CN105334277B - Quick pretreatment method and detection method for grape wine farming residual analysis - Google Patents
Quick pretreatment method and detection method for grape wine farming residual analysis Download PDFInfo
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Abstract
The present invention relates to the methods for carrying out pre-treatment to grape wine, and the grape wine is the sample of pending pesticide residue determination, which is characterized in that the method includes three extraction, purification, concentration steps.The invention further relates to the method for carrying out pesticide residue determination to grape wine, this method carries out pre-treatment using pre-treating method of the present invention to wine samples.Pre-treating method of the present invention can be realized carries out quick pre-treatment to the wine samples that will carry out the residual detection of agriculture, and step is few, time-consuming short, is not necessarily to a large amount of organic solvent, very environmentally friendly, and cost is relatively low.
Description
Technical field
The present invention relates to for grape wine farming residual analysis quick pretreatment method and carried out using the pre-treating method
Detection method.Specifically, the present invention by wine samples carry out quick pretreatment, to use gas-chromatography-matter
Spectrum analysis method is carried out at the same time detection to the residual quantity of Multiple Pesticides in grape wine.
Background technology
Fungicide is that have killing effect to pathogenic microorganism or inhibit the medicament of growth, is had a wide range of application.Wine brewing Portugal
Grape easy infection fungal disease, therefore need in planting process repeatedly to spray fungicide, including sulphur preparation, copper agent, amine, virtue
The fragrant same clan, benzimidazole, imidodicarbonic diamide class triazole type etc..Insecticide and herbicide are also to prevent harmful organism from protecting plant
Important pesticide includes commonly organic phosphates, organochlorine class, pyrethroid, carbamates and diphenyl ether etc..It is residual
The pesticide stayed not only inhibits alcoholic fermentation, and wine product is also made to constitute potential threat to health.
Grape wine is the beverage that new fresh grape or grape juice are obtained through everfermentation, contains a large amount of polyphenol, sugar, pigment, dimension
Raw element and minerals, matrix is complicated, and to the Detecting Pesticide of trace, there are severe jammings.It is appropriate to be carried out to wine samples
Pre-treatment after, then using gas chromatography-mass spectrography simultaneously qualitative and quantitative analysis Multiple Pesticides residual.Currently, research both at home and abroad
The pre-treating method of Pesticide Residues in Wine mainly has liquid-liquid extraction, mechanical shaking extraction, Solid Phase Extraction, solid phase microextraction, gel
The methods of permeation chromatography, these methods operation have shortcomings, if step is more, take it is longer, operating personnel need to it is a large amount of
Organic solvent exposure, pollute environment, and cost is higher.
Invention content
In view of the above technical problems, there is an urgent need in the art to can shorten time for sample pretreatment, save solvent, reduce at
This detection method.
In this regard, it is an object of the invention to overcome, existing Sample Pretreatment Technique processing time is long, is lacked more than consumption solvent etc.
Point and deficiency, can be to the residual quantity of Multiple Pesticides in grape wine using quick, effective and inexpensive sample pretreatment process
It is carried out at the same time detection.
The first aspect of the present invention is related to the method for carrying out pre-treatment to grape wine, which is that pending pesticide is residual
The sample of allowance detection, the pre-treating method include the following steps：
(1) it extracts：Internal standard compound, the acetonitrile containing 1% acetic acid, sodium chloride, anhydrous sodium acetate are added into the grape wine, shakes
It shakes, then ultrasonic extraction in the presence of ice bag, shakes after adding drier, is then centrifuged for detaching；
(2) it purifies：It will be mixed, be shaken with adsorbent and drier by the supernatant extracting solution obtained in the step (1), then
It centrifuges；
(3) it concentrates：To be concentrated by the supernatant scavenging solution that is obtained in the step (2), be filtered by filter membrane, with wait for into
The pesticide residue determination of one step.
In a preferred embodiment, pre-treating method of the present invention can with one in following technical characteristic or
It is multinomial：Internal standard compound is Heptachlor epoxide B；Drier in step (1) is anhydrous magnesium sulfate；Adsorbent is Graphon and N- third
Base ethylenediamine bonded silica gel；Drier in step (2) is anhydrous magnesium sulfate；Concentration in step (3) uses the nitrogen at 30 DEG C
The mode blown carries out；The filter membrane is the nylon leaching film that aperture is 0.22 μm.
