CN102213700A - Method for measuring content of pyrethroid pesticides in mainstream smoke of cigarettes - Google Patents
Method for measuring content of pyrethroid pesticides in mainstream smoke of cigarettes Download PDFInfo
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Abstract
The invention relates to a method for measuring the content of pyrethroid pesticides in mainstream smoke of cigarettes and belongs to the technical field of tobacco chemical analysis. The method comprises the following steps of: extracting a sample by using acetone, purifying the sample by a self-prepared mixed chromatographic column, and detecting on a gas chromatograph; selecting an appropriate adsorbent according to the properties of complex matrixes of five pyrethroid pesticides and smoke, optimizing the using amount of the adsorbent, filling the five adsorbents or water absorbers into a glass chromatographic column from top to bottom, and activating by using 5 milliliters of acetone and 5 milliliters of normal hexane; and transferring sample test solution to be purified into the chromatographic column, eluting repeatedly twice by using 5 milliliters of mixed solvent of the acetone and the normal hexane in a volume ratio of 3:2 at the speed of less than or equal to 5.0 milliliters /minute, collecting eluent, concentrating to 0.5 milliliter on a rotary evaporator, fixing the volume to 2.0 milliliters by using the mixed solvent of the acetone and the normal hexane in a volume ratio of 3:2 to reach 2.0 milliliters, and analyzing on a gas chromatograph-electrochemical display (GC-ECD). The method has the advantages of simplicity, convenience, high efficiency and accuracy.
Description
Technical field:
The present invention relates to pyrethroid pesticide content detecting method in a kind of cigarette mainstream flue gas, belong to technical field of tobacco chemical analysis.
Background technology:
Pyrethroid pesticide is the splendid pesticide of a class effect, because of it has efficiently, low toxicity, knock down fast, residual characteristics such as few, is widely used in controls of insect such as tea place, orchard, rural power animal house.Theoretically, the use agricultural chemicals of having a boundless sense of responsibility and appointing, the strict agriculture working specification according to good is used agricultural chemicals, and the active component of agricultural chemicals and catabolite thereof still can have residual on tobacco, this residual reasonable levels of often thinking.But because China's agricultural production is peasant's formula mode of production, producer's quality is uneven, and some peasants are not according to the reasonable usage criteria applying pesticides of agricultural chemicals, and blindly applying pesticides, overdose and overclocking time applying pesticides causes serious tobacco residues of pesticides.At present, the problem of residues of pesticides has more and more caused the concern of tobacco circle and the whole society in the tobacco.And tobacco is as a kind of special consumer goods, prop up by cigarette and to enter human body after burning forms flue gas, therefore, residues of pesticides not only are somewhat dependent upon their actual contents in tobacco to the harm of human body in the tobacco, the more important thing is and depend on their transfer amount in flue gas.Burn and suck in the process at cigarette, chemical constitution in the tobacco has been passed through pyrolysis, synthetic, distillation, condensation and redistilled complicated physics and chemical reaction, a lot of new materials have been produced, simultaneously, also there are some chemical substances to comprise that residues of pesticides have transferred in the flue gas with certain rate of transform, directly influence smoker's health.Therefore, set up pyrethroid pesticide content detecting method in a kind of cigarette mainstream flue gas, the transfer amount and the rate of transform of pyrethroid pesticide in main flume in the research cigarette smoking process had significance.
At present, the research of pyrethroid pesticide mainly concentrates on the mensuration aspect of tobacco leaf, pipe tobacco and offal in the tobacco
[1-6], the analyzing and testing of pyrethroid pesticide is then less relatively in the cigarette mainstream flue gas
[7]Studies show that the chemical constitution in the tobacco has kind more than 4000, chemical constitution in the flue gas has kind more than 6000, that is to say, compare with the detection of pyrethroid pesticide in the tobacco, the analyzing and testing of pyrethroid pesticide is the process of separating trace components of extracting from more complicated matrix in the flue gas, as seen, the analytical approach of pyrethroid pesticide can not be applicable to pyrethroid pesticide Determination on content in the cigarette mainstream flue gas fully in the present existing tobacco.In addition, because the material of the cambridge filter of filter tip and capture mainstream smoke total particulate matter differs greatly, so the inventor in the patent of on July 26th, 2010 application " cigarette filter to flue gas in the detection method of pyrethroid pesticide residue amount " (application number: 201010236318, publication number: 101915813A) behind the cigarette smoking in the filter tip detection method of pyrethroid pesticide also can not satisfy the requirement that pyrethroid pesticide is measured in the flue gas fully.In order to investigate kinds of cigarettes pyrethroid pesticide transfer amount and rate of transform in main flume in combustion process, need set up pyrethroid pesticide content detecting method in a kind of easy cigarette mainstream flue gas accurately.
