; Column temperature: 80 DEG C of initial temperatures, keep 0.3min, 30 DEG C/min rises to 180 DEG C, keeps 5min, and 20 DEG C/min rises to 260 DEG C, keeps 23min: carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 1mL/min; Detecting device: micro-pond electron capture detector; Detector temperature: 300 DEG C; Make-up gas: high pure nitrogen, 60mL/min;
Part II, measures 7 kinds of pyrethroid pesticide residual quantities in Part I described in the fresh leaf sample of tea, and quantitative detecting method comprises the following steps:
The first step, extracts the fresh leaf sample of tea;
Take the fresh leaf sample of the tea of having pulverized, be placed in 50mL centrifuge tube, then to add containing volume fraction be the acetonitrile solution of 1% acetic acid, wherein, the input ratio of the fresh leaf sample of described tea and described acetonitrile solution, for to drop into 1mL acetonitrile solution in the fresh leaf sample of every 0.5g tea, mixes, ultrasonic extraction 10～15min; Add again anhydrous sodium acetate and anhydrous magnesium sulfate, wherein, the fresh leaf sample of described tea, anhydrous sodium acetate and anhydrous magnesium sulfate three's mass ratio is 5:2:1, vortex 1.5min～2.5min, with the centrifugal 3.5min～4.5min of rotating speed of 9000r/min, get supernatant and be the fresh leaf sample extracting solution of tea to be clean;
Second step, purifies the fresh leaf sample extracting solution of described tea to be clean;
Separately get a 10mL centrifuge tube, add C18, N-propyl group ethylenediamine, ketjenblack EC and anhydrous magnesium sulfate, add the fresh leaf sample extracting solution of described tea to be clean, wherein, the content of C18, N-propyl group ethylenediamine, ketjenblack EC and the anhydrous magnesium sulfate dropping in the fresh leaf sample extracting solution of tea to be clean is respectively 37.5mg/mL, 37.5mg/mL, 30mg/mL and 75mg/mL, vortex 1.5min～2.5min, with the centrifugal 4.5min～5.5min of rotating speed of 9000r/min; After centrifugal, pipette 2.0mL supernatant to scale test tube, under 50～60 DEG C of water-baths, supernatant is slowly blown to 50～70 μ L with nitrogen; In supernatant, add again normal hexane to be settled to 1.0mL, cross after organic system filter membrane, obtain for measuring the fresh leaf sample extraction of the residual tea of pyrethroid pesticide scavenging solution;
The 3rd step, residual with the pyrethroid pesticide in the fresh leaf sample extraction of tea described in gas chromatography determination scavenging solution, record chromatographic peak retention time and chromatographic peak area, after qualitative by chromatographic peak retention time, the typical curve of the pyrethroid pesticide that the chromatographic peak area that fresh described tea leaf sample extraction scavenging solution is detected and described Part I obtain compares, and obtains the measured value of the every kind of pyrethroid pesticide containing in the fresh leaf sample extraction of described tea scavenging solution; Again described measured value is brought in quantitative computing formula, finally obtains pyrethroid pesticide residual quantity to be measured in the fresh leaf sample of tea;
Quantitatively computing formula: ω=(ρ × v × f)/m, in formula: ω is pyrethroid pesticide residual quantity to be measured in sample, and unit is mg/kg; ρ is measured value, and unit is mg/L; M is the sample size taking, and unit is g; V is constant volume, and unit is mL; F is extension rate;
Wherein, measure the chromatographic condition of the pyrethroid pesticide in the chromatographic condition of the pyrethroid pesticide in the fresh leaf sample extraction of described tea scavenging solution and the 3rd step of described Part I identical.
