CN102262089B - Method for quickly and quantitatively detecting pesticide residue of cyanogens-containing synthetic pyrethroids in tea - Google Patents
Method for quickly and quantitatively detecting pesticide residue of cyanogens-containing synthetic pyrethroids in tea Download PDFInfo
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- CN102262089B CN102262089B CN201110109145.1A CN201110109145A CN102262089B CN 102262089 B CN102262089 B CN 102262089B CN 201110109145 A CN201110109145 A CN 201110109145A CN 102262089 B CN102262089 B CN 102262089B
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Abstract
The invention relates to a method for quickly detecting pesticide residue of cyanogens-containing synthetic pyrethroids in tea. The method comprises the following steps of: leaching cyanogens-containing synthetic pyrethroids in tea in advance; removing interference components in the tea and then heating the pesticide residue of cyanogens-containing synthetic pyrethroids for full alkaline hydrolysis to generate cryanide ions; adding acid to generate HCN (Hydrocyanic Acid) gas; transferring, absorbing and measuring the concentration of a CN (Cyanide) ion by using an air suction device; and realizing accurate quantitative measurement by using thiocyanate-isonicotinic acid pyrazolone spectrophotometry development. According to the method, an alkaline hydrolysis reaction and HCN gas transfer are thoroughly realized by heating, stirring and extracting air, thus the detection sensitivity is high; and meanwhile, interference substances in the tea are eliminated so as to facilitate the accurate quantitative detection. In addition, the method has low cost, is realized by adopting simple equipment, is simple and convenient and is easy to popularize; and the strict on technical requirements is inferior to that of instrument analysis; and the method is a simple accurate analysis method for detecting pesticide residue of fresh leaves in the production of tea and analyzing the quality of finished tea.
Description
Technical field
The present invention relates to a kind of method that detects Pesticide Residues in Tea, specifically, is to the method containing the residual quantitative determination of cyanogen pyrethroid pesticide in tealeaves.
Background technology
Pesticide Residues in Tea is not only drunk directly human body is produced to injury by bubble, and its potential threat and inrichment more make it to become a serious problem of society today.Current Tea Production mainly use and also in tealeaves residual phenomena pyrethroid pesticide most serious of all, most of for containing cyanogen pyrethroid.But for the easy detection technique accurately of such agricultural chemicals, make it be difficult to obtain Real-Time Monitoring and control due to not in Tea Production and trade.
Tea component complexity, contains a large amount of pigments and other interfering materials, and the method for existing mensuration Pesticide Residues amount can not be directly used in the detection of Pesticide Residues in Tea.Current pesticide residue analysis method shows as: accurately its treatment step of detection method is loaded down with trivial details reliably, and requirement for experiment condition is high, as gas chromatography, and the methods such as gas chromatography mass spectrometry; The method sensitivity of simple and fast is low, is mainly used in qualitative analysis, and measurement result poor reliability, as thin layer chromatography etc.
Residues of pesticides common analysis is that instrument detects, and its sample pretreatment process is time-consuming, effort, and skill level and working experience to operating personnel are had relatively high expectations, required analytical instrument costliness, and analyst's professional skill requires high; Enzyme process detects only to organophosphorus pesticide sensitivity, does not act on pyrethroid pesticide; Immunoassay technology complexity, cost is higher, and prior art is limited, and progress is slow.
Chinese patent application CN101865902A, " a kind of method for quick of cyano-containing Determination of Pyrethroid Pesticide Residues " disclosed, the method is only for qualitative reaction, and lixiviate and reaction are placed in to same separating funnel, interference component in tealeaves can not be excluded, through verification experimental verification, the characteristic component in tealeaves can make reaction present false positive, thereby can not be used for the residual detection of tealeaves pyrethroid pesticide.Chinese patent CN1763509 " fast detecting that pyrethroid pesticide is residual " is also because same cause can not be used for the residual detection of tealeaves agriculture.Above-mentioned two methods all have air-generating reaction insufficient in addition, and the shortcoming that gas transfer efficiency is low makes quantitatively to detect the recovery low.
In non-patent literature, wangdan red employing method based on Chinese patent application CN101865902A, and use the HCN gas producing in nitrogen blowing transfer reaction device, finally detect by the method for o-dinitrobenzene colour developing, though part has solved transfer efficiency problem, but still there is false positive phenomenon, can not control reaction Pesticides and fully be hydrolyzed.
