CN103353488B - 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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- CN103353488B CN103353488B CN201310242216.4A CN201310242216A CN103353488B CN 103353488 B CN103353488 B CN 103353488B CN 201310242216 A CN201310242216 A CN 201310242216A CN 103353488 B CN103353488 B CN 103353488B
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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 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 there is prevention effect, 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, as difoltan in regulation vegetable and fruit in Japanese positive list must not detect, in radish and apple, the maximum residue limit(MRL) of Bravo (MRL) is respectively 0.1mg/kg and 2.0mg/kg, and European Union specifies that the maximum residue limit(MRL) of captan in radish and spinach is 0.1mg/kg etc.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, some documents and standard method are after sample is smashed, before extraction, add phosphoric acid or ZnAc solution to improve captan, folpet, the stability of difoltan and Bravo, but these four kinds of agricultural chemicals will be degraded in the time that some sample is smashed, therefore as a positive, in the time of sample preparation, directly sample is smashed, even if add again phosphoric acid and change the pH value of extraction environment before extracting, can not obtain quantitative result accurately and reliably.
Summary of the invention
For the defect existing in prior art, the object of the present invention is to provide a kind of residual method of Bravo in vegetables and fruits, captan, difoltan and folpet of measuring, the method recovery is high, mensuration is more accurate.
For reaching above object, the technical scheme that the present invention takes is:
Measure the residual method of Bravo in vegetables and fruits, captan, difoltan and folpet, it is characterized in that: concrete steps comprise:
1, the preparation of sample: leaf vegetables sample is cut into the section of 2-3 cm, fruit class sample is cut into the approximately piece of 2-3cm of length;
2, use phosphoric acid processing sample: add phosphoric acid solution to process sample, blend, mix, be prepared into even sample;
3, extract object with acetonitrile: in step 2 gained sample, add acetonitrile, carry out high speed homogenization and centrifugal, obtain extract after centrifugal, then extract is carried out to reduced pressure concentration;
4, remove phosphoric acid and the water-solubility impurity in extract: solid phase is supported the inner Hydromatrix-of filling of liquid-liquid extraction post diatomite adsorbant, after concentrating, extract is crossed solid phase and is supported liquid-liquid extraction post, balance 10min, use water-fast eluent ethyl acetate, collect eluent, be concentrated near dry, to be clean;
5, further purify with florisil silica pillar and aminopropyl powder: with 10mL normal hexane activation pillar, the sample residue of above-mentioned preparation is transferred in florisil silica pillar with 3 × 2mL normal hexane, then use 5% ethyl acetate-normal hexane 15mL wash-out, collect eluent, and in 40 DEG C of water-baths, be evaporated to closely dry, be accurately settled to 2.0mL with normal hexane, add aminopropyl powder 150mg, mixed 2 minutes of whirlpool, crosses 0.45 μ m organic phase filter membrane and enters sample introduction bottle, for gas Chromatographic Determination;
6, detect with Agilent7890A gas chromatograph-electron capture detector: utilize Agilent7890A gas chromatograph-electron capture detector to measure, select DB-5 quartz capillary column, chromatogram column temperature is made as to 60 DEG C, keep 1.25min; Rise to 180 DEG C with 20 DEG C/min, keep 7min; Rise to 230 DEG C with 5 DEG C/min again, keep 7min; Rise to 270 DEG C with 30 DEG C/min again, keep 5min; Detector temperature is made as 300 DEG C, and injector temperature is made as 250 DEG C, does carrier gas with High Purity Nitrogen, post flow is made as to 1.4mL/min, and make-up gas flow 30mL/min, puts sample introduction bottle in the sample disc of gas chromatograph, after instrument stabilizer, sample introduction is measured, sample size 1 μ L; External standard method is quantitative, calculates the measured value of agricultural chemicals.
Below the further optimization to technique scheme:
Add the consumption that phosphoric acid solution is processed sample to be: to take 100g sample, add 5% phosphoric acid solution 50g.
The step of extracting object with acetonitrile comprises: take the sample 15g handling well with 5% phosphoric acid solution, be placed in 100mL plastic centrifuge tube, add acetonitrile 40mL, high speed homogenization 2min, carry out centrifugal 5min with 5000r/min speed, extract moves in rotary evaporation bottle, on Rotary Evaporators under 40 DEG C of water bath condition reduced pressure concentration.
Described Hydromatrix-diatomite adsorbant be fossil taking diatom as raw material, the adsorbent with the wettable specific surface of high water of making through high temperature purification.
In described step 4, the consumption of ethyl acetate is 100ml.
In described step 4, eluent is placed in to Rotary Evaporators, the pressure of controlling Rotary Evaporators is 0.016MPa, in 40 DEG C of water-bath reduced pressure concentrations.
