CN103353488A - Method for determining residues of chlorothalonil, captan, captafol and folpet in vegetables and fruits - Google Patents
Method for determining residues of chlorothalonil, captan, captafol and folpet in vegetables and fruits Download PDFInfo
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Abstract
The invention relates to a method for determining the residues of chlorothalonil, captan, captafol and folpet in vegetables and fruits. The method specifically includes the steps of: preparing a sample; treating the sample with phosphoric acid; extracting a target object with acetonitrile; removing the phosphoric acid and water soluble impurities from the extracted solution; conducting further purification with a Florisil small column and aminopropyl powder; and carrying out detection by an Agilent7890A gas chromatograph-electron capture detector. The determination method employs 5% phosphoric acid to treat a fruit and vegetable sample, thus avoiding loss of the four pesticides during sample crushing. The method is suitable for determining the four pesticide residues in all vegetables and fruits, has recovery rates all over 80%, and can make determination of the four pesticide residues in vegetables and fruits more accurate and reliable.
Description
Technical field
The present invention relates to detection and the applied technical field of residues of pesticides, particularly measure the mensuration of Bravo, captan, difoltan and folpet persticide residue in the vegetable and fruit.
Background technology
Bravo is a kind of substituted benzene broad-spectrum germicide of non-internal-absorting; captan, folpet and difoltan are the phthalmide broad spectrum protection germifuge of a class multiaction point; these four kinds of germifuge are good to the fungal disease insect killing effect of various crop; poisoning is little; and prevention effect is arranged, be widely used on the crops such as fruit and vegetable.Developed countries has clearly limited the maximum residue limit(MRL) of these several agricultural chemicals in vegetable and fruit, must not detect such as difoltan in the regulation vegetable and fruit in the Japanese positive list, the maximum residue limit(MRL) of Bravo (MRL) is respectively 0.1mg/kg and 2.0mg/kg in radish and the apple, and the maximum residue limit(MRL) of captan is 0.1mg/kg etc. in European Union regulation radish and the spinach.These four kinds of agricultural chemicals are unstable under alkaline environment, the interpolation recovery in some vegetable and fruit is lower than 35%, existing document detection method and standard method, majority does not relate to these four kinds of agricultural chemicals unsettled problem under alkaline environment, the document that has and standard method are then after sample is smashed, adding phosphoric acid or ZnAc solution improve captan before extracting, folpet, the stability of difoltan and Bravo, but these four kinds of agricultural chemicals will be degraded when some sample is smashed, therefore as a positive, when sample preparation, directly sample is smashed, even add again the pH value that phosphoric acid changes extraction environment before extracting, can not obtain accurately and reliably quantitative result.
Summary of the invention
For the defective that exists in the prior art, the object of the present invention is to provide a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring, the method recovery is high, mensuration is more accurate.
For reaching above purpose, the technical scheme that the present invention takes is:
A kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring, it is characterized in that: concrete steps comprise:
1, the preparation of sample: with the leaf vegetables sample be cut into 2-3 cm the section, fruit class sample is cut into the piece of the about 2-3cm of length;
2, process sample with phosphoric acid: add phosphoric acid solution sample is processed, blend, mix, be prepared into even sample;
3, extract object with acetonitrile: add acetonitrile in the step 2 gained sample, carry out high speed homogenization and centrifugal, obtain extract after centrifugal, then extract is carried out reduced pressure concentration;
4, phosphoric acid and the water-solubility impurity in the removal extract: solid phase is supported the inner Hydromatrix-of filling of liquid-liquid extraction post diatomite adsorbant, to concentrate rear extract and cross solid phase support liquid-liquid extraction post, balance 10min, use water-fast eluent ethyl acetate, collect eluent, be concentrated near doing, to be clean;