Chinese patent application CN101334408 discloses " a kind of enzyme-linked immunosorbent assay method of analyzing residuals of cyano pyrethroid pesticides; belong to immuno analytical method field; do envelope antigen containing artificial synthetic haptens m-phenoxybenzoic cyanohydrin ester succinate and ovalbumin coupled complex; technical sophistication, cost is higher.
Summary of the invention
The object of this invention is to provide in a kind of fast detecting tealeaves and contain the residual method of cyanogen pyrethroid pesticide, the drawback existing to solve prior art, has overcome common instrument analytical approach length consuming time, and technical requirement is high, the shortcoming that cost is high; And can get rid of interfering material in tealeaves, highly sensitive, cost is low, easy easy popularization.
Realizing technical scheme of the present invention is: to residual with petroleum ether extraction containing cyanogen pyrethroid pesticide in tealeaves, by extract in reaction system through exhaust and hydrolysis, after producing cryanide ion, add sulfuric acid to produce HCN gas, and by adding thermal agitation and exhaust by abundant HCN transfer absorbed and detecting its method step:
1) lixiviate extraction: take 3g and grind dry tea sample in triangular flask, adding reagent 20mL boiling range is 60-90 ℃ of sherwood oil, ultrasonic-leaching 15min;
2) exhaust hydrolysis reaction: leaching liquor is filled into air-generating reaction device, adds reagent 10mL6mol/L NaOH, by extract in reaction system through exhaust and hydrolysis, close collection valve, open vent valve, open pump, 65 ℃ of stirring in water bath, reaction 6min bleeds;
3) aerogenesis is collected: open collection valve, the row of cutting out Ye valve, adds reagent 20mL20% sulfuric acid by addition funnel, bleeds and collects 10min;
4) detect: get receiving flask and add buffer solution and the reagent 0.2mL1% toluene-sodium-sulfonchloramide that reagent 5mL pH is 6.8, after placement 3min, add reagent 5mL isonicotinic acid-pyrazolone solution, 30min is in 638nm place colorimetric in reaction.
Damping fluid of the present invention, by 34g anhydrous potassium dihydrogenphosphate, 89.5g disodium hydrogen phosphate is dissolved in 1L distilled water;
Isonicotinic acid-pyrazolone solution of the present invention, is dissolved in 100mL0.5% sodium hydroxide solution by 1.5g isonicotinic acid, and 0.25g pyrazolone is dissolved in 20mL DMF, mixes by 5:1.
The assembling of this reaction aerogenesis apparatus is made up of simple devices such as the conventional glass apparatus in laboratory and aspiration pumps, and the process of getting rid of extract is the concentration process in conventional sense, and this process is reacted with alkaline hydrolysis and carried out simultaneously, and accelerates gas by exhaust and discharge.
The invention has the advantages that:
1 is applicable to tealeaves: by petroleum ether extraction, lixiviate and course of reaction are separated, get rid of interfering material in tealeaves, improve detection accuracy, in tealeaves pyrethroid detects, have good stability;
2 methods are quick: reaction, by concentrating in conventional sense, purifies and reacts and carry out simultaneously;
3 is highly sensitive: agricultural chemicals reaction is thorough, and HCN gas transfer efficiency is high, can reach 0.25mg/kg to the detection limit containing cyanogen pyrethroid;
4 easy being easy to are promoted: equipment is simple, and cost is low, and it is strict that technical requirement is not so good as instrumental analysis;
5 this method can be fast, accurately and residual containing cyanogen pyrethroid pesticide in quantitative measurement tealeaves.
The present invention and pertinent literature technical characteristics and implementation result relatively in table 1:
The major advantage of table 1 the present invention and prior art
Accompanying drawing explanation
Fig. 1 is reaction unit figure
Fig. 2 is the impact of hydrolysis time on reaction process
Fig. 3 affects reaction process for the temperature of reaction of bleeding
Fig. 4 affected reaction process for the reaction time of bleeding
Fig. 5 is variable concentrations sample detection effect
Fig. 6 is that qualitative detection compares chromatic effect
Wherein, Drexel bottle 1, addition funnel 2, generation reaction unit 3, heating magnetic stirring apparatus 4, vent valve 5, collection valve 6, receiving flask 7, air sampler 8.