Related content in technique scheme is explained as follows:
1, in such scheme, the standard reserving solution mass concentration of described Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, these 7 kinds of agricultural chemicals of decis is 1000mg/L, is purchased from Inst. of Environment Protection & Scientific Research Monitor, Ministry of Agric;
Normal hexane is HPLC level, and manufacturer is Oceanpak company of Sweden; N-propyl group ethylenediamine (English referred to as PSA), particle diameter is 40～60 μ m, manufacturer is Agela Technologies company of the U.S.; Ketjenblack EC (English referred to as GCB), particle diameter 120～400 orders, manufacturer is Agela Technologies company of the U.S.; C18, aperture 6nm, granularity 40～60 μ m, manufacturer is Sepax Technologies company of the U.S.; Acetonitrile, acetic acid, anhydrous sodium acetate, anhydrous magnesium sulfate, all need be at 620 DEG C of calcination 4h, are analysis pure, and manufacturer is Shanghai Chemical Reagent Co., Ltd., Sinopharm Group; Experimental water is ultrapure water (18.4M Ω).
2, in such scheme, before the matrix hybrid standard working solution of preparation pyrethroid pesticide, first prepare pyrethroid pesticide hybrid standard storing solution, agricultural chemicals hybrid standard storing solution prepares to be placed in 4 DEG C of refrigerators and preserves, and is mixed with the agricultural chemicals matrix hybrid standard working solution of debita spissitudo when use taking blank matrix extract as solvent;
Wherein, the compound method of pyrethroid pesticide hybrid standard storing solution is: 7 kinds of pyrethroid pesticide standard reserving solution concentration are 1000mg/L, get respectively 1mL and be placed in 5mL volumetric flask, dilute constant volume with normal hexane, being mixed with concentration is single mark solution of 200mg/L, preserves in-20 DEG C of lucifuge sealings.Response according to each agricultural chemicals on μ ECD detecting device, single mark solution gamma cyhalothrin is got 0.1mL, and Fenpropathrin, cyfloxylate are respectively got 0.25mL, and all the other pyrethroid pesticide list mark solution are respectively got 0.5mL, be placed in 10mL volumetric flask, use normal hexane constant volume.In 7 kinds of pyrethroid pesticide hybrid standard storing solutions: gamma cyhalothrin concentration is 2mg/L, Fenpropathrin, cyfloxylate concentration are respectively 5mg/L, and Permethrin, cypermethrin, fenvalerate, decis concentration are respectively 10mg/L.
3, in such scheme, use 7 kinds of pyrethroid pesticides of gas chromatography determination, qualitative with retention time, peak area external standard method is quantitative; For the pyrethroid pesticide that contains more than 2 and 2 isomeride, calculate the measured value of this kind of pyrethroid pesticide with the peak area sum of each isomeride.
4, in such scheme, preferably scheme be the condition of ultrasonic extraction in the first step of described Part I and the first step of described Part II be ultrasonic power between 80W～100W, ultrasonic temperature is at 20～30 DEG C.
Principle of work of the present invention and beneficial effect are: 2003, the people such as the Anastassiades M of agricultural research service centre of United States Department of Agriculture have proposed one and have been called as " QuEChERS " (Quick, Easy, Cheap, Effective, Rugged and Safe) many residual sample of novel agrochemical preparation method.The method dirigibility is strong, applied range, can be per sample and the feature of target analytes, select applicable extraction solvent and purify filler, there is the advantages such as quick, easy, efficient, safe, be successfully applied at present the analysis and research of hundreds of residues of pesticides in food, but application report in the fresh leaf of tea is less." QuEChERS " method recommendation gas chromatography-mass spectrography (GC-MS) or HPLC-MS (HPLC-MS) carry out follow-up detection analysis, although GC-MS, HPLC-MS not only can be qualitative but also can be quantitative, the trend of pesticide residue analysis method development, but instrument is expensive, high to operative technique requirement, thus limit its widespread use.Gas chromatograph (GC) is as the conventional analytical instrument in laboratory, its moderate cost, applied range, is equipped with the detecting device that specificity is stronger, can obtain good selectivity and lower detectability, be one of the most general detection means of testing agency of current vast basic unit application.
Detect department for current basic unit and mostly there is no expensive gas chromatograph-mass spectrometer, only has common gas chromatograph, the deficiency of pre-treatment complex operation, the present invention adopts improved " QuEChERS ", and method is extracted, is purified the fresh leaf of tea, adopt micro-pond electron capture detector (English name GC/ μ ECD) respectively organic phosphates and pyrethrin pesticide to be detected, set up in the fresh leaf of tea 7 kinds pyrethroid pesticide remained fast and convenient, reliable analytical approach saves time.