The analytical approach of pyrethroid pesticide mainly contains gas chromatography in the tobacco
[1,3,4,5](charged muon capture detecting device) method, high performance liquid chromatography-mass spectrometry method
[2]And GC-MS(gas chromatography-mass spectrography)
[6]Deng.Wherein, the application of gas chromatography (charged muon capture detecting device) method is comparatively extensive.Because the composition of flue gas is very complicated, interfering material is many when carrying out pesticide residue determination, therefore for the detection limit that reduces method with avoid matrix to bring interference, need carry out purified treatment to sample.Using at present is column chromatography with the most suitable sample purification technology at most, as: (1) purifies sample extracting solution with gel permeation chromatography and silica gel column chromatography
[4]Or sample solution purified with Aquapak A-440 post and florisil silica chromatographic column
[5]Though these two kinds of methods have stronger selectivity, sample needs through twice column chromatography, if the loss that complex operation is time-consuming, solvent consumption is many, the big misoperation of amount of samples causes object easily; (2) sample extracting solution is purified with the finished product solid-phase extraction column
[8], advantages such as that this method has is efficient, quick, easy, environmental protection, but the limitations restrict of finished product solid-phase extraction column selectivity and adsorption capacity its application during trace pyrethroid pesticide is measured in this complex matrices of flue gas; (3) sample extracting solution is used the magnesium silicate chromatographic column
[7]Or florisil silica chromatographic column
[9]Purify, this method only need purify through primary column chromatography, but because single its adsorptive power that makes of column packing is limited, thereby further influenced final purification separation effect.
About the existing report of the assay method of pyrethroid pesticide in the cigarette mainstream flue gas.But by literature search, find open report with content same document of the present invention.
List of references:
[1] Li Jinpei, 6 kinds of pyrethroid pesticide residual quantities in the wide bore capillary column gas Chromatographic Determination tobacco, " analytical chemistry ", calendar year 2001, the 7th phase, 793-795 page or leaf
[2] Mu Xiaoli, Jiang Lamei, Du Wen, pyrethroid pesticide is residual in the high performance liquid chromatography one series connection analytical reagent composition tobacco, " agricultural chemicals ", in May, 2009, the 48th the 5th phase of volume, 365-367 page or leaf
[3] Zou Ximei, Lin Zhuguang, Peng Shunv, Chen Zhaobin, 29 kinds of agricultural chemicals is residual in gas chromatography-electron impact ion source analytical reagent composition cigarette and the tobacco leaf, in March, 2009, the 27th the 2nd phase of volume, 169-175
[4] GB/T 13595-2004, the mensuration of tobacco and tobacco product pyrethroid insectide, organophosphorus insecticide, nitrogenous persticide residue
[5] Liu Yuehua, what is super, Huanghai Sea great waves, Yang Guangyu, the prune roc, it is residual that vapor-phase chromatography is surveyed in the tobacco pyrethroid and organic phosphates farming, " chemical research and application ", in April, 2009, the 21st the 4th phase of volume, 459-162
[6] Hou Ying, Cao Qiue, Xie Xiaoguang, Wang Baoxing, Xu Jicang, Yang Lei, Yang Yan, Yang Yong uses Stir Bar Sorptive Extraction one thermal desorption one gas chromatography and mass spectromentry and measures in tobacco leaf and the tealeaves pyrethroid pesticide remained, " chromatogram ", in January, 2007, the 25th the 1st phase of volume, 25-29
[7] Cai Jibao, Liu Baizhan, Zhu Xiaolan, Su Qingde, the mensuration of the pyrethrin pesticide residual quantity and the capture rate of transform thereof in the tobacco, " analytical test journal ", in March, 2002, the 21st the 2nd phase of volume, 29-31
[8] Mouding honor, Yang Mingquan, Dong Yong, Wang Baoxing, Yang Yan, Zou Yue, the mensuration of pyrethroid insecticides residual quantity in the tobacco, " tobacco science and technology ", 2008 the 8th phases, 38-40
[9] Lv Jing Li Wei lattice Zhang Qiao, the how residual gas chromatography analysis method of pyrethroid pesticide in tobacco, " Chinese tobacco science ",, the 2nd phase, 9～12 pages in 1992
Summary of the invention:
The object of the present invention is to provide a kind of operation steps simply, efficiently, pyrethroid pesticide Determination on content method in the cigarette mainstream flue gas accurately.
