CN106290662A - Organochlorine pesticide and the method for quick of pyrethroid pesticide and pre-treating method thereof in Folium Camelliae sinensis - Google Patents
Organochlorine pesticide and the method for quick of pyrethroid pesticide and pre-treating method thereof in Folium Camelliae sinensis Download PDFInfo
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Abstract
The present invention relates to a kind of detect the pre-treating method of organochlorine and pyrethroid pesticide residual in Tea Samples, the method comprises the steps of: a kind of method that organochlorine pesticide in Tea Samples and pyrethroid pesticide are carried out pre-treatment, and described method includes comprising the steps of: (1) pulverizes；(2) extract；(3) purify；(4) filter, obtain the liquid sample analyzed for GC-ECD.The present invention is simple and quick, shortens time for sample pretreatment, and needs the solvent consumed few, effectively reduces matrix interference, for organochlorine in Folium Camelliae sinensis and pyrethroid pesticide remain detection simultaneously provide a kind of quickly, effectively and the Sample Pretreatment Technique of low cost.
Description
Technical field
The present invention relates to organochlorine pesticide and the quick sample pretreatment method of pyrethroid pesticide in a kind of Folium Camelliae sinensis, further relate to use this pre-treating method, use gas chromatography-electron capture detector to analyze organochlorine pesticide and the detection technique of pyrethroid pesticide residual quantity in Folium Camelliae sinensis, belong to field of detection of food safety.
Background technology
Organochlorine pesticide was once widely used in agricultural production in countries in the world, its Stability Analysis of Structures, the most degradable, pollution environment, China forbids production and application organochlorine pesticide in nineteen eighty-three, but even to this day, in water body and soil, the organochlorine pesticide of remaining produces harm yet by crops to human health.The chemical constitution of pyrethroid pesticide is similar with natural pyrethrum, belongs to biomimetic insecticide, has the advantages such as high-efficiency low-toxicity due to it, has obtained commonly used in the tea place of China, so pyrethroid pesticide remained problem ratio is more serious in Folium Camelliae sinensis.
In order to reduce pest and disease damage, improve tea yield, tea grower has often sprayed substantial amounts of chemical pesticide in planting process, and this phenomenon constitutes contradiction with the food safety requirements of increasingly stringent.At present, Pesticide Residues in Tea has been formulated harsh Limited Doses by the developed countries and regions such as European Union, Japan, North America, it has also become be unfavorable for the TBT (Technical Barriers to Trade) of China's tea export.For guaranteeing the quality safety of China's Folium Camelliae sinensis, substantial amounts of Tea Production business needs the Detection Technologies of Pesticide Residues that tea raw material and finished product are carried out the monitoring of pesticide residues level.
Containing purine alkaloid, saccharide, pigment, vitamin and mineral matter and other components in Folium Camelliae sinensis, substrate is complicated, and the Detecting Pesticide of trace is had severe jamming.Mostly need pre-treating method that Tea Samples is processed when using chromatography separation detection organochlorine and pyrethroid pesticide.At present, the pre-treating method of research Pesticide Residues in Tea mainly has the methods such as surname extraction, mechanical shaking extraction, accelerated solvent extraction, dispersive liquid-liquid microextraction, Solid-Phase Extraction, gel permeation chromatography both at home and abroad.Some step of these methods is more, and some is the longest, and some needs operator and substantial amounts of organic solvent exposure, pollutes environment, relatively costly.
Summary of the invention
It is an object of the invention to overcome existing Sample Pretreatment Technique to process time length, consume that solvent is many, high in cost of production shortcoming and defect, develop a kind of quickly, organochlorine pesticide and the analysis method of pyrethroid pesticide and pretreatment technology thereof in low cost, high efficiency Folium Camelliae sinensis.