Described High Purity Nitrogen is the nitrogen of purity > 99.999%.
The bushing pipe of clean deactivation inside surface for the injection port bushing pipe of gas chromatograph.
The present invention adopts above technical scheme, compared with prior art has the following advantages:
This detection method is to 5% phosphoric acid processing for fruit and vegetable sample, avoid sample in the loss of pulverizing four kinds of agricultural chemicals in preparation process, support the deacidification of liquid-liquid extraction technology and water-solubility impurity by solid phase again, after extract is concentrated, purify with Florisil solid-phase extraction column and aminopropyl powder, with the detection of gas chromatograph-electron capture detector, in the time detecting rape, radish, cucurbita pepo, cauliflower, peach, apple, 7 kinds of fruit and vegetable matrix of wax gourd, noiseless phenomenon occurs; This assay method is applicable to the mensuration to these four kinds of residues of pesticides in all vegetables and fruit, and the recovery is all greater than 80%, and this assay method makes in vegetables and fruit these four kinds of residues of pesticides quantitative determinations more accurately and reliably.
Brief description of the 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 present 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 the chromatogram through the acid-treated blank radish of 5% phosphorus in the embodiment of the present invention;
Fig. 3 is the chromatogram through the mixed mark of acid-treated interpolation 0.02 mg/kg of 5% phosphorus radish in the embodiment of the present invention.
Embodiment
Embodiment 1
Except as otherwise noted, the percentage adopting in the present invention is percent by weight.
Measure the residual method of Bravo in vegetables and fruits, captan, difoltan and folpet, concrete steps are as follows:
1, the preparation of sample:
The section that leaf vegetables sample is cut into 2-3 cm, fruit class sample is cut into the approximately piece of 2-3cm of length.
2, use phosphoric acid processing sample:
Accurately take 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 in the time that smashing, the matrix samples such as cucurbita pepo, rape, radish, cauliflower, peach will degrade, so adopt the method that adds phosphoric acid in the time of sample preparation, avoided sample in the loss of pulverizing four kinds of agricultural chemicals in preparation process.Use phosphoric acid solution processing sample, 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, before stripping and slicing sample adds phosphoric acid, interpolation 2 μ g agricultural chemicals mixed standard solutions do interpolation recovery.
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, basic identical without the recovery situation of phosphoric acid processing, 0% phosphoric acid solution processing, all 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 is also lower than 80%; The interpolation recovery of the acid-treated 4 kinds of agricultural chemicals of 5% phosphorus is all higher than 85%; 10%, the acid-treated recovery situation of 15%, 20%, 25% phosphorus and 5% phosphoric acid process basic identical, but phosphoric acid concentration height one be that pre-processing device is had to impact, the 2nd, waste that consumption is large, therefore selects 5% phosphoric acid to process sample.
When cucurbita pepo, rape, radish, cauliflower, peach, apple, 7 kinds of different substrates sample preparations of wax gourd, process with the interpolation recovery without phosphoric acid solution processing and contrast with phosphoric acid solution:
When 7 kinds of different substrates sample preparations, process with the interpolation recovery without phosphoric acid solution processing and contrast with phosphoric acid solution:
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 length and are the fritter of 2-3cm, be prepared into respectively three kinds of different interpolation recovery samples by following three kinds of modes, A: directly sample is blended while preparing sample, take 10g sample, add 0.2 μ g Bravo, captan, folpet and difoltan agricultural chemicals mixed standard solution, 5 points of kinds are mixed in whirlpool, and agricultural chemicals is fully mixed with sample; B: directly sample is blended while preparing sample, take 10g sample, add 0.2 μ g Bravo, captan, folpet and difoltan agricultural chemicals mixed standard solution, 5 points of kinds are mixed in whirlpool, agricultural chemicals is fully mixed with sample, then before solubilizer extracts, add 5% phosphoric acid 2.5mL; C: take 100g stripping and slicing sample, add 2 μ g agricultural chemicals mixed standard solutions, add 5% phosphoric acid solution 50g, blend after mixing and take sample 15g.
Tri-kinds of interpolation recovery samples of A, B, C that preparation is taken, according to the operation of 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 table 1, while preparing sample, directly sample is blended, Bravo, captan, folpet, these four kinds of agricultural chemicals of difoltan are as very low in the interpolation recovery in cucurbita pepo, rape, radish in some matrix, all lower than 35%, and directly sample is blended while preparing sample, after adding pesticide standard solution, 5 points of kinds are mixed in whirlpool, make agricultural chemicals fully contact mixing with sample, before extracting, adding phosphoric acid solution does not act on the raising of adding the recovery again, but before sample preparation, first add phosphoric acid solution and blend again sample, the recovery is significantly increased, and is 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 sample preparation process, just can not obtain quantitative result accurately so do not add phosphoric acid solution processing before sample preparation.And directly sample is blended while preparing sample, do not have influential matrix as apple, wax gourd for the interpolation recovery of these four kinds of agricultural chemicals, prepare and first add phosphoric acid solution before sample and blend again, for the recovery also without any impact, so when the Bravo in vegetables and fruit, captan, folpet, difoltan are detected, prepare and all can first add phosphoric acid before sample and blend again.