In a preferred embodiment, the dosage of each reagent is：Grape wine 10g；Acetonitrile 20mL containing 1% acetic acid；Chlorination
Sodium 4g；Anhydrous sodium acetate 1g；Drier 6g in step (1)；As the Graphon 25-100mg of adsorbent, preferably
50mg；N- propyl ethylenediamines bonded silica gel 100-300mg, preferably 250mg as adsorbent；Drier 1g in step (2).
In further preferred embodiment, in the step (2), carried by the supernatant obtained in the step (1) using 10mL
Take liquid；And/or in the step (3), using 5mL by the supernatant scavenging solution that is obtained in the step (2).
In a highly preferred embodiment, described method includes following steps：
(1) it extracts：Heptachlor epoxide B is added into grape wine described in 10g, 20mL is added and contains the acetonitrile of 1% acetic acid, 4g chlorinations
Sodium, 1g anhydrous sodium acetates shake 2min, then ultrasonic extraction 20min in the presence of ice bag, after adding 6g anhydrous magnesium sulfates
2min is shaken, 5min is then centrifuged with 3000r/min；
(2) it purifies：By 10mL by the supernatant extracting solution that is obtained in the step (1) and 50mg Graphons, 250mg
N- propyl ethylenediamine bonded silica gels and the mixing of 1g anhydrous magnesium sulfates shake 2min, then centrifuge 3min with 6000r/min；
(3) it concentrates：5mL is concentrated at 30 DEG C with the mode that nitrogen is blown by the supernatant scavenging solution obtained in the step (2)
To 1mL, the nylon leaching film for being 0.22 μm by aperture is filtered, to wait for further pesticide residue determination.
In further preferred embodiment, step (1) carries out in 50mL centrifuge tubes, and step (2) is in 15mL poly- third
It is carried out in alkene centrifuge tube, step (3) carries out in the 5mL glass centrifuge tubes with accurate scale.
The second aspect of the present invention is related to the method for carrying out pesticide residue determination to grape wine, which includes making
The step of pre-treatment is carried out to grape wine with the pre-treating method described in first aspect present invention.In a preferred embodiment,
Pesticide residue determination is carried out by GC/MS after the completion of pre-treatment step.
Pre-treating method of the present invention, which can be realized, carries out quickly the wine samples that will carry out the residual detection of agriculture
Pre-treatment, step is few, time-consuming short, is not necessarily to a large amount of organic solvent, very environmentally friendly, and cost is relatively low.
One important feature of pre-treating method of the present invention is that ultrasonic extraction is carried out in the presence of ice bag.Although logical
It crosses for example to tie up to extracting liq in refrigerator and refrigerates certain time and extract can also reach similar extraction effect again, but in this way
Step (1) the required time can be greatly increased, for realizing that quick pretreatment is unfavorable.If controlling room temperature or ultrasonic machine
The temperature (such as passing through air-conditioning or constant temperature sensing and controlling device) of water-bath shortens the time, and can obviously increase testing cost,
Be unfavorable for this method brewery practical application.In fact, the temperature during reducing ultrasonic process using ice bag, it can not only
Rapid extraction is realized, simultaneously because ice bag can reuse so that method of the invention is at two aspect of time and economic cost
All there is apparent advantage.
In addition, although some residual detection pre-treatments of agriculture for samples such as water fruits and vegetables, Chinese herbal medicines exist in the prior art
Technology, but its targeted sample substrate differs larger (even the matrix of fruit grape with the grape wine matrix of the present invention
It is different from grape wine matrix).Grape wine is to use dedicated vinifera, using fresh grape or grape juice as raw material, is passed through
Ferment the product containing certain alcoholic strength generated.For vinifera compared with fruit grape, sugar, acidity and aldehydes matter are (main
It is tannin) content higher；Through yeast fermentation and oak barrel during aging after, in grape wine also the alcohol containing 12-14%, higher alcohol and
The substances such as ester, Oak Lactone.Therefore, wine samples should not be handled with the existing pre-treating method for other matrix.
Description of the drawings
Fig. 1 is 0.100 μ g/mL52 kind standard sample of pesticide total ion chromatograms.