Pyrethroid pesticide Determination on content method in the cigarette mainstream flue gas of the present invention, the sample acetone extraction, after mixing the chromatography column purification, self-control on gas chromatography (the sub-acquisition detector of distribution) instrument, detects, this method is selected suitable adsorbent according to the character of 5 kinds of pyrethroid pesticides and the character of this complex matrices of flue gas, the use amount of adsorbent is optimized the back to be filled to adsorbent in the glass chromatography column according to certain order and (to load absorbent cotton from top to bottom successively, the 2g anhydrous sodium sulfate, 2g silicon magnesium type adsorbent, the 2g neutral alumina, 0.5g acticarbon, the 2g anhydrous sodium sulfate), the mixing of several adsorbents is used, make this self-control mixing chromatographic column have selectivity and the adsorptive power stronger preferably, reached isolation of purified effect preferably impurity.
Pyrethroid pesticide Determination on content method in the cigarette mainstream flue gas of the present invention, concrete steps are as follows:
A. with cigarette to be measured balance 48h under the atmospheric environment condition that the tobacco and the tobacco product of GB/T 16447-2004 regulation are regulated and tested, select the cigarette of the equal quality ± 0.102g of 20 set levels and average resistance to suction ± 49Pa;
B. on smoking machine, load onto cigarette to be measured and prop up, under standard smoking condition, aspirate; Capture mainstream smoke total particulate matter with cambridge filter, capture main flume gas phase part with the trapping bottle that 20m L acetone is housed;
C. after cigarette smoking finishes, take off and capture the cambridge filter that mainstream smoke total particulate matter is arranged, filter disc is put into 250mL triangle tool plug conical flask, add 80mL acetone, place on the ultrasonic Extraction instrument and extract 30min, extract through be equipped with 7.5g anhydrous sodium sulfate and 7.5g sodium chloride the funnel filtration drying after on Rotary Evaporators, be concentrated into 0.5mL, bath temperature requires less than 42 ℃, be settled to 2mL with normal hexane, to be clean;
D. the acetone soln that capture is had the main flume gas phase, through be equipped with 7.5g anhydrous sodium sulfate and 7.5g sodium chloride the funnel filtration drying after on Rotary Evaporators, be concentrated into 0.5mL, bath temperature requires to be settled to 2mL less than 42 ℃ with normal hexane, and is to be clean;
E. in glass chromatography column, load absorbent cotton, 2g anhydrous sodium sulfate, 2g silicon magnesium type adsorbent, 2g neutral alumina, 0.5g acticarbon, 2g anhydrous sodium sulfate from top to bottom successively;
F. the glass chromatography column that the e step is obtained is fixed on the iron stand, successively with 5mL acetone and 5mL normal hexane drip washing activation;
G. sample test solution to be clean is transferred in the chromatographic column, when the sample liquid level arrives the filling material upper surface, (V: V=3: 2) mixed solvent repeats twice of wash-out (speed is no more than 5.0mL/min) with 5mL acetone-normal hexane, collect eluent, on Rotary Evaporators, be concentrated into 0.5mL, (V: V=3: 2) mixed solvent is settled to 2.0mL, analyzes on GC-ECD with acetone-normal hexane.
The invention has the advantages that: assay method is easy, efficient, accurate, can effectively measure the content of pyrethroid pesticide in the cigarette mainstream flue gas, lay the first stone for investigating kinds of cigarettes pyrethroid pesticide transfer amount and rate of transform in main flume in combustion process, for the low exploitation that endangers cigarette product provides more scientific comprehensive analysis data and theoretical the support.
Embodiment:
Below the present invention is described in detail.