Bravo, captan, difoltan and folpet persticide residue in these assay method energy Accurate Determining vegetables and fruit, not only greatly improved extraction efficiency and added the recovery, also strengthened clean-up effect.Existing detection method only has the good recovery to the residual quantity of Bravo, captan, difoltan and folpet in a part of vegetables and 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 to the mensuration to these four kinds of agricultural chemicals in all vegetables and fruit, and the recovery is all greater than 80%.This assay method makes in vegetables and fruit this residues of pesticides quantitative determination more accurately and reliably.
3, extract object with acetonitrile:
Take the sample 15.0g handling well with 5% phosphoric acid solution, be placed in 100mL plastic centrifuge tube, add acetonitrile 40mL, high speed homogenization 2min on homogenizer, carry out centrifugal 5min with 5000r/min speed, extract moves in rotary evaporation bottle, is evaporated to 20 mL left and right on Rotary Evaporators under 40 DEG C of water bath condition.
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 in extracting object, also can extract more impurity, and the impurity phase that acetonitrile extracts is to less, so select acetonitrile to make extraction solvent.
4, remove phosphoric acid and the water-solubility impurity in extract:
Solid phase is supported the inner Hydromatrix-of filling of liquid-liquid extraction post diatomite adsorbant, this adsorbent is taking the fossil of diatom as raw material, through high temperature purification, there is the wettable specific surface of high water, the organic solvent extract that contains moisture content after concentrated is crossed to solid phase and support liquid-liquid extraction post, in extract, only there is organic solvent not have the moisture content recovery can be very low, balance 10min, with the water-fast eluent ethyl acetate of 100ml, phosphoric acid and water-solubility impurity are retained in the diatom scholar adsorbent of solid phase support liquid-liquid extraction post like this, water-fast agricultural chemicals is got off by eluent ethyl acetate.Collect eluent, control the pressure of Rotary Evaporators at 0.016MPa, be evaporated near dry, to be clean in 40 DEG C of water-baths;
Mineral acid can cause damage mutually to the fixing of gas chromatographic column, causes partial fixing liquid to run off, and reduces column performance, pollutes gas phase detecting device, so need to remove the phosphoric acid solution in extract in the time of sample purification.Traditional liquid-liquid extraction method (LLE) can be removed the phosphoric acid in extract, but this method complex operation, with glass apparatus separating funnel extraction 2-3 times, emulsion easily occurs in extraction process, affects the recovery and clean-up effect.Solid phase supports that liquid-liquid extraction method (SSLLE) is a kind of method of phosphoric acid and water-solubility impurity in 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, result is reproducible.
5, further purify with florisil silica pillar and aminopropyl powder:
With 10mL normal hexane activation pillar, the sample residue of above-mentioned preparation is transferred in florisil silica pillar with 3 × 2mL normal hexane, then use 5% ethyl acetate-normal hexane 15mL wash-out, collect eluent, and in 40 DEG C of water-baths, be evaporated to closely dry, be accurately settled to 2.0mL with normal hexane, add aminopropyl powder 150mg, mixed 2 minutes of whirlpool, crosses 0.45 μ m organic phase filter membrane and enters sample introduction bottle, for gas Chromatographic Determination.
Very large owing to affected by instrument state when machine testing on four kinds of agricultural chemicals, captan, folpet and difoltan are particularly serious, therefore need to select a kind of purification method of good purification, reduce the pollution to instrument injection port as far as possible.Purify and need 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, in the time that experiment eluent is 10mL, these four kinds of agricultural chemicals can be eluted completely, consider the Repeatability and Reproducibility of experiment, determine that 5% ethyl acetate-normal hexane elution volume is 15mL.For further increasing clean-up effect, obtain result and good Data duplication more accurately and reliably, purifying with the laggard step of the little column purification of SPE aminopropyl powder, to remove the impurity such as fatty acid and polarity pigment in sample.