Specific implementation mode
In following illustrative specific implementation modes of the present invention, used instrument includes：7890A-5975C gas phases
Chromatography-mass spectroscopy instrument (Agilent companies of the U.S.), TG16-II table model high speed centrifuges (the ordinary instrument and meter Co., Ltd in Changsha),
BSA224S-CW electronic balances (German Sai Duolisi groups), SB-3200DTDN supersonic wave cleaning machines (the new sesame biotechnology in Ningbo
Limited liability company), TTL-DC II nitrogen evaporators (with Tai Lian developments in science and technology Co., Ltd), QL-902 vortex mixers (Haimen its
Woods Bell's instrument manufacturing Co., Ltd).
In following illustrative specific implementation modes of the present invention, used standard sample of pesticide includes：It is Propamocarb, interior
Inhale phosphorus, Spanon, thimet, terbufos, pyrimethanil, Bravo, phosphamidon, heptachlor, fenifrothion, malathion, Entex,
Parathion, procymidone, fenamiphos, Profenofos, Flusilazole, nitrofen, p, p`-DDE, p, p`-DDD, o, p`-DDT, p, p`-
DDT, Tebuconazole, epoxiconazole, Permethrin, Prochloraz, Fluoxastrobin, DDVP, Bassa, phonamiphos, sulfotep, α -666, β -
666, γ -666, δ -666, Fonofos, isazofos, parathion-methyl, metalaxyl, drinox, diethofencarb, chlopyrifos, own azoles
Alcohol, dieldrite, nitrile bacterium azoles, endrin, olefin conversion, propiconazole, propargite, Fenpropathrin, Resistox, fenvalerate (Germany
Dr.Ehrenstorfer GmbH companies).
In following illustrative specific implementation modes of the present invention, used other reagents include：Acetonitrile (chromatography
It is pure, Fisher companies)；Heptachlor epoxide B (German Dr.Ehrenstorfer GmbH companies)；Acetic acid (analyzes pure, Beijing chemical industry
Factory)；Anhydrous magnesium sulfate, anhydrous sodium chloride (analyzing pure, Sinopharm Chemical Reagent Co., Ltd.)；Anhydrous sodium acetate (analysis is pure,
Beijing Chemical Plant)；Graphon (GCB), N- propyl ethylenediamine bonded silica gels (PSA) (the limited public affairs of Beaune Ai Jieer science and technology
Department)；Wine samples are purchased from supermarket.
Embodiment
1. the preparation of standard solution
The hybrid standard storing solution that standard solution acetone is diluted to and is configured to 10 μ g/mL, stores under the conditions of -18 DEG C.
2. the pre-treatment of sample
Extraction：Grape wine after taking 10g to shake up is placed in 50mL centrifuge tubes, and appropriate internal standard compound (Heptachlor epoxide B) is added,
20mL acetonitriles (containing 1% acetic acid), 4g sodium chloride and 1g anhydrous sodium acetates is added, shakes ultrasonic extraction 20min after 2min manually,
It needs bag on the rocks to prevent water temperature from quickly increasing when ultrasonic, 2min is quickly shaken after 6g anhydrous magnesium sulfates are added, in low speed centrifuge
In with 3000r/min centrifuge 5min.
Purification：15mL polypropylene centrifuge tubes are taken, 50mg Graphons, 250mg N- propyl ethylenediamine bonded silicas is added
Glue and 1g anhydrous magnesium sulfates are transferred to above-mentioned supernatant extracting solution 10mL, and after shaking 2min manually, 3min is centrifuged with 6000r/min.
Concentration：It takes 5mL to carry the glass centrifuge tube of accurate scale, supernatant scavenging solution 5mL is added, is used under the conditions of 30 DEG C
Nitrogen is concentrated into 1mL, after sample crosses 0.22 μm of nylon leaching film, waits for that GC/MS is analyzed.
3.GC/MS instrument conditions
Chromatographic column：DB-5ms capillary columns, 30m × 0.25mm × 0.25 μm, constant current mode, flow velocity 1.0mL/min；
Injection port：Not shunt mode, 280 DEG C of temperature, 1 μ L of sample size；
Temperature program：100 DEG C of holding 1min, rise to 150 DEG C, 5 DEG C/min rises to 300 DEG C with 20 DEG C/min；Operation temperature afterwards
300 DEG C of degree simultaneously keeps 2min, rear run time 5min；
Carrier gas：He, purity >=99.999%.