One, experimental section
1. instrument and reagent
Agilent 6890 gas chromatographs-electron capture (ECD) detecting device (U.S. An Jielun company), HP-5MS fused-silica capillary column (30m * 0.25 μ m * 0.32mm) (U.S. Angilent), standard 20 duct smoking machine (R20 types, Germany Borgwaldt technick company), climatic chamber (KBF240 type, Germany), SB2200T ultrasonic Extraction instrument (Shanghai must anticipate company limited), quartz glass chromatography post, M110 muffle furnace (German Heraeus company), electric drying oven with forced convection (101C-3, Shanghai City experimental apparatus Co., Ltd., Factory), (scale of tail pipe is respectively 1mL to the concentrated bottle of 100mL magnetic tape trailer pipe, 2mL, 3mL, 4mL, 5mL), 250mL triangle tool plug conical flask, graduated cylinder.
Ethyl acetate, cyclohexane, normal hexane, acetone, methyl alcohol, acetonitrile, benzene (chromatographically pure, U.S. DIMA company); Anhydrous sodium sulfate (analyze pure, west, Shantou City Gansu Province chemical industry company limited); Acticarbon (the new really Fine Chemical Co., Ltd in Shanghai produces); Absorbent cotton (first class, Shanghai Sheng Beinuo medical devices company limited sells); The glass chromatography column of band silica sand; Neutral alumina (1.5 * 10
5～2.5 * 10
5Nm chromatography Shanghai Du Yuan Fine Chemical Co., Ltd); Silicon magnesium type adsorbent (7.5 * 10
4～1.5 * 10
5Nm, Chemical Reagent Co., Ltd., Sinopharm Group produces).
The activation of neutral alumina: in muffle furnace under 450 ℃ of conditions calcination 4.5h, be cooled to room temperature, add percentage by weight and be 5% distilled water and take off work, concuss is until there not being bulk on oscillator, 130 ℃ of activation 4h in drying box, cooling back airtight preservation in exsiccator.
The activation of silicon magnesium type adsorbent: in muffle furnace under 650 ℃ of conditions calcination 5h, be cooled to room temperature, add percentage by weight and be 5% distilled water and take off work, concuss is until there not being bulk on oscillator, 130 ℃ of activation 5.5h in drying box, cooling is placed on airtight preservation in the exsiccator.
Standard items: cyfloxylate (purity 98%), cypermethrin (isomer mixture) (purity 99%), cis fenvalerate (purity 98%), decis (purity 99%), Fenpropathrin (purity 98%) (German Dr.Ehrenstorfer company).
2. the preparation of standard solution
The preparation of single standard storing solution: take by weighing every kind of standard items of 0.1g (being accurate to 1mg) respectively in the 100mL volumetric flask, (V: V=3: 2) dilution constant volume, obtain concentration is the single standard storing solution of 1mg/mL to the mixed solvent of usefulness acetone and normal hexane.
The preparation of hybrid standard storing solution: pipette 10mL single standard storing solution respectively to the 100mL volumetric flask, (V: V=3: 2) dilution constant volume, obtain concentration is the hybrid standard storing solution of 100 μ g/mL to the mixed solvent of usefulness acetone and normal hexane.
The preparation of working solution: pipette 0.04mL, 0.2mL, 1mL, 5mL, 20mL mixing storing solution respectively to the 100mL volumetric flask, (V: V=3: 2) dilution constant volume, obtaining concentration is the working solution of 0.04 μ g/mL, 0.2 μ g/mL, 1 μ g/mL, 5 μ g/mL, 20 μ g/mL with the mixed solvent of acetone and normal hexane.
3. experimental procedure
With cigarette to be measured balance 48h under the atmospheric environment condition that the tobacco and the tobacco product of GB/T 16447-2004 regulation are regulated and tested, select the cigarette of the equal quality ± 0.102g of 20 set levels and average resistance to suction ± 49Pa.On smoking machine, load onto cigarette to be measured and prop up, under standard smoking condition, aspirate; Capture mainstream smoke total particulate matter with cambridge filter, capture main flume gas phase part with the trapping bottle that 20m L acetone is housed.