6, detect with Agilent7890A gas chromatograph-electron capture detector:
Utilize Agilent7890A gas chromatograph-electron capture detector to measure, (30m × 0.25mm × 0.25 μ m), is made as 60 DEG C by chromatogram column temperature, keeps 1.25min to select DB-5 quartz capillary column; Rise to 180 DEG C with 20 DEG C/min, keep 7min; Rise to 230 DEG C with 5 DEG C/min again, keep 7min; Rise to 270 DEG C with 30 DEG C/min again, keep 5min.Detector temperature is made as 300 DEG C, and injector temperature is made as 250 DEG C.Do carrier gas with the High Purity Nitrogen of purity > 99.999%, post flow is made as to 1.4mL/min, make-up gas flow 30mL/min, puts sample introduction bottle in the sample disc of gas chromatograph, and after 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 quantitative result and good Data duplication accurately, the injection port bushing pipe of gas chromatograph need be with the bushing pipe of clean deactivation inside surface, and ensures that the post effect of chromatographic column wants high, to reduce the decomposition or the absorption that cause after kind of 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 in 100g negative sample, to add 1 μ g mixed standard solution, adds 5% phosphoric acid solution 50g, blends after mixing and takes sample 15g, 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
From data in table 2, 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 the recovery is high and precision good.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. measure the residual method of Bravo in vegetables and fruits, captan, difoltan and folpet, it is characterized in that: concrete steps comprise:
(1) preparation of sample: leaf vegetables sample is cut into the section of 2-3 cm, fruit class sample is cut into length and is respectively the piece of 2-3cm;
(2) use phosphoric acid processing sample: add phosphoric acid solution to process sample, blend, mix, be prepared into even sample;
(3) extract object with acetonitrile: in step (2) gained sample, add acetonitrile, carry out high speed homogenization and centrifugal, obtain extract after centrifugal, then extract is carried out to reduced pressure concentration;
(4) remove phosphoric acid and the water-solubility impurity in extract: solid phase is supported the inner Hydromatrix-of filling of liquid-liquid extraction post diatomite adsorbant, after concentrating, extract is crossed solid phase and is supported liquid-liquid extraction post, balance 10min, use water-fast eluent ethyl acetate, collect eluent, be concentrated near dry, to be clean;
(5) further purify with florisil silica pillar and aminopropyl powder: with 10mL normal hexane activation pillar, the sample residue of above-mentioned preparation is transferred in florisil silica pillar with 3 × 2mL normal hexane, then use 5% ethyl acetate-normal hexane 15mL wash-out, collect eluent, and in 40 DEG C of water-baths, be evaporated to closely dry, be accurately settled to 2.0mL with normal hexane, add aminopropyl powder 150mg, mixed 2 minutes of whirlpool, crosses 0.45 μ m organic phase filter membrane and enters sample introduction bottle, for gas Chromatographic Determination;
(6) detect with Agilent7890A gas chromatograph-electron capture detector: utilize Agilent7890A gas chromatograph-electron capture detector to measure, select DB-5 quartz capillary column, chromatogram column temperature is made as to 60 DEG C, keep 1.25min; Rise to 180 DEG C with 20 DEG C/min, keep 7min; Rise to 230 DEG C with 5 DEG C/min again, keep 7min; Rise to 270 DEG C with 30 DEG C/min again, keep 5min; Detector temperature is made as 300 DEG C, and injector temperature is made as 250 DEG C, does carrier gas with High Purity Nitrogen, post flow is made as to 1.4mL/min, and make-up gas flow 30mL/min, puts sample introduction bottle in the sample disc of gas chromatograph, after 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 vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, is characterized in that: add the consumption that phosphoric acid solution is processed sample to be: take 100g sample, add 5% phosphoric acid solution 50g.
3. a kind of residual method of Bravo in 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 the sample 15g handling well with 5% phosphoric acid solution, be placed in 100mL plastic centrifuge tube, add acetonitrile 40mL, high speed homogenization 2min, carry out centrifugal 5min with 5000r/min speed, extract moves in rotary evaporation bottle, on Rotary Evaporators under 40 DEG C of water bath condition reduced pressure concentration.
4. a kind of residual method of Bravo in vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, it is characterized in that: described Hydromatrix-diatomite adsorbant be fossil taking 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 vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, is characterized in that: in described step (4), the consumption of ethyl acetate is 100ml.
6. a kind of residual method of Bravo in vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1 or 5, it is characterized in that: in described step (4), eluent is placed in to Rotary Evaporators, the pressure of controlling Rotary Evaporators is 0.016MPa, in 40 DEG C of water-bath reduced pressure concentrations.
7. a kind of residual method of Bravo in vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, is characterized in that: described High Purity Nitrogen is the nitrogen of purity > 99.999%.
8. a kind of residual method of Bravo in vegetables and fruits, captan, difoltan and folpet of measuring according to claim 1, is characterized in that: the bushing pipe of clean deactivation inside surface for the injection port bushing pipe of gas chromatograph.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109709231A (en) * | 2019-01-28 | 2019-05-03 | 中南大学 | The remaining determination method of Bravo in water environment |
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