5, further purify with florisil silica pillar and aminopropyl powder: with 10mL normal hexane activation pillar, be transferred in the florisil silica pillar with the sample residue of 3 * 2mL normal hexane with above-mentioned preparation, then use 5% ethyl acetate-normal hexane 15mL wash-out, collect eluent, and be evaporated near doing 40 ℃ of water-baths, accurately be settled to 2.0mL with normal hexane, add aminopropyl powder 150mg, mixed 2 minutes of whirlpool is crossed 0.45 μ m organic phase filter membrane and is entered the sample introduction bottle, for the gas phase chromatographic determination;
6, detect with Agilent7890A gas chromatograph-electron capture detector: utilize Agilent7890A gas chromatograph-electron capture detector to measure, select the DB-5 quartz capillary column, chromatogram column temperature is made as 60 ℃, keep 1.25min; Rise to 180 ℃ with 20 ℃/min, keep 7min; Rise to 230 ℃ with 5 ℃/min again, keep 7min; Rise to 270 ℃ with 30 ℃/min again, keep 5min; Detector temperature is made as 300 ℃, and injector temperature is made as 250 ℃, does carrier gas with High Purity Nitrogen, the post flow is made as 1.4mL/min, and make-up gas? flow 30mL/min puts the sample introduction bottle in the sample disc of gas chromatograph, behind instrument stabilizer, sample introduction is measured, sample size 1 μ L; External standard method is quantitative, calculates the measured value of agricultural chemicals.
Below be the further optimization to technique scheme:
The consumption that the adding phosphoric acid solution is processed sample is: take by weighing the 100g sample, add 5% phosphoric acid solution 50g.
The step of extracting object with acetonitrile comprises: take by weighing the sample 15g that handles well with 5% phosphoric acid solution, place the 100mL plastic centrifuge tube, add acetonitrile 40mL, high speed homogenization 2min, carry out centrifugal 5min with 5000r/min speed, extract moves in the rotary evaporation bottle, on the Rotary Evaporators under 40 ℃ of water bath condition reduced pressure concentration.
Described Hydromatrix-diatomite adsorbant be fossil take diatom as raw material, the adsorbent with the wettable specific surface of high water of making through high temperature purification.
The consumption of ethyl acetate is 100ml in the described step 4.
In the described step 4, eluent is placed Rotary Evaporators, the pressure of control Rotary Evaporators is 0.016MPa, in 40 ℃ of water-bath reduced pressure concentrations.
Described High Purity Nitrogen is the nitrogen of purity＞99.999%.
The injection port bushing pipe of gas chromatograph is with the bushing pipe of clean deactivation inside surface.
The present invention adopts above technical scheme, compared with prior art has the following advantages:
This detection method is processed with 5% phosphoric acid the fruit and vegetable sample, avoid the loss of sample four kinds of agricultural chemicals in pulverizing preparation process, support the deacidification of liquid-liquid extraction technology and water-solubility impurity with solid phase again, purify with Florisil solid-phase extraction column and aminopropyl powder after extract is concentrated, detect with gas chromatograph-electron capture detector, noiseless phenomenon occurs when detecting rape, radish, cucurbita pepo, cauliflower, peach, apple, 7 kinds of fruit and vegetable matrix of wax gourd; This assay method is applicable in all vegetables and the fruit mensuration to these four kinds of residues of pesticides, and the recovery is all greater than 80%, and this assay method is so that these four kinds of residues of pesticides quantitative determinations are more accurately and reliably in vegetables and the fruit.
Description of drawings
Fig. 1 adds the recovery contrast of the mixed target radish of 0.02mg/kg under variable concentrations phosphoric acid is processed in the embodiment of the invention:
The concentration of X-axis-phosphoric acid solution (%)
Y-axis-recovery (%)
Curve 1-Bravo curve 2-captan curve 3-folpet curve 4-difoltan;
Fig. 2 is through the chromatogram of the acid-treated blank radish of 5% phosphorus in the embodiment of the invention;
Fig. 3 is through the mixed chromatogram of marking radish of acid-treated interpolation 0.02 mg/kg of 5% phosphorus in the embodiment of the invention.
Embodiment
Embodiment 1
Except as otherwise noted, the percentage that adopts among the present invention is percent by weight.
A kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring, concrete steps are as follows:
1, the preparation of sample:
With the leaf vegetables sample be cut into 2-3 cm the section, fruit class sample is cut into the piece of the about 2-3cm of length.
2, process sample with phosphoric acid:
Accurately take by weighing the 100g sample, add 5% phosphoric acid solution 50g, blend, mix, be prepared into even sample.
Because Bravo, captan, difoltan and four kinds of agricultural chemicals of folpet are unstable in alkaline environment, and when smashing, the matrix samples such as cucurbita pepo, rape, radish, cauliflower, peach will degrade, so when sample preparation, adopt the method that adds phosphoric acid, avoided the loss of sample four kinds of agricultural chemicals in pulverizing preparation process.Process sample with phosphoric acid solution, not only can improve the recovery of these four kinds of agricultural chemicals in these matrix, the interference that can also remove some pigments and impurity.
In order to choose best phosphoric acid solution concentration, respectively sample to be processed with 0%, 3%, 5%, 10%, 15%, 20%, 25% phosphoric acid solution, interpolation 2 μ g agricultural chemicals mixed standard solutions were done the interpolation recovery before the stripping and slicing sample added phosphoric acid.
Add the recovery contrast of the mixed target radish of 0.02mg/kg under variable concentrations phosphoric acid is processed and see Fig. 1;
See Fig. 2 with the acid-treated blank radish chromatogram of 5% phosphorus;
See Fig. 3 through the mixed target radish chromatogram of acid-treated interpolation 0.02 mg/kg of 5% phosphorus.
Experiment shows, and is basic identical without the recovery situation that phosphoric acid is processed, 0% phosphoric acid solution is processed, and all is lower than 35%; The acid-treated recovery of 3% phosphorus obviously improves, but the recovery of difoltan is still on the low side, is 68.8%, and the recovery of Bravo and captan also is lower than 80%; The interpolation recovery of the acid-treated 4 kinds of agricultural chemicals of 5% phosphorus all is higher than 85%; 10%, the acid-treated recovery situation of 15%, 20%, 25% phosphorus and 5% phosphoric acid process basic identical, but the phosphoric acid concentration height one be influential to pre-processing device, the 2nd, therefore waste that consumption is large selects 5% phosphoric acid that sample is processed.
Process and the interpolation recovery contrast of processing without phosphoric acid solution with phosphoric acid solution when cucurbita pepo, rape, radish, cauliflower, peach, apple, 7 kinds of different substrates sample preparations of wax gourd:
Process and the interpolation recovery contrast of processing without phosphoric acid solution with phosphoric acid solution during 7 kinds of different substrates sample preparations:
Get cucurbita pepo, rape, radish, cauliflower, peach, apple and 5 kinds of samples of wax gourd, rape is cut into the section of 2-3 cm, other 4 kinds of samples are cut into the fritter that length is 2-3cm, be prepared into respectively three kinds of different interpolation recovery samples by following three kinds of modes, A: directly sample is blended during the preparation sample, take by weighing the 10g sample, add 0.2 μ g Bravo, captan, folpet and difoltan agricultural chemicals mixed standard solution, 5 minutes kinds are mixed in the whirlpool, and agricultural chemicals is fully mixed with sample; B: directly sample is blended during the preparation sample, take by weighing the 10g sample, add 0.2 μ g Bravo, captan, folpet and difoltan agricultural chemicals mixed standard solution, 5 minutes kinds are mixed in the whirlpool, agricultural chemicals is fully mixed with sample, then before solubilizer extracts, add 5% phosphoric acid 2.5mL; C: take by weighing 100g stripping and slicing sample, add 2 μ g agricultural chemicals mixed standard solutions, add 5% phosphoric acid solution 50g, blend and take by weighing sample 15g after mixing.
Three kinds of interpolations of A, B, C recovery sample that preparation is taken by weighing operates according to the sample pre-treatments step, the results are shown in Table 1.