Mass detector testing conditions：Salbutamol Selected Ion Monitoring pattern (SIM)；Electron impact ion source (EI) 70eV；Ion
230 DEG C of source temperature；150 DEG C of level four bars temperature；280 DEG C of interface temperature.
4. the range of linearity
In the case of the pre-treating method in using embodiment hereof, 52 kinds of pesticide separation are good (see Fig. 1).With sky
The mixed mark storing solution of 10 μ g/mL is diluted to a concentration of 1.000 by white wine matrix step by step, 0.500,0.200,0.100,
0.050, the mixed mark solution of 0.020,0.010 μ g/mL is measured, with the peak area ratio of pesticide composition and internal standard compound to concentration
Than drawing standard curve, linear equation and related coefficient are shown in Table 1.
1 linear equation of table and related coefficient
Concentration model of the 52 kinds of listed pesticides in 0.010~1.000 μ g/mL it can be seen from the data in above-mentioned table 1
In enclosing, linearly dependent coefficient R is all higher than 0.99, shows there is good linear dependence.
5. mark-on reclaims and Precision Experiment
Weigh the grape wine after 10g shakes up, add mixed mark solution make the addition concentration of sample be respectively 0.02mg/kg,
0.04mg/kg, 0.20mg/kg are analyzed by the experimental method in foregoing embodiments, the average recycling under each pitch-based sphere
Rate, relative standard deviation and quantitative limit are shown in Table 2 (in terms of 10 times of signal-to-noise ratio of quota ion, i.e. LOQ=10 × S/N).
52 kinds of listed pesticides are added at basic, normal, high 3 under concentration level it can be seen from the data of table 2, are had
There are the preferable rate of recovery and smaller relative standard deviation (RSD), detection quantitative limit that can meet the needs of enterprise's routine testing.
Claims (11)
1. a kind of method carrying out pre-treatment to grape wine, the grape wine is the sample of pending pesticide residue determination,
It is characterized in that, described method includes following steps：
(1) it extracts：Be added into grape wine described in 10g acetonitrile containing 1% acetic acid of Heptachlor epoxide B, 20mL, 4g sodium chloride, 1g without
Water sodium acetate, shaking, then ultrasonic extraction in the presence of ice bag, shakes after adding 6g drier, is then centrifuged for detaching；
(2) it purifies：Will by the supernatant extracting solution that is obtained in the step (1) with as the 25-100mg Graphons of adsorbent
It mixes, shaking, then centrifuges with 100-300mg N- propyl ethylenediamine bonded silica gels and 1g drier；
(3) it concentrates：It will be concentrated by the supernatant scavenging solution obtained in the step (2), be filtered by filter membrane, to wait for further
Pesticide residue determination；
Wherein, pesticide of the pesticide selected from following type is one or more：Propamocarb, demeton, Spanon, first are mixed
Phosphorus, terbufos, pyrimethanil, Bravo, phosphamidon, heptachlor, fenifrothion, malathion, Entex, parathion, procymidone, benzene
Line phosphorus, Profenofos, Flusilazole, nitrofen, p, p`-DDE, p, p`-DDD, o, p`-DDT, p, p`-DDT, Tebuconazole, epoxiconazole,
Permethrin, Prochloraz, Fluoxastrobin, DDVP, Bassa, phonamiphos, sulfotep, α -666, β -666, γ -666, δ -666,
It is worm sulphur phosphorus, isazofos, parathion-methyl, metalaxyl, drinox, diethofencarb, chlopyrifos, hexaconazole, dieldrite, nitrile bacterium azoles, different
Dieldrite, olefin conversion, propiconazole, propargite, Fenpropathrin, Resistox, fenvalerate.
2. the method as described in claim 1, which is characterized in that in the step (1)：The drier is anhydrous slufuric acid
Magnesium.
3. the method as described in claim 1, which is characterized in that in the step (2)：The drier is anhydrous slufuric acid
Magnesium.
4. the method as described in claim 1, which is characterized in that in the step (3)：The concentration is using the nitrogen at 30 DEG C
The mode blown carries out；And/or the filter membrane is the nylon leaching film that aperture is 0.22 μm.