For reaching solution the problems referred to above, in Folium Camelliae sinensis of the present invention, the pretreatment technology of organochlorine pesticide and pyrethroid pesticide method for quick mainly comprises the steps of:
(1) pulverizing tea sample, obtains stem tea powder to be measured；
(2) the stem tea powder to be measured obtained in step (1) add acetonitrile and extract with ultrasonic, be centrifuged and remove supernatant；
(3) by the supernatant obtained in step (2) and adsorbent vortex mixed, scavenging solution after being centrifuged, is obtained；
(4) the scavenging solution nitrogen obtained in step (3) is concentrated to dryness, then redissolves with normal hexane, then utilize filter to filter, obtain the liquid sample analyzed for GC-ECD.
The present invention sample-pretreating method preferred embodiment in, in step (1), the screen size≤2.0mm of Folium Camelliae sinensis to be measured.
In an embodiment of the sample-pretreating method of the present invention, in step (2), for stem tea powder to be measured described in 2.50g, the addition of described acetonitrile is 10mL；Described supersound extraction carries out 20min altogether；And/or described being centrifuged carries out 5min with 3000r/min.
In an embodiment of the sample-pretreating method of the present invention, in step (3), the adsorbent used is Graphon and brothers amine；Preferably for the supernatant obtained in the step (2) of 1.5mL, the usage amount of described Graphon and described brothers amine is 20-45mg and 30-60mg respectively；More preferably, for the described supernatant of 1.5mL, the usage amount of described Graphon and described brothers amine is 30-35mg and 40-45mg respectively；Described vortex mixed carries out 3min altogether；And/or described being centrifuged carries out 3min with 6000r/min.
In an embodiment of the sample-pretreating method of the present invention, the nitrogen in step (4) is concentrated under room temperature temperate condition and carries out, and preferably carries out at 30 DEG C；The residue normal hexane that nitrogen is concentrated to dryness redissolves to 0.8mL；Using nylon leaching film to carry out described filtration, the aperture of the most described nylon leaching film is 0.22 μm.
On the other hand, the invention provides a kind of method detecting organochlorine pesticide in Tea Samples and pyrethroid pesticide, described method includes:
A () carries out processing Folium Camelliae sinensis to be measured with pre-treating method of the present invention, to obtain liquid sample；
B () uses GC-ECD to be analyzed the liquid sample obtained in step (a).
The present invention, with organochlorine and pyrethroid pesticide for analyzing object, uses dispersive solid-phase extraction technology as pre-treatment means, and gas chromatography-electron capture detector, as analytical tool, establishes the method for quick of Multiple Pesticides residual in Folium Camelliae sinensis.
Method of the present invention compared with prior art has the advantage that
The pretreatment technology of the present invention can quickly process Tea Samples, while effectively extracting Organochlorine Pesticides and pyrethroid pesticide, remove major part Folium Camelliae sinensis substrate to greatest extent, reduce the interference of original composition in Folium Camelliae sinensis, also there is wide linear detection range.On the other hand, compared with prior art, the method for the present invention substantially reduces the process time of Tea Samples, in actually detected, can complete 20 samples to process in 2 hours simultaneously, and processing cost is significantly reduced, the processing cost of each sample can be decreased to less than 5 yuan.Therefore, the pretreatment technology of the present invention and detection method can be applicable to extensive quickly detection, are with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the GC-ECD chromatogram (0.050 μ g/mL) of 25 kinds of organochlorines and pyrethroid pesticide standard substance.