After cigarette smoking finishes, take off and capture the cambridge filter that mainstream smoke total particulate matter is arranged, filter disc is put into 250mL triangle tool plug conical flask, add 80mL acetone, place on the ultrasonic Extraction instrument and extract 30min, extract through be equipped with 7.5g anhydrous sodium sulfate and 7.5g sodium chloride the funnel filtration drying after on Rotary Evaporators, be concentrated into 0.5mL (bath temperature requires less than 42 ℃), be settled to 2mL with normal hexane, to be clean; Simultaneously, the acetone soln that capture is had a main flume gas phase through be equipped with 7.5g anhydrous sodium sulfate and 7.5g sodium chloride the funnel filtration drying after on Rotary Evaporators, be concentrated into 0.5mL (bath temperature requires less than 42 ℃), be settled to 2mL with normal hexane, to be clean; In glass chromatography column, load absorbent cotton, 2g anhydrous sodium sulfate, 2g silicon magnesium type adsorbent, 2g neutral alumina, 0.5g acticarbon, 2g anhydrous sodium sulfate from top to bottom successively; This glass chromatography column that fills is fixed on the iron stand, successively with 5mL acetone and 5mL normal hexane drip washing activation; Then sample test solution to be clean is transferred in the chromatographic column, when the sample liquid level arrives the filling material upper surface, (V: V=3: 2) mixed solvent repeats twice of wash-out (speed is no more than 5.0mL/min) with 5mL acetone-normal hexane, collect eluent, be concentrated into 0.5mL on Rotary Evaporators, (V: V=3: 2) mixed solvent is settled to 2.0mL, analyzes on GC-ECD (63Ni) with acetone-normal hexane, adopt the standard specimen addition method qualitative, external standard method is quantitative.
GC conditions is: chromatographic column: the Agilent HP-5 (fused-silica capillary column of 30m * 0.25 μ m * 0.32mm); Carrier gas: nitrogen (20ml/min); 260 ℃ of injector temperatures are not shunted; Sample size 1 μ L; Post flow 2.0ml/min; 280 ℃ of detecting device (ECD) temperature;
Post heating schedule: 70 ℃ of initial temperatures (keeping 2.0min)
10 ℃/min Rise to 200 ℃ (keeping 2.0min)
2.5 ℃/min Rise to 220 ℃ (keeping 3min)
5 ℃/min Rise to 260 ℃ (keeping 2min), move 1min at last, move 53min altogether.
Two, result and discussion
1. condition optimizing
1.1 extraction choice of Solvent
This method has been studied different solvents, and (acetone, acetonitrile, benzene, methyl alcohol, ethyl acetate-normal hexane mixed solvent (V: V=1: 1)) are to the extraction effect (recovery that different solvents extracts test sees Table 1) of pyrethroid pesticide in the main flume, found that: (V: V=1: 1) three kinds of solvents are to the extraction effect of pyrethroid pesticide in the main flume better (recovery＞90%), wherein acetone extraction effect best (recovery＞97%) for acetone, acetonitrile and ethyl acetate-normal hexane mixed solvent; Relatively poor (recovery＜70% is so this method is selected 5 kinds of pyrethroid pesticides on the acetone extraction filter tip for use and benzene and methyl alcohol are to the extraction effect of pyrethroid pesticide in the main flume.
Table 1 different solvents extracts the recovery and the relative standard deviation of test
1.2 the selection of decontaminating column
Cigarette smoke components after aspirating is very complicated, and when carrying out the mensuration of pyrethroid pesticide, interfering material is many, for the sensitivity that improves sample detection, reduce the interference of matrix to object, need carry out purified treatment to sample.As everyone knows, column chromatography is the common technology of sample purification, and in the column chromatography test use amount of the kind of adsorbent and adsorbent to the equal important influence of purification separation effect of object, so should be at different matrix and suitable adsorbent and the use amount thereof of object selection.The present invention selects for use chromatographic column that four kinds of listing in the table 2 are filled with different use amount adsorbents that the clean-up effect of 5 kinds of pyrethroid pesticides in the cigarette mainstream flue gas has been carried out studying (recovery of different chromatography column purifications tests sees Table 2) according to the 5 kinds of pyrethroid pesticides and the character of flue gas matrix.Result of study shows: use chromatographic column 1 (use amount that is acticarbon and silicon magnesium type adsorbent is all greatly the time), chromatographic column is all stronger to the adsorptive power of impurity and object, solvent is difficult to object is eluted from chromatographic column, the peak of 5 kinds of pyrethroid pesticides is all less in the chromatogram, the recovery of test lower (recovery of 5 kinds of pyrethroid pesticides is 43.6%～50.9%); Decline along with activated charcoal and silicon magnesium type adsorbent use amount, the peak area of 5 kinds of pyrethroid pesticides increases gradually in the chromatogram, the recovery of test also increases gradually, when using chromatographic column 4 and chromatographic column 5 to purify, it is maximum that the peak area of 5 kinds of pyrethroid pesticides reaches, but when using chromatographic column 5, because the use amount of acticarbon and silicon magnesium type adsorbent is all less, adsorptive power to impurity is relatively poor, more impurity peaks has appearred in the chromatogram, influenced the mensuration of object, the recovery of test is lower than the recovery when using chromatographic column 4, so this method selects for use 4 pairs of samples of chromatographic column to purify.