The recovery contrast of three kinds of different interpolation recovery samples of table 1
Can be found out by data in the table 1, directly sample is blended during the preparation sample, Bravo, captan, folpet, these four kinds of agricultural chemicals of the difoltan interpolation recovery in some matrix such as cucurbita pepo, rape, radish is very low, all be lower than 35%, and preparation directly blends sample during sample, 5 minutes kinds are mixed in the whirlpool after adding pesticide standard solution, make agricultural chemicals fully contact mixing with sample, add again the raising not effect of phosphoric acid solution to adding the recovery before extracting, but add first phosphoric acid solution before the sample preparation and blend again sample, the recovery then is significantly increased, all greater than 80%.
Can reach a conclusion thus, the positive of this class matrix if directly sample is smashed, will cause the loss of these four kinds of agricultural chemicals in the sample preparation process, just can not obtain accurately quantitative result so do not add the phosphoric acid solution processing before the sample preparation.And preparation directly blends sample during sample, do not have influential matrix such as apple, wax gourd for the interpolation recovery of these four kinds of agricultural chemicals, adding first phosphoric acid solution before the preparation sample blends again, for the recovery also without any impact, so during to the Bravo in vegetables and the fruit, captan, folpet, difoltan detection, all can add first phosphoric acid before the preparation sample and blend again.
Bravo, captan, difoltan and folpet persticide residue in these assay method energy Accurate Determining vegetables and the fruit have not only greatly improved extraction efficiency and have added the recovery, have also strengthened clean-up effect.Existing detection method only has the preferably recovery to the residual quantity of Bravo, captan, difoltan and folpet in a part of vegetables and the fruit matrix, but the recovery in the matrix such as cucurbita pepo, rape, radish, cauliflower, peach is lower than 35%.And this assay method is applicable in all vegetables and the fruit mensuration to these four kinds of agricultural chemicals, and the recovery is all greater than 80%.This assay method is so that this residues of pesticides quantitative determination is more accurately and reliably in vegetables and the fruit.
3, extract object with acetonitrile:
Take by weighing the sample 15.0g that handles well with 5% phosphoric acid solution, place the 100mL plastic centrifuge tube, add acetonitrile 40mL, high speed homogenization 2min on homogenizer, carry out centrifugal 5min with 5000r/min speed, extract moves in the rotary evaporation bottle, in being evaporated to about 20 mL under 40 ℃ of water bath condition on the Rotary Evaporators.
Extract the selection of solvent: according to the needs of purification style, extract the solvent that solvent need to dissolve each other with water, acetonitrile and acetone are good selections, but acetone is when extracting object, also can extract more impurity, and the impurity phase that acetonitrile extracts is to less, so select acetonitrile to make the extraction solvent.
4, phosphoric acid and the water-solubility impurity in the removal extract:
Solid phase is supported the inner Hydromatrix-of filling of liquid-liquid extraction post diatomite adsorbant, this adsorbent is take the fossil of diatom as raw material, through high temperature purification, the wettable specific surface of high water is arranged, the organic solvent extract that contains moisture content after concentrated is crossed solid phase support the liquid-liquid extraction post, only there is organic solvent not have the moisture content recovery can be very low in the extract, balance 10min, with the water-fast eluent ethyl acetate of 100ml, phosphoric acid and water-solubility impurity are retained in solid phase and support that water-fast agricultural chemicals is then got off by eluent ethyl acetate in the diatom scholar adsorbent of liquid-liquid extraction post like this.Collect eluent, the pressure of control Rotary Evaporators is evaporated near doing at 0.016MPa in 40 ℃ of water-baths, and is to be clean;
Mineral acid can cause partial fixing liquid to run off to the fixedly phase injury of gas chromatographic column, reduces column performance, pollutes the gas phase detecting device, so need to remove the phosphoric acid solution in the extract when sample purification.Traditional liquid-liquid extraction method (LLE) can be removed the phosphoric acid in the extract, but this method complex operation will emulsion easily occur with glass apparatus separating funnel extraction 2-3 times in extraction process, affect the recovery and clean-up effect.Solid phase supports that liquid-liquid extraction method (SSLLE) is the method for phosphoric acid and water-solubility impurity in a kind of effective removal extract, the emulsion that this method has avoided traditional liquid-liquid extraction method to cause, and the post recovery is high, good purification, as a result good reproducibility.