nullIn Fig. 1, chromatographic peak is respectively as follows: (1) α-BHC (α-Gamma Hexaochlorocyclohexane)、(2) β-BHC (β-Gamma Hexaochlorocyclohexane)、(3) γ-BHC (γ-Gamma Hexaochlorocyclohexane)、(4) δ-BHC (δ-Gamma Hexaochlorocyclohexane)、(5) Heptachlor (heptachlor)、(6) Aldrin (drinox)、(7)o,p’-DDD(o,P '-dichloro-diphenyl-dichlorothane)、(8)o,p’-DDE(o,P '-drip her)、(9)o,p’-DDT(o,P '-clofenotane)、(10)p,p’-DDD(p,P '-dichloro-diphenyl-dichlorothane)、(11)p,p’-DDE(p,P '-drip her)、(12)p,p’-DDT(p,P '-clofenotane)、(13) α-Endosulfan (α-5a,6,9,9a-hexahydro-6,9-methano-2,4)、(14) β-Endosulfan (β-5a,6,9,9a-hexahydro-6,9-methano-2,4)、(15) Endosulfan-sulfate (5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric ester)、(16) Bifenthrin (Biphenthrin)、(17) Fenpropathrin (Fenpropathrin)、(18) Cyfluthrin (gamma cyhalothrin)、(19) Permethrin (Permethrin)、(20) λ-Cyhalothrin (cypermethrin)、(21) Flucythrinate (flucythrinate)、(22) Esfenvalerate (esfenvalerate)、(23) Deltamethrin (decis)、(24) Tetradifon (tetradiphon)、(25) Pyridaben (pyridaben).
Fig. 2 shows the result using the method for the present invention to test three kinds of actual Tea Samples.Wherein, the corresponding relation of each chromatographic peak label is identical with Fig. 1.
Detailed description of the invention
The present invention uses Graphon (GCB) and brothers amine (PSA) to adsorb tea extract.Above-mentioned adsorbent can adsorb the Multiple components in Folium Camelliae sinensis, gets rid of the interference to Detecting Pesticide, the most not appreciable impact organochlorine and the accuracy of detection of pyrethroid pesticide.
In the prior art, there is also some pre-treatment steps being applicable to On Detection of Organophosphorus Pesticide.But, major part organophosphorus pesticide is polarity or highly polar, and organochlorine and pyrethroid pesticide are low poles or nonpolar；Part organophosphorus pesticide is unstable, easily decompose, and organochlorine and pyrethroid pesticide is stable, be not easily decomposed in a short time.So when processing organophosphorus pesticide, using the vortex mechanical shaking extraction of such as 4-8min, this is a kind of comparatively gentle extracting mode, will not cause the decomposition of organophosphorus pesticide；And when processing more stable organochlorine and pyrethroid pesticide, the most preferably use the supersound extraction of such as 20min.The most ultrasonic rising that simultaneously there is strong intermolecular interaction and temperature, further enhances the extraction efficiency of organochlorine and pyrethroid pesticide.
Additionally, organophosphorus pesticide needs to detect with gas chromatogram-flame photometric detector (GC-FPD), this is a kind of high selectivity, highly sensitive detector.When on detector equipped with the optical filter of phosphorus, detector only detects can launch the organic phosphorus compound that wavelength is 526nm.That is, in addition to organophosphorus pesticide, the substrate in other Folium Camelliae sinensis, organic solvent equal no signal on FPD, so sample can go up machine testing through simple extraction and purification during pre-treatment.
Mostly containing halogen in organochlorine and pyrethroid pesticide, need with gas chromatography-electron capture detector (GC-ECD) detection.This is a kind of and the compound containing electronegative element (halogen, oxygen, nitrogen, sulfur etc.) is had highly sensitive detector, and electronegativity is the strongest, and detection sensitivity is the highest.Owing to using acetonitrile (nitrogen atom) as Extraction solvent, after substantial amounts of acetonitrile enters ECD, by causing, ECD's is saturated, not only affects the detection of organochlorine and pyrethroid pesticide, even can damage ECD time serious.So after extracting and purifying, needing all to dry up acetonitrile, then with after normal hexane (only carbon atoms and hydrogen atom) replacement acetonitrile dissolving pesticide, carry out GC-ECD detection.
Embodiment
The present invention is specifically described below by embodiment.It is to be understood that the present invention is not limited to these embodiments.
The GC-ECD detection that the embodiment of the present invention is used uses GC-2010Plus gas chromatograph (joining ECD detector, Shimadzu Corporation of Japan), and uses following operating parameter:
Chromatographic column: DB-35ms capillary column, 30m × 0.25mm × 0.25 μm；
Heating schedule: 150 DEG C keep 2min, then rise to 300 DEG C with 10 DEG C/min, keep 30min；
Carrier gas: N2, purity >=99.999%；
Flow rate model: uniformly linear rate pattern, initial flow rate 1.0mL/min；
Detector temperature: 320 DEG C；
Injection port: shunt mode, split ratio 10:1, injector temperature 280 DEG C；
Sample size: 1 μ L.
The standard sample of pesticide purity that the embodiment of the present invention uses is 87.0%～99.6%, and equal city is purchased from Dr.Ehrenstorfer GmbH company of Germany.The Graphon (GCB), brothers amine (PSA) city that use are purchased from Beijing BESEP company.The solvent (acetonitrile, normal hexane, petroleum ether, acetone, toluene) used is chromatographically pure, and city is purchased from Fisher company of the U.S..Tea Samples is commercial products.
In an embodiment of the present invention, the pre-treating method used specifically comprises the following steps that
(1) preparation of standard solution
Accurately weigh the standard substance of 25 kinds of pesticide, be configured to the standard reserving solution of 1mg/mL with toluene-acetone mixed solution, store under the conditions of-18 DEG C.
Blended standard reserving solution: the most accurately pipette various standard sample of pesticide according to 25 kinds of pesticide response value on instrument appropriate, be configured to hybrid standard storing solution with normal hexane, preserve in refrigerator, be diluted according to actual needs during use.
(2) sample pre-treatments
(2-1) pulverize: take Tea Samples 100g, pulverize with pulverizer, sift out≤2.0mm granule with round-hole mesh.Mixing, loads in clean container, seals, stored refrigerated.
(2-2) extract: take 2.50g (being accurate to 0.01g) stem tea powder in 50mL centrifuge tube, add 10mL acetonitrile, supersound extraction 20min, be centrifuged 5min in 3000r/min.
(2-3) purify: take a 10mL centrifuge tube, add 30-35mg GCB, 40-45mg PSA adsorbent, proceed to above-mentioned supernatant extracting solution 1.5mL, vortex mixed 3min, be centrifuged 3min in 6000r/min.
(2-4) concentrating: take a 5mL (accurate scale) glass centrifuge tube, add supernatant scavenging solution 0.8mL, under the conditions of 30 DEG C, nitrogen redissolves to 0.8mL with normal hexane after blowing near doing, and after 0.22 μm nylon leaching film crossed by sample, carries out GC-ECD analysis.
Embodiment 1: the drafting of working curve
With blank 25 kinds of organochlorines of Folium Camelliae sinensis substrate preparation and the mixed mark working solution of pyrethroid pesticide, working concentration curve with peak area, the range of linearity, linear equation and correlation coefficient are shown in Table 1.
Fig. 1 shows above-mentioned mixed mark working solution reference colour spectrogram under the concentration of 0.050 μ g/mL.As seen from Figure 1, according to the experimental technique of the present invention, 25 kinds of organochlorines separate well with pyrethroid pesticide.
Table 1 range of linearity, linear equation and correlation coefficient
Embodiment 2: method mark-on reclaims and Precision Experiment
Weigh 2.5g blank Folium Camelliae sinensis substrate, being separately added into appropriate standard sample of pesticide, the spiked levels making each pesticide is 10 times of quantitative limit (LOQ:S/N=10), experiment operation repetitive 5 times, the average recovery rate of computational methods and relative standard deviation, the results are shown in Table 2.
Table 2 is average recovery rate, relative standard deviation and the detection limit that 25 kinds of pesticide add experiment
By above Tables 1 and 2 it can be seen that the pretreatment technology of the present invention and use the detection method of this technology to have good detection separating degree for multiple organochlorine and pyrethroid, the range of linearity is wider, it is possible to obtain outstanding Detection accuracy.
Compared with the prior art: at present, the residual limit standard of standard GB/T 2763-2014 maximum agriculture recommends multiple method to the agriculture residual in detection Folium Camelliae sinensis, the detection method that wherein NY/T 761-2008 and GB/T 5009.19-2008 standard is used is consistent with this method, is GC-ECD detection method.But the pre-treating method of NY/T 761-2008 is liquid-liquid extraction combines Solid phase extraction, need to carry out 2 nitrogen altogether and blow concentration；And the pre-treating method of GB/T 5009.19-2008 is liquid-liquid extraction attached gel chromatographic purification.The pre-treatment time length (process single sample and take around 1.5-2 hour) of these 2 kinds of standard methods, cost height, consumption organic solvent amount are big.By comparison, method of the present invention has simple and quick (processing single sample required time less than 1h), consumes the many merits such as few, the low cost of solvent.
Embodiment 3: actual sample test experience
By the experimental technique of the present invention, the persticide residue in 3 kinds of commercially available actual Tea Samples is detected, with Tea Samples to be measured preparation mixed mark working solution, with quantified by external standard method.Result is as shown in Figure 2.From Figure 2 it can be seen that 3 kinds of actual Tea Samples are all not apparent from detect 25 kinds of organochlorines and pyrethroid pesticide.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing; but; the present invention is not limited to the detail in above-mentioned embodiment; in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
Claims (6)
1. one kind carries out pre-treatment to the organochlorine pesticide in Tea Samples and pyrethroid pesticide
Method, said method comprising the steps of:
(1) pulverize described Tea Samples, obtain stem tea powder to be measured；
(2) the stem tea powder described to be measured obtained in step (1) adds acetonitrile and with super
Sound extracts, and is centrifuged and removes supernatant；
(3) by the described supernatant obtained in step (2) and adsorbent vortex mixed, after being centrifuged
Obtain scavenging solution；
(4) the described scavenging solution nitrogen obtained in step (3) is concentrated to dryness, then with just own
Alkane redissolves, and then utilizes filter to filter, and obtains the testing liquid sample analyzed for GC-ECD
Product.
In the most described step (1), described to be measured
The granularity of stem tea powder is≤2.0mm.
3. method as claimed in claim 1 or 2, wherein, described step (2) meets as follows
One or more in condition:
For stem tea powder to be measured described in 2.50g, the addition of described acetonitrile is 10mL；
Described supersound extraction carries out 20min altogether；And/or
Described being centrifuged carries out 5min with 3000r/min.
4. the method as according to any one of claim 1-3, wherein, described step (3) meets
One or more in following condition:
Described adsorbent is Graphon and brothers amine；Preferably for 1.5mL described on
Clear liquid, the usage amount of described Graphon and described brothers amine be respectively 20-45mg and
30-60mg；More preferably, for the described supernatant of 1.5mL, described Graphon and described
The usage amount of brothers amine is 30-35mg and 40-45mg respectively；
Described vortex mixed carries out 3min altogether；And/or
Described being centrifuged carries out 3min with 6000r/min.
5. the method as according to any one of claim 1-4, wherein, described step (4) meets
One or more in following condition:
Described nitrogen is concentrated at 30 DEG C and carries out；
Residue normal hexane after nitrogen is concentrated to dryness redissolves to 0.8mL；
Described filter is nylon leaching film, and the aperture of the most described nylon leaching film is 0.22 μm.
6. the side that organochlorine pesticide in Tea Samples and pyrethroid pesticide are detected
Method, said method comprising the steps of:
A () uses the method according to any one of claim 1-5 to carry out described Tea Samples before
Process, obtain liquid sample；
B () uses GC-ECD to detect described liquid sample.
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