Two kinds of chromatographic column filling materials of table 2.1 consumption
1.3 eluting solvent proportioning
In modern stratographic analysis, degree of separation is not only imitated relevant with the type of chromatographic column with post, and the selection of eluting solvent also is vital, the proportioning of eluting solvent particularly, and eluting solvent proportioning difference, the separating effect of object is difference just.So according to the character of the selected chromatographic column of the character of 5 kinds of pyrethroid pesticides and this method, the mixed solvent that this method is chosen acetone and normal hexane mixes chromatographic column and carries out wash-out making by oneself.Acetone and normal hexane have been contrasted at different proportionings (V: V=2: 8, V: V=3: in the time of 2) to the elute effect of decontaminating column.The result shows: work as V
Acetone: V
Normal hexane=2: 8 o'clock, acetone ratio was little, and impurity and object all are not easy to mix the chromatographic column wash-out from self-control, and consuming time, solvent-oil ratio is big, also influences measurement result, the recovery low (less than 60%).Work as V
Interior ketone: V
Normal hexane=3: 2 o'clock, acetone ratio was big relatively, and object is easily by wash-out, and the recovery is higher than 90%.So it is that 3: 2 mixed solvent carries out wash-out to the selected chromatographic column of this method that acetone and normal hexane proportioning are selected in this experiment for use.
2. the repeatability of method
Selected two cigarette samples, burn and suck in back one day the content 5 times of pyrethroid pesticide in the replicate determination cigarette mainstream smoke total particulate matter, calculate in the mainstream smoke total particulate matter 5 kinds of pyrethroid pesticides relative standard deviation of measurement result (seeing Table 2) in a few days according to conventional method; Measured the content of pyrethroid pesticide in two cigarette mainstream smoke total particulate matters in continuous 5 days, calculate in the mainstream smoke total particulate matter 5 kinds of pyrethroid pesticides relative standard deviation of measurement result (seeing Table 2) in the daytime according to conventional method.Owing to all do not detect the existence of 5 kinds of pyrethroid pesticides in all samples suction back main flume gas phase of the present invention's research, in order further to study 5 kinds of repeatability that pyrethroid pesticide detects in the main flume gas phase, capture the standard specimen that adds 5 kinds of pyrethroid pesticides in the acetone trapping solution that the main flume gas phase is arranged (addition: 5 μ g/20mL acetone trapping solutions), measure and calculate in the main flume gas phase 5 kinds of pyrethroid pesticides relative standard deviation of measurement result (seeing Table 2) in a few days and in the daytime then in suction back.
In the table 2 day and in the daytime the relative standard deviation of repeated experiment measurement result (RSD%)
Find out by the data in the table, in a few days the relative standard deviation of 5 kinds of pyrethroid pesticide measurement results is all less than 6% in two cigarette sample mainstream smoke total particulate matters in the repeated experiment, and the relative standard deviation of 5 kinds of pyrethroid pesticide measurement results is all less than 4.2% in the main flume gas phase; In the daytime the relative standard deviation of 5 kinds of pyrethroid pesticide measurement results is all less than 9.1% in two cigarette sample mainstream smoke total particulate matters in the repeated experiment, and the relative standard deviation of 5 kinds of pyrethroid pesticide measurement results is all less than 4.7% in the main flume gas phase; The repeated fine of this assay method is described.
3. the accuracy of method
Capture the cambridge filter that mainstream smoke total particulate matter is arranged in the suction back and capture the standard specimen (addition: 20 μ g/ filter discs or 20 μ g/20mL acetone trapping solutions) that adds 5 kinds of pyrethroid pesticides in the acetone soln that main flume gas phase part is arranged, with the recovery that calculates 5 kinds of pyrethroid pesticides of mensuration behind the blank sample check analysis according to conventional method, recovery experimental result sees Table 3.
Table 3 recovery experimental result
Find out that by the data in the table recovery of 5 kinds of pyrethroid pesticides illustrates that all greater than 92% the accuracy of this assay method is fine in mainstream smoke total particulate matter and the gas phase.
4. sample analysis result
Measure the content (annotate: cyfloxylate and cypermethrin carry out quantitatively with four chromatographic peak peak area sums of four isomeride) that 5 kinds of cigarette samples aspirate 5 kinds of pyrethroid pesticides in back mainstream smoke total particulate matters and the gas phase with this method, the results are shown in Table 4.
In table 45 kind of cigarette sample suction back mainstream smoke total particulate matter and the gas phase
The assay result (ug/20 props up) of pyrethroid pesticide
Annotate: in the table/represent not detect.Experiment cigarette 1 and experiment cigarette 2 spray four kinds of pyrethroid pesticides for gradation is excessive consciously in tobacco leaf plantation process according to the experimental study needs, and the cigarette sample that contains different persticide residues that obtains routinely after tobacco leaf picking rolled, only use for experimental study.
Claims (1)
1. pyrethroid pesticide Determination on content method in the cigarette mainstream flue gas is characterized in that the concrete steps of this assay method are as follows:
A. with cigarette to be measured balance 48h under the atmospheric environment condition that the tobacco and the tobacco product of GB/T 16447-2004 regulation are regulated and tested, select the cigarette of the equal quality ± 0.102g of 20 set levels and average resistance to suction ± 49Pa;
B. on smoking machine, load onto cigarette to be measured and prop up, under standard smoking condition, aspirate; Capture mainstream smoke total particulate matter with cambridge filter, capture main flume gas phase part with the trapping bottle that 20m L acetone is housed;
C. after cigarette smoking finishes, take off and capture the cambridge filter that mainstream smoke total particulate matter is arranged, filter disc is put into 250mL triangle tool plug conical flask, add 80mL acetone, place on the ultrasonic Extraction instrument and extract 30min, extract through be equipped with 7.5g anhydrous sodium sulfate and 7.5g sodium chloride the funnel filtration drying after on Rotary Evaporators, be concentrated into 0.5mL, bath temperature requires less than 42 ℃, be settled to 2mL with normal hexane, to be clean;
D. the acetone soln that capture is had the main flume gas phase, through be equipped with 7.5g anhydrous sodium sulfate and 7.5g sodium chloride the funnel filtration drying after on Rotary Evaporators, be concentrated into 0.5mL, bath temperature requires to be settled to 2mL less than 42 ℃ with normal hexane, and is to be clean;
E. in glass chromatography column, load absorbent cotton, 2g anhydrous sodium sulfate, 2g silicon magnesium type adsorbent, 2g neutral alumina, 0.5g acticarbon, 2g anhydrous sodium sulfate from top to bottom successively;
F. the glass chromatography column that the e step is obtained is fixed on the iron stand, successively with 5mL acetone and 5mL normal hexane drip washing activation;
G. sample test solution to be clean is transferred in the chromatographic column, when the sample liquid level arrives the filling material upper surface, with the 5mL volume ratio is that 3: 2 acetone-normal hexane mixed solvent repeats twice of wash-out, elution rate is no more than 5.0mL/min, collect eluent, being concentrated into 0.5mL on Rotary Evaporators, is that acetone-normal hexane mixed solvent of 3: 2 is settled to 2.0mL, analyzes on GC-ECD with volume ratio.
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| CN107490651A (en) * | 2017-10-16 | 2017-12-19 | 花锦 | Pyrethroid pesticide remained detection method in a kind of asparagus and its product |
| CN110927368A (en) * | 2019-11-28 | 2020-03-27 | 中国农业大学 | Method for detecting residual pesticide in closed environment of agricultural product logistics |
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| CN102698469A (en) * | 2012-06-19 | 2012-10-03 | 苏州国环环境检测有限公司 | Purifying column |
| CN103293267A (en) * | 2013-06-08 | 2013-09-11 | 国家烟草质量监督检验中心 | GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing pyrethroid pesticide residue in tobacco and tobacco product |
| CN105891361B (en) * | 2016-04-06 | 2018-08-24 | 浙江中烟工业有限责任公司 | Pyrethroid pesticide remained GC-MS/MS analysis methods in cigarette mainstream smoke condensate |
| CN105891361A (en) * | 2016-04-06 | 2016-08-24 | 浙江中烟工业有限责任公司 | GC-MS/MS analysis method for pyrethroid pesticide residues in cigarette main stream smoke particulate matter |
| CN105911156A (