The fresh leaf sample of tea is the ultrasonic extraction of acetonitrile solution of 1% acetic acid with containing volume fraction, purify with appropriate PSA, C18 and GCB mixed fillers again, supernatant liquid nitrogen blows and is concentrated near doing, use n-hexane dissolution constant volume, HP-5 quartz capillary column and programmed temperature separates, GC/ μ ECD detects, and finally uses matrix external standard method quantitative.Confirm by test, the method range of linearity is wide, and the technical indicators such as detection sensitivity, accuracy and precision all meet the requirement of retention analysis, for pyrethroid pesticide remained analysis and research in the fresh leaf of tea provide reliable means.
Compare with national standard method with existing Pesticide Residues in Tea detection method, pre-treatment of the present invention is simple to operate, and extraction and cleanup only needs several steps to complete, and adopting ultrasonic method while extracting, result is stable, reproducible, facilitate the processing of follow-up batch sample, practicality is stronger; Purification process avoids using decontaminating column and a large amount of solvent elution, and agricultural chemicals loss is few, and the recovery is high, and the time and the organic solvent that expend greatly reduce simultaneously, save testing cost, and environmental pollution is little, also safer to operator.Detect and analyze the conventional gas chromatograph (being furnished with μ ECD) in employing laboratory, moderate cost, Operation and Maintenance is simple, and technical requirement is strict not as application of gas chromatorgraphy/mass, is more suitable for applying in testing agency of vast basic unit.Quantivative approach adopts the calibration of matrix matching standard solution quantitatively, has reduced the matrix effect of agricultural chemicals to be measured, and measurement result is more accurate.Quantitative detecting method of the present invention all meets the requirement that pesticide multi-residues is analyzed on the indices such as accuracy, precision, sensitivity, for tea quality control provides monitoring method and the foundation of science, has certain popularizing value.
Brief description of the drawings
Accompanying drawing 1 is the matrix hybrid standard working solution chromatogram of 7 kinds of pyrethroid pesticides in the embodiment of the present invention;
Accompanying drawing 2 is 7 kinds of pyrethroid pesticides matrix effect figure in the fresh leaf of tea in the embodiment of the present invention;
Accompanying drawing 3 is for adding 7 kinds of pyrethroid pesticide standard colors spectrograms for the fresh leaf of tea of the recovery and precision mensuration in the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment: the quantitative detecting method of pyrethroid pesticide in the fresh leaf of a kind of tea
Take from local certain tea plantation in Suzhou City for the fresh leaf of examination tea, smash and mix through comminutor, pack clean container into, be placed in-20 DEG C of refrigerators and preserve, for subsequent use.Described quantitative detecting method is made up of two parts:
Part I, sets up respectively the typical curve of the tested pyrethroid pesticide of known gradient concentration by vapor-phase chromatography; The foundation of described typical curve is made up of following steps:
The first step, prepares blank matrix extract, and preparation method is made up of following steps:
(1) take the fresh leaf sample of blank tea that 5.0g does not contain tested pyrethroid pesticide after measured, be placed in 50mL centrifuge tube, in centrifuge tube, add 10mL to contain the acetonitrile solution that volume fraction is 1% acetic acid again, mix, ultrasonic extraction 10～15min, ultrasonic power is between 80W～100W, ultrasonic temperature is at 20～30 DEG C, add again 2g anhydrous sodium acetate and 1g anhydrous magnesium sulfate, vortex 2min, then,, with the centrifugal 4min of rotating speed of 9000r/min, get supernatant and be blank matrix extract to be clean;
(2) separately get a 10mL centrifuge tube, add 0.15g C18,0.15g N-propyl group ethylenediamine, 0.12g ketjenblack EC and 0.3g anhydrous magnesium sulfate, add blank matrix extract to be clean described in 4mL, vortex 2min, with the centrifugal 5min of rotating speed of 9000r/min; After centrifugal, pipette 2.0mL supernatant to scale test tube, then under 50～60 DEG C of water-baths, supernatant is slowly blown to 50～70 μ L with nitrogen; In supernatant, add again normal hexane to be settled to 1.0mL, cross after 0.22 μ m organic system filter membrane, obtain the blank matrix extract of pyrethroid pesticide;