5. the method as described in claim 1, which is characterized in that the dosage of each reagent is：Graphon as adsorbent
50mg；N- propyl ethylenediamine bonded silica gels 250mg as adsorbent.
6. the method as described in claim 1 is characterized in that altogether, in the step (2), using 10mL by the step (1)
In obtained supernatant extracting solution.
7. the method as described in claim 1, which is characterized in that in the step (3), using 5mL by the step (2)
Obtained supernatant scavenging solution.
8. method according to any one of claims 1-4, which is characterized in that described method includes following steps：
(1) it extracts：Heptachlor epoxide B is added into grape wine described in 10g, be added 20mL containing the acetonitrile of 1% acetic acid, 4g sodium chloride,
1g anhydrous sodium acetates shake 2min, and then ultrasonic extraction 20min in the presence of ice bag, shakes after adding 6g anhydrous magnesium sulfates
2min is shaken, 5min is then centrifuged with 3000r/min；
(2) it purifies：By 10mL by the supernatant extracting solution that is obtained in the step (1) and 50mg Graphons, 250mg N- third
Base ethylenediamine bonded silica gel and the mixing of 1g anhydrous magnesium sulfates shake 2min, then centrifuge 3min with 6000r/min；
(3) it concentrates：5mL is concentrated at 30 DEG C with the mode that nitrogen is blown by the supernatant scavenging solution obtained in the step (2)
1mL, the nylon leaching film for being 0.22 μm by aperture is filtered, to wait for further pesticide residue determination.
9. method as claimed in claim 8, which is characterized in that the step (1) carries out in 50mL centrifuge tubes, the step
(2) it is carried out in 15mL polypropylene centrifuge tubes, the step (3) carries out in the 5mL glass centrifuge tubes with accurate scale.
10. a kind of method carrying out pesticide residue determination to grape wine, which is characterized in that the detection method includes the right to use
The step of profit requires the method described in any one of 1-9 to carry out pre-treatment to the grape wine.
11. method as claimed in claim 10, which is characterized in that the method includes leading to after the completion of the pre-treatment step
It crosses GC/MS and carries out pesticide residue determination, testing conditions are as follows：
Chromatographic column：DB-5ms capillary columns, 30m × 0.25mm × 0.25 μm, constant current mode, flow velocity 1.0mL/min；Injection port：
Not shunt mode, 280 DEG C of temperature, 1 μ L of sample size；Temperature program：100 DEG C of holding 1min, 150 DEG C are risen to 20 DEG C/min, and 5
DEG C/min rises to 300 DEG C；300 DEG C of running temperature and 2min is kept afterwards, rear run time 5min；Carrier gas：He, purity >=
99.999%；
Mass detector testing conditions：Salbutamol Selected Ion Monitoring Mode S IM；Electron impact ion source EI70eV；Ion source temperature 230
℃；150 DEG C of level four bars temperature；280 DEG C of interface temperature.
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| CN106248854B (en) * | 2016-08-31 | 2018-05-25 | 贵州茅台酒股份有限公司 | A kind of method of 100 kinds of pesticide residues in measure white wine |
| CN106596776B (en) * | 2016-12-20 | 2019-06-07 | 鹿泽启 | The pre-treating method of pyrethroid pesticide remained test sample in grape wine |
| CN109254104A (en) * | 2018-09-26 | 2019-01-22 | 新疆农垦科学院 | The detection method of residues of organophosphate pesticides in a kind of grape wine |
| CN109709231A (en) * | 2019-01-28 | 2019-05-03 | 中南大学 | The remaining determination method of Bravo in water environment |
| CN109709232B (en) * | 2019-01-28 | 2020-09-08 | 中南大学 | Method for detecting and analyzing chlorothalonil residue in aquatic animal tissue |
| CN111207958B (en) * | 2020-01-08 | 2022-08-02 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN113325112A (en) * | 2021-06-08 | 2021-08-31 | 贵州茅台酒股份有限公司 | Method for simultaneously and rapidly detecting residual quantity of various pesticides |
| CN114778723A (en) * | 2022-04-18 | 2022-07-22 | 眉县食品药品安全检验检测中心 | Method for detecting aspartame in wine |
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