5, further purify with florisil silica pillar and aminopropyl powder:
With 10mL normal hexane activation pillar, be transferred in the florisil silica pillar with the sample residue of 3 * 2mL normal hexane with above-mentioned preparation, then use 5% ethyl acetate-normal hexane 15mL wash-out, collect eluent, and be evaporated near doing 40 ℃ of water-baths, accurately be settled to 2.0mL with normal hexane, add aminopropyl powder 150mg, mixed 2 minutes of whirlpool is crossed 0.45 μ m organic phase filter membrane and is entered the sample introduction bottle, for the gas phase chromatographic determination.
Because it is very large affected by instrument state during machine testing on four kinds of agricultural chemicals, captan, folpet and difoltan are then particularly serious, therefore need to select a kind of purification method of good purification, reduce the pollution to the instrument injection port as far as possible.Purify manually filling chromatographic column with silmag, more loaded down with trivial details.Graphite charcoal post is very strong to the suction-operated of Bravo, silica gel is very strong to the suction-operated of captan, difoltan and folpet, be difficult to wash-out with 5% ethyl acetate-normal hexane, adopt florisil silica pillar (Florisil) to purify, 5% ethyl acetate-normal hexane wash-out, and optimized the consumption of eluent, these four kinds of agricultural chemicals can be eluted fully when the experiment eluent is 10mL, consider the Repeatability and Reproducibility of experiment, determine that 5% ethyl acetate-normal hexane elution volume is 15mL.Be further to increase clean-up effect, obtain more accurately and reliably result and good Data duplication, purifying with the aminopropyl powder going on foot with the little column purification of SPE laggard, to remove the impurity such as fatty acid in the sample and polarity pigment.
6, detect with Agilent7890A gas chromatograph-electron capture detector:
Utilize Agilent7890A gas chromatograph-electron capture detector to measure, select DB-5 quartz capillary column (30m * 0.25mm * 0.25 μ m), chromatogram column temperature is made as 60 ℃, keep 1.25min; Rise to 180 ℃ with 20 ℃/min, keep 7min; Rise to 230 ℃ with 5 ℃/min again, keep 7min; Rise to 270 ℃ with 30 ℃/min again, keep 5min.Detector temperature is made as 300 ℃, and injector temperature is made as 250 ℃.High Purity Nitrogen with purity＞99.999% is done carrier gas, and the post flow is made as 1.4mL/min, and make-up gas? flow 30mL/min puts the sample introduction bottle in the sample disc of gas chromatograph, and behind instrument stabilizer, sample introduction is measured, sample size 1 μ L.
External standard method is quantitative, calculates the measured value of agricultural chemicals.
In order to obtain accurately quantitative result and good Data duplication, the injection port bushing pipe of gas chromatograph need be with the bushing pipe of clean deactivation inside surface, and guarantees that the post effect of chromatographic column wants high, to reduce decomposition or the absorption that causes behind kind of the agricultural chemicals sample introduction.
The recovery and precision to Bravo, captan, difoltan and four kinds of agricultural chemicals of folpet in cucurbita pepo, rape, radish, apple, wax gourd, cauliflower, 7 kinds of matrix of peach are measured by above-mentioned steps:
Determination of recovery rates is to add 1 μ g mixed standard solution in the 100g negative sample, adds 5% phosphoric acid solution 50g, blends to take by weighing sample 15g after mixing, and according to the operation of sample pre-treatments step, the results are shown in Table 2.