Embodiment
Embodiment 1:
Pluck bud two or three leaf summer teas take Hua Zhong Agriculture University's Tea Science base and make dry tea as raw material, take 3g mortar and grind, pack 50ml triangular flask into, add reagent one, ultrasonic (KQ-300DZ type numerical control supersonic) lixiviate 15min; Leaching liquor is filtered into reaction unit (3) with cotton; Reagent one washs filter residue twice, merging filtrate; In there-necked flask, add reagent two, coupling arrangement (see photo), shut-off valve (6), open valve (5), open (TH-110B type air sampler) (8), 65 ℃ of stirring in water bath (DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus), reaction 6min bleeds; Open valve (6), shut-off valve (5), adds reagent three by addition funnel (2), bleeds and collects 10min; Close pump (8), take off receiving flask (7) and add reagent four and reagent five, after placement 3min, add reagent six, 30min is at 638nm place colorimetric (752 single beam ultraviolet-visible spectrophotometer) in reaction.
Embodiment 2: in tealeaves, interference component exclusion condition is selected
As embodiment 1 method, adopt respectively different preprocessing process for Tea Samples, own interference component in tealeaves is got rid of in expection.Result is as shown in table 2, and the fundamental property of interference component in tealeaves own has been made to preliminary judgement, be polarity less and need with the basis of alkali reaction on acid adding generate HCN gas.By sherwood oil lixiviate processing, lixiviate and hydrolysis reaction are separated, got rid of the interference component of itself in tealeaves, solved the false positive problem that contains the residual detection of cyanogen pyrethroid agriculture in tealeaves, enable by change color, by the clear qualitative judgement of naked eyes, also to have strengthened the accuracy of quantitative detection.
The effect comparison that table 2 pre-treating method is got rid of interference component
Remarks: "+" is chromogenic reaction, "-" do not develop the color for reacting
Embodiment 3: carrier gas quality is on detecting the impact of effect
As embodiment 1 method, the method that in the time twitching air transfer HCN gas, adopts respectively nitrogen blowing, adds Drexel bottle and direct exhaust before exhaust device.As accompanying drawing 1, in the Drexel bottle of reaction unit front end, pack interference gas in 5% NaOH filtered air into.Record respectively result as table 3, not only can reach the effect suitable with nitrogen blowing by the exhaust method of adding Drexel bottle, and simplify device, reduce costs, be easy to promote the use.
The different carrier gas of table 3 are on detecting the impact (absorbance) of effect
Embodiment 4: absorption liquid is selected and stability
As embodiment 1 method, adopt respectively damping fluid, 1%KOH, 2%KOH as collecting liquid, and respectively reacted collection liquid is done boil, freezing, room temperature places the processing such as 24h.Record absorbance as table 4, result shows uses 1%KOH as not only good stability of absorption liquid, and is easy to the acid or alkali environment adjusting of chromogenic reaction, and color developing effect is best.
The different absorption liquids of table 4 and the impact (absorbance) of processing on testing result
Embodiment 5: hydrolysis time condition optimizing
As embodiment 1 method, arrange that hydrolysis time is respectively 1,2,3,4,6,8,10min, according to colorimetric estimation result as Fig. 2, before 6min, reaction does not fully occur, overlong time, along with can making CN ion, subsidiary reaction generation reduces, therefore that the reaction time is controlled at 6min is suitable.
Embodiment 6: temperature of reaction condition optimizing
As embodiment 1 method, hydrolysising reacting temperature is set and is respectively 40,50,60,70,80,90 ℃, according to colorimetric estimation result, as Fig. 3, in reaction, best bath temperature is 60-70 ℃, it is not thorough that temperature is crossed low reaction, and excess Temperature causes the gas of producing can not be fully absorbed and lose.
Embodiment 7: the reaction time condition optimizing of bleeding
As embodiment 1 method, arrange respectively that the acquisition time of bleeding is 0,2,4,6,10,15,20min, according to colorimetric estimation result as Fig. 4, the soak time of bleeding is that 10min is advisable, prolongation absorbance along with the time below 10min increases, illustrate that gas is not transferred fully before 10min, after 10min, first stablize and decline, illustrating bleeds for a long time has a certain impact to absorption liquid stability.