Second step, the matrix hybrid standard working solution of preparation pyrethroid pesticide taking the blank matrix extract that obtains in the described first step as solvent, wherein, described pyrethroid pesticide refers to Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis; In the matrix hybrid standard working solution of described pyrethroid pesticide, the concentration range of each pyrethroid pesticide is:
The 3rd step, with chromatographic peak retention time and the chromatographic peak area of each pesticide composition in the matrix hybrid standard working solution of pyrethroid pesticide described in gas chromatography determination, qualitative with chromatographic peak retention time, then taking mass concentration as horizontal ordinate, draw out the typical curve of pyrethroid pesticide taking chromatographic peak area as ordinate;
Wherein, the chromatographic condition of mensuration pyrethroid pesticide is:
Chromatographic column: the capillary chromatographic column that model is HP-5, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 DEG C, dottle pin purges 3mL/min; Column temperature: 80 DEG C of initial temperatures, keep 0.3min, 30 DEG C/min rises to 180 DEG C, keeps 5min, and 20 DEG C/min rises to 260 DEG C, keeps 23min: carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 1mL/min; Detecting device: micro-pond electron capture detector; Detector temperature: 300 DEG C; Make-up gas: high pure nitrogen, 60mL/min;
Part II, measures 7 kinds of pyrethroid pesticide residual quantities in Part I described in the fresh leaf sample of tea, and quantitative detecting method comprises the following steps:
The first step, extracts the fresh leaf sample of tea;
Take the fresh leaf sample of the tea of having pulverized 5.0g, be placed in 50mL teflon centrifuge tube, add 10mL to contain the acetonitrile solution of 1% acetic acid, mix, ultrasonic extraction 10min, ultrasonic power is between 80W～100W, ultrasonic temperature, at 20～30 DEG C, adds 2g anhydrous sodium acetate and 1g anhydrous magnesium sulfate, vortex 2min, with the centrifugal 4min of 9000r/min rotating speed, get supernatant and be the fresh leaf sample extracting solution of tea to be clean;
Second step, purifies the fresh leaf sample extracting solution of described tea to be clean;
Separately get a 10mL teflon centrifuge tube, add 0.15g C18,0.15g PSA, 0.12g GCB and 0.3g anhydrous magnesium sulfate, add the above-mentioned extract to be clean of 4mL, vortex 2min, with the centrifugal 5min of 9000r/min rotating speed; After centrifugal, pipette 2.0mL supernatant to scale test tube, under 50～60 DEG C of water-baths, supernatant is slowly blown to 50～70 μ L with nitrogen; In supernatant, add again normal hexane to be settled to 1.0mL, cross after 0.22 μ m organic system filter membrane, obtain for measuring the fresh leaf sample extraction of the residual tea of pyrethroid pesticide scavenging solution;
The 3rd step, residual with the pyrethroid pesticide in the fresh leaf sample extraction of tea described in gas chromatography determination scavenging solution, record chromatographic peak retention time and chromatographic peak area, after qualitative by chromatographic peak retention time, the typical curve of the pyrethroid pesticide that the chromatographic peak area that fresh described tea leaf sample extraction scavenging solution is detected and described Part I obtain compares, and obtains the measured value of the every kind of pyrethroid pesticide containing in the fresh leaf sample extraction of described tea scavenging solution; Again described measured value is brought in quantitative computing formula, finally obtains pyrethroid pesticide residual quantity to be measured in the fresh leaf sample of tea;
Quantitatively computing formula: ω=(ρ × v × f)/m, in formula: ω is pyrethroid pesticide residual quantity to be measured in sample, and unit is mg/kg; ρ is measured value, and unit is mg/L; M is the sample size taking, and unit is g; V is constant volume, and unit is mL; F is extension rate;
Wherein, measure the chromatographic condition of the pyrethroid pesticide in the chromatographic condition of the pyrethroid pesticide in the fresh leaf sample extraction of described tea scavenging solution and the 3rd step of described Part I identical.
In above embodiment, instrument and equipment used has: 7890A gas chromatograph, be furnished with the micro-pond of 63Ni electron capture detector (μ ECD), 7693 automatic samplers and Chemstation chromatographic work station (Agilent company of the U.S.); KQ-500DE numerical control supersonic instrument (Kunshan Ultrasonic Instruments Co., Ltd.); TG16-WS table model high speed centrifuge (Hunan Xiang Yi Laboratory Instruments development corporation, Ltd.); HSC-24B Nitrogen evaporator (Tianjin Hengao Technology Development Co., Ltd.); K600 type comminutor (German Bo Lang company); VM-10 vortex oscillator (Daihan Scientific company of Korea S); SX2-4-10 muffle furnace (Shanghai leap Medical Devices Co., Ltd.); EXCEED-AD-24 type ultrapure water machine (Chengdu Tangshi Kangning Science and Technology Development Co., Ltd).
Medicine used and reagent: Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis, mass concentration is 1000mg/L, is purchased from Inst. of Environment Protection & Scientific Research Monitor, Ministry of Agric; Normal hexane, HPLC level (Oceanpak company of Sweden); N-propyl group ethylenediamine (PSA), 40～60 μ m (Agela Technologies company of the U.S.); Ketjenblack EC (GCB), 120～400mesh (Agela Technologies company of the U.S.); C18, aperture 6nm, granularity 40～60 μ m (Sepax Technologies company of the U.S.); Acetonitrile, acetic acid, anhydrous sodium acetate, anhydrous magnesium sulfate (620 DEG C of calcination 4h) are analyzes pure (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group); Experimental water is ultrapure water (18.4M Ω).
The preparation of hybrid standard storing solution:
The compound method of pyrethroid pesticide hybrid standard storing solution is: 7 kinds of pyrethroid pesticide standard reserving solution concentration are 1000mg/L, get respectively 1mL and be placed in 5mL volumetric flask, dilute constant volume with normal hexane, being mixed with concentration is single mark solution of 200mg/L, preserves in-20 DEG C of lucifuge sealings.Response according to each agricultural chemicals on μ ECD detecting device, single mark solution gamma cyhalothrin is got 0.1mL, and Fenpropathrin, cyfloxylate are respectively got 0.25mL, and all the other pyrethroid pesticide list mark solution are respectively got 0.5mL, be placed in 10mL volumetric flask, use normal hexane constant volume.In 7 kinds of pyrethroid pesticide hybrid standard storing solutions: gamma cyhalothrin concentration is 2mg/L, Fenpropathrin, cyfloxylate concentration are respectively 5mg/L, and Permethrin, cypermethrin, fenvalerate, decis concentration are respectively 10mg/L.
Above-mentioned agricultural chemicals hybrid standard storing solution is all placed in 4 DEG C of refrigerators and preserves, and when use, is the matrix hybrid standard working fluid that solvent is mixed with respectively debita spissitudo with blank matrix extract.
The test findings of the present embodiment:
1, the gas chromatography of test agricultural chemicals separates
Adopt above-mentioned GC conditions to measure the matrix hybrid standard working solution of 7 kinds of pyrethroid pesticides, standard specimen separating effect is better, peak shape symmetry, and baseline stability, illustrates that instrument condition is applicable to.Under this chromatographic condition, the each agricultural chemicals retention time of pyrethroid is about respectively Fenpropathrin 16.497min, gamma cyhalothrin 17.865min, Permethrin 19.400min, 19.693min; Cyfloxylate 21.499min; Cypermethrin 21.834min, 22.130min, 22.501min; Fenvalerate 25.183min, 26.086min; (shown in accompanying drawing 1, in accompanying drawing 1, label 1 is Fenpropathrin to decis 28.760min, and concentration is 0.1mg/L, label 2 is gamma cyhalothrin, and concentration is 0.04mg/L, and label 3 is Permethrin, concentration is 0.2mg/L, and label 4 is cyfloxylate, and concentration is 0.1mg/L, label 5 is cypermethrin, concentration is 0.2mg/L, and label 6 is fenvalerate, and concentration is 0.2mg/L, label 7 is decis, and concentration is 0.2mg/L).
2, matrix effect
Matrix effect refers to the impact of the matrix components of other except determinand on determinand measured value in sample.Matrix effect is for the situation of different samples and determinand and difference.In gas chromatographic analysis, most of agricultural chemicals show matrix enhancement effect in various degree, be the agricultural chemicals of the same concentrations response in matrix than it height in neat solvent, the existence of being commonly considered as sample mesostroma composition has reduced the chance of chromatographic system avtive spot and determinand molecular action, and determinand detection signal is strengthened.The method of eliminating matrix effect impact has matrix matching standard solution method, standard addition method, multiple purifying method, analysis protectant application and statistical method correction etc.In the present invention, adopt the ratio of the response of determinand in matrix hybrid standard working solution and neat solvent mixed standard solution to represent matrix effect, ratio more approaches 1, shows that matrix effect is less.
Test findings shows, 7 kinds of agricultural chemical compounds analyzing all exist matrix enhancement effect in various degree, and wherein the matrix enhancement effect of Fenpropathrin, Permethrin, decis is not obvious, and the matrix effect of other 4 kinds of agricultural chemicals is stronger, as shown in Figure 2.So the present invention, when quantitative by external standard method, is that solvent is prepared standard specimen with blank matrix extract, to eliminate matrix interference, reduces error.(in accompanying drawing 2, label 1 represent to contain Fenpropathrin matrix hybrid standard working solution and neat solvent mixed standard solution, concentration is 0.1mg/kg; Matrix hybrid standard working solution and the neat solvent mixed standard solution of label 2 for containing gamma cyhalothrin, concentration is 0.04mg/kg; In like manner, label 3 represents to contain Permethrin, and concentration is 0.2mg/kg; Label 4 represents to contain cyfloxylate, and concentration is 0.1mg/kg; Label 5 represents to contain cypermethrin, and concentration is 0.2mg/kg; Label 6 is fenvalerate, and concentration is 0.2mg/kg; Label 7 is decis, and concentration is 0.2mg/kg; A
mrepresent the response of each agricultural chemicals in matrix matching mixed standard solution; A
srepresent the response of each agricultural chemicals in neat solvent mixed standard solution).
3, the range of linearity of method, regression equation and detection limit
7 kinds of pyrethroid pesticide matrix mixed standard solutions that preparation mass concentration is 0.004～2.0mg/L, measure by the chromatographic condition of the pyrethroid pesticide in the 3rd step of described Part I, (represent with ρ with mass concentration, unit is mg/L) be horizontal ordinate, taking peak area (y) as ordinate drawing standard curve, 7 kinds of agricultural chemicals are good in its concentration range internal linear, related coefficient (r
2) be all greater than 0.996, be shown in Table 1.Respectively with 3 times of noise signal in minimum interpolation horizontal chromatography figure and 10 times detection limit (LOD) and the quantitative limit (LOQ) of calculating each agricultural chemicals.As calculated, the LOD of 7 kinds of pyrethroid pesticides is between 0.0017～0.013mg/kg, and LOQ is between 0.0056～0.043mg/kg.
Table 1 is for the range of linearity, regression equation, related coefficient, detection limit and the quantitative limit of examination agricultural chemicals
4, the recovery of method and precision
Adopt blank sample mark-on method to carry out the method recovery and precision mensuration.Take 5.0g after measured not containing some parts of the fresh leaf sample of blank tea for examination agricultural chemicals, add respectively the agricultural chemicals hybrid standard working fluid of 3 kinds of variable concentrations levels, the interpolation level of pyrethroid pesticide is 0.01～0.5mg/kg, parallel 3 duplicate samples of each concentration level, after vortex mixes, standing 1h makes standard solution fully be absorbed by sample, carries out sample pre-treatments and chromatographic condition mensuration according to described Part II.Adopt matrix external standard method quantitative, calculate average recovery rate and the relative standard deviation (being RSD) thereof of each agricultural chemicals, ginseng is shown in Table 2, and sample mark-on chromatogram is referring to accompanying drawing 3.
As shown in Table 2, in the fresh leaf of tea, the average recovery rate of pyrethroid pesticide is that 78.3%～100.2%, RSD (n=3) is 1.3%～9.9%, and illustration method has good accuracy and repeatability.
Table 27 kind reclaims result (n=3) for trying the interpolation of agricultural chemicals in the fresh leaf of tea
Wherein, in accompanying drawing 3, label 1 is Fenpropathrin, and concentration is 0.1mg/L, label 2 is gamma cyhalothrin, and concentration is 0.04mg/L, and label 3 is Permethrin, concentration is 0.2mg/L, and label 4 is cyfloxylate, and concentration is 0.1mg/L, label 5 is cypermethrin, concentration is 0.2mg/L, and label 6 is fenvalerate, and concentration is 0.2mg/L, label 7 is decis, and concentration is 0.2mg/L.
5, actual sample analysis
Adopt this method to the fresh leaf sample of tea of taking from local certain tea plantation in Suzhou totally 16 parts carried out 7 kinds of pyrethroid pesticide residue detection, wherein 1 part detects effective cypermethrin and cypermethrin, content is respectively 0.248mg/kg and 0.0607mg/kg; 1 part detects gamma cyhalothrin, and content is 0.0235mg/kg; 1 part detects decis, and content is 0.0431mg/kg.Result of study shows, this method can be used for 7 kinds of detections that pyrethroid pesticide is residual in the fresh leaf of tea.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that Spirit Essence is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (2)
1. a quantitative detecting method for pyrethroid pesticide in the fresh leaf of tea, is characterized in that: described quantitative detecting method is made up of two parts:
Part I, sets up respectively the typical curve of the tested pyrethroid pesticide of known gradient concentration by vapor-phase chromatography; The foundation of described typical curve is made up of following steps:
The first step, prepares blank matrix extract, and preparation method is made up of following steps:
(1) take the fresh leaf sample of blank tea that 5.0 g do not contain tested pyrethroid pesticide after measured, be placed in 50 mL centrifuge tubes, be the acetonitrile solution of 1% acetic acid to adding 10 mL in centrifuge tube containing volume fraction again, mix, ultrasonic extraction 10～15 min, then add 2 g anhydrous sodium acetates and 1 g anhydrous magnesium sulfate, vortex 1.5min ~ 2.5min, then,, with the centrifugal 3.5min ~ 4.5min of rotating speed of 9000 r/min, get supernatant and be blank matrix extract to be clean;
(2) separately get 10 mL centrifuge tubes, add 0.15g C18,0.15g N-propyl group ethylenediamine, 0.12 g ketjenblack EC and 0.3g anhydrous magnesium sulfate, add blank matrix extract to be clean described in 4mL, vortex 1.5min ~ 2.5min, with the centrifugal 4.5min ~ 5.5min of rotating speed of 9000 r/min; After centrifugal, pipette 2.0 mL supernatants to scale test tube, then under 50～60 DEG C of water-baths, supernatant is slowly blown to 50 ~ 70 μ L with nitrogen; In supernatant, add again normal hexane to be settled to 1.0 mL, cross after organic system filter membrane, obtain the blank matrix extract of pyrethroid pesticide;
Second step, the matrix hybrid standard working solution of preparation pyrethroid pesticide taking the blank matrix extract that obtains in the described first step as solvent, wherein, described pyrethroid pesticide refers to Fenpropathrin, gamma cyhalothrin, Permethrin, cyfloxylate, cypermethrin, fenvalerate, decis; In the matrix hybrid standard working solution of described pyrethroid pesticide, the concentration range of each pyrethroid pesticide is:
The 3rd step, with chromatographic peak retention time and the chromatographic peak area of each pesticide composition in the matrix hybrid standard working solution of pyrethroid pesticide described in gas chromatography determination, qualitative with chromatographic peak retention time, then taking mass concentration as horizontal ordinate, draw out the typical curve of pyrethroid pesticide taking chromatographic peak area as ordinate;
Wherein, the chromatographic condition of mensuration pyrethroid pesticide is:
Chromatographic column: the capillary chromatographic column that model is HP-5, specification is 30m × 0.32mm × 0.25 μ m; Sample size: 1.0 μ L, Splitless injecting samples; Injector temperature: 220 DEG C, dottle pin purges 3mL/min; Column temperature: 80 DEG C of initial temperatures, keep 0.3min, 30 DEG C/min rises to 180 DEG C, keeps 5min, and 20 DEG C/min rises to 260 DEG C, keeps 23min: carrier gas: high pure nitrogen, purity >=99.999%; Constant current mode, flow velocity 1mL/min; Detecting device: micro-pond electron capture detector; Detector temperature: 300 DEG C; Make-up gas: high pure nitrogen, 60mL/min;
Part II, measures 7 kinds of pyrethroid pesticide residual quantities in Part I described in the fresh leaf sample of tea, and quantitative detecting method comprises the following steps:
The first step, extracts the fresh leaf sample of tea;
Take the fresh leaf sample of the tea of having pulverized, be placed in 50 mL centrifuge tubes, add containing volume fraction is the acetonitrile solution of 1% acetic acid again, wherein, the input ratio of the fresh leaf sample of described tea and described acetonitrile solution for to drop into 1mL acetonitrile solution in the fresh leaf sample of every 0.5g tea, mix ultrasonic extraction 10～15 min; Add again anhydrous sodium acetate and anhydrous magnesium sulfate, wherein, the fresh leaf sample of described tea, anhydrous sodium acetate and anhydrous magnesium sulfate three's mass ratio is 5:2:1, vortex 1.5min ~ 2.5min, with the centrifugal 3.5min ~ 4.5min of rotating speed of 9000 r/min, get supernatant and be the fresh leaf sample extracting solution of tea to be clean;
Second step, purifies the fresh leaf sample extracting solution of described tea to be clean;
Separately get 10 mL centrifuge tubes, add C18, N-propyl group ethylenediamine, ketjenblack EC and anhydrous magnesium sulfate, add the fresh leaf sample extracting solution of described tea to be clean, wherein, the content of C18, N-propyl group ethylenediamine, ketjenblack EC and the anhydrous magnesium sulfate dropping in the fresh leaf sample extracting solution of tea to be clean is respectively 37.5mg/mL, 37.5mg/mL, 30 mg/mL and 75mg/mL, vortex 1.5min ~ 2.5min, with the centrifugal 4.5min ~ 5.5min of rotating speed of 9000 r/min; After centrifugal, pipette 2.0mL supernatant to scale test tube, under 50～60 DEG C of water-baths, supernatant is slowly blown to 50 ~ 70 μ L with nitrogen; In supernatant, add again normal hexane to be settled to 1.0mL, cross after organic system filter membrane, obtain for measuring the fresh leaf sample extraction of the residual tea of pyrethroid pesticide scavenging solution;
The 3rd step, residual with the pyrethroid pesticide in the fresh leaf sample extraction of tea described in gas chromatography determination scavenging solution, record chromatographic peak retention time and chromatographic peak area, after qualitative by chromatographic peak retention time, the typical curve of the pyrethroid pesticide that the chromatographic peak area that fresh described tea leaf sample extraction scavenging solution is detected and described Part I obtain compares, and obtains the measured value of the every kind of pyrethroid pesticide containing in the fresh leaf sample extraction of described tea scavenging solution; Again described measured value is brought in quantitative computing formula, finally obtains pyrethroid pesticide residual quantity to be measured in the fresh leaf sample of tea;
Quantitatively computing formula: ω=(ρ × v × f)/m, in formula: ω is pyrethroid pesticide residual quantity to be measured in sample, and unit is mg/kg; ρ is measured value, and unit is mg/L; M is the sample size taking, and unit is g; V is constant volume, and unit is mL; F is extension rate;
Wherein, measure the chromatographic condition of the pyrethroid pesticide in the chromatographic condition of the pyrethroid pesticide in the fresh leaf sample extraction of described tea scavenging solution and the 3rd step of described Part I identical.
2. the quantitative detecting method of pyrethroid pesticide in the fresh leaf of a kind of tea according to claim 1, it is characterized in that: in the first step of described Part I and the first step of described Part II the condition of ultrasonic extraction be ultrasonic power between 80W ~ 100W, ultrasonic temperature is at 20～30 DEG C.
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