The recovery and relative standard deviation (n=6) that 7 kinds of different samples of table 2 add 4 kinds of agricultural chemicals
By data in the table 2 as seen, the interpolation recovery of these four kinds of agricultural chemicals in 7 kinds of vegetables and fruit is all greater than 80%, and relative standard deviation is all less than 10.4%, and recovery height and precision are good.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. measure the residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet for one kind, it is characterized in that: concrete steps comprise:
(1) preparation of sample: with the leaf vegetables sample be cut into 2-3 cm the section, fruit class sample is cut into the piece of the about 2-3cm of length;
(2) process sample with phosphoric acid: add phosphoric acid solution sample is processed, blend, mix, be prepared into even sample;
(3) extract object with acetonitrile: add acetonitrile in step (2) the gained sample, carry out high speed homogenization and centrifugal, obtain extract after centrifugal, then extract is carried out reduced pressure concentration;
(4) phosphoric acid and the water-solubility impurity in the removal extract: solid phase is supported the inner Hydromatrix-of filling of liquid-liquid extraction post diatomite adsorbant, to concentrate rear extract and cross solid phase support liquid-liquid extraction post, balance 10min, use water-fast eluent ethyl acetate, collect eluent, be concentrated near doing, to be clean;
(5) further purify with florisil silica pillar and aminopropyl powder: with 10mL normal hexane activation pillar, be transferred in the florisil silica pillar with the sample residue of 3 * 2mL normal hexane with above-mentioned preparation, then use 5% ethyl acetate-normal hexane 15mL wash-out, collect eluent, and be evaporated near doing 40 ℃ of water-baths, accurately be settled to 2.0mL with normal hexane, add aminopropyl powder 150mg, mixed 2 minutes of whirlpool is crossed 0.45 μ m organic phase filter membrane and is entered the sample introduction bottle, for the gas phase chromatographic determination;
(6) detect with Agilent7890A gas chromatograph-electron capture detector: utilize Agilent7890A gas chromatograph-electron capture detector to measure, select the DB-5 quartz capillary column, chromatogram column temperature is made as 60 ℃, keep 1.25min; Rise to 180 ℃ with 20 ℃/min, keep 7min; Rise to 230 ℃ with 5 ℃/min again, keep 7min; Rise to 270 ℃ with 30 ℃/min again, keep 5min; Detector temperature is made as 300 ℃, and injector temperature is made as 250 ℃, does carrier gas with High Purity Nitrogen, the post flow is made as 1.4mL/min, and make-up gas? flow 30mL/min puts the sample introduction bottle in the sample disc of gas chromatograph, behind instrument stabilizer, sample introduction is measured, sample size 1 μ L; External standard method is quantitative, calculates the measured value of agricultural chemicals.
2. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1 is characterized in that: adding the consumption that phosphoric acid solution processes sample is: take by weighing the 100g sample, add 5% phosphoric acid solution 50g.
3. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1 is characterized in that: the step of extracting object with acetonitrile comprises:
Take by weighing the sample 15g that handles well with 5% phosphoric acid solution, place the 100mL plastic centrifuge tube, add acetonitrile 40mL, high speed homogenization 2min, carry out centrifugal 5min with 5000r/min speed, extract moves in the rotary evaporation bottle, on the Rotary Evaporators under 40 ℃ of water bath condition reduced pressure concentration.
4. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, it is characterized in that: described Hydromatrix-diatomite adsorbant be fossil take diatom as raw material, the adsorbent with the wettable specific surface of high water of making through high temperature purification.
5. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1 is characterized in that: the consumption of ethyl acetate is 100ml in the described step (4).
6. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1 or 5, it is characterized in that: in the described step (4), eluent is placed Rotary Evaporators, the pressure of control Rotary Evaporators is 0.016MPa, in 40 ℃ of water-bath reduced pressure concentrations.
7. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, it is characterized in that: described High Purity Nitrogen is the nitrogen of purity＞99.999%.
8. a kind of residual method of Bravo in the vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1 is characterized in that: the injection port bushing pipe of gas chromatograph is with the bushing pipe of clean deactivation inside surface.
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| CN110057928A (en) * | 2019-02-27 | 2019-07-26 | 中国热带农业科学院农产品加工研究所 | A kind of ultra performance liquid chromatography tandem mass spectrometry detecting captan residual quantity in tomato |
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