Claims (3)
1. in tealeaves, contain the residual fast quantitative measurement method for detecting of cyanogen pyrethroid pesticide, it is characterized in that: to residual with petroleum ether extraction containing cyanogen pyrethroid pesticide in tealeaves, by extract in reaction system through exhaust and hydrolysis, after producing cryanide ion, add sulfuric acid to produce HCN gas, and by adding thermal agitation and exhaust by abundant HCN transfer absorbed and detecting its method step:
1) lixiviate extraction: take 3g and grind dry tea sample in triangular flask, adding reagent 20mL boiling range is 60-90 ℃ of sherwood oil, ultrasonic-leaching 15min;
2) exhaust hydrolysis reaction: leaching liquor is filled into air-generating reaction device (3), add reagent 10mL6mol/L NaOH, air-generating reaction device (3) top is connected to addition funnel (2) to be placed in heating magnetic stirring apparatus (4), and connect Drexel bottle (1) in its one end, the other end separately connects vent valve (5) and collects valve (6), collect after valve (6) connects receiving flask (7) and access again air sampler (8) together with vent valve (5), close and collect valve (6), open vent valve (5), open air sampler (8), 65 ℃ of stirring in water bath, reaction 6min bleeds,
3) aerogenesis is collected: open and collect valve (6), close vent valve (5), add reagent 20mL20% sulfuric acid by addition funnel (2), bleed and collect 10min;
4) detect: get receiving flask (7) and add buffer solution and the reagent 0.2mL1% toluene-sodium-sulfonchloramide that reagent 5mL pH is 6.8, after placing 3min, add reagent 5mL isonicotinic acid-pyrazolone solution, reaction 30min, with 752 single beam ultraviolet-visible spectrophotometers in 638nm place colorimetric.
2. in tealeaves according to claim 1, contain the residual fast quantitative measurement method for detecting of cyanogen pyrethroid pesticide, it is characterized in that: described buffer solution, by 34g anhydrous potassium dihydrogenphosphate, 89.5g disodium hydrogen phosphate is dissolved in 1L distilled water.
3. in tealeaves according to claim 1, contain the residual fast quantitative measurement method for detecting of cyanogen pyrethroid pesticide, it is characterized in that: described isonicotinic acid-pyrazolone solution, be dissolved in 100mL0.5% sodium hydroxide solution by 1.5g isonicotinic acid, 0.25g pyrazolone is dissolved in 20mL N, N dimethyl formamide, mixes by 5:1.
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| CN106226292B (en) * | 2016-04-21 | 2018-07-03 | 中国科学院大连化学物理研究所 | A kind of fast inspection card of cyano-containing pyrethroid pesticide and preparation and application |
| CN105907577B (en) * | 2016-06-28 | 2023-03-07 | 盐城工学院 | Cordyceps sinensis wine leaching device |
| CN106198519B (en) * | 2016-07-05 | 2019-01-25 | 广州市食品检验所 | The ninhydrin colorimetry of cypermethrin content in a kind of quick detection vegetables or fruit |
| CN106442507A (en) * | 2016-11-03 | 2017-02-22 | 百奥森（江苏）食品安全科技有限公司 | Detection test paper for pyrethroid pesticide residues in foods |
Citations (3)
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| CN1763509A (en) * | 2004-10-18 | 2006-04-26 | 福建出入境检验检疫局检验检疫技术中心 | Quick detection method for pyrethroid pesticide residue |
| CN101334408A (en) * | 2008-07-22 | 2008-12-31 | 江南大学 | Enzyme linked immunological adsorption detection method for analyzing residuals of cyano pyrethroid pesticides |
| CN101865902A (en) * | 2009-04-17 | 2010-10-20 | 桑华春 | Fast test method of pyrethroid pesticide residue containing cyan |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1763509A (en) * | 2004-10-18 | 2006-04-26 | 福建出入境检验检疫局检验检疫技术中心 | Quick detection method for pyrethroid pesticide residue |
| CN101334408A (en) * | 2008-07-22 | 2008-12-31 | 江南大学 | Enzyme linked immunological adsorption detection method for analyzing residuals of cyano pyrethroid pesticides |
| CN101865902A (en) * | 2009-04-17 | 2010-10-20 | 桑华春 | Fast test method of pyrethroid pesticide residue containing cyan |
Non-Patent Citations (3)
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| 杨蕾等.SBSE-TDS-GC-MS快速测定茶叶中拟除虫菊酯类农药残留.《食品科学》.2007,第28卷(第11期), * |
| 林子俺等.超声波提取-高效液相色谱测定茶叶中拟除虫菊酯农药残留.《光谱实验室》.2007,第24卷(第04期), * |
| 马海乐等.采用MECC在线堆积同步检测茶叶中七种残留农药.《农业工程学报》.2008,第24卷(第08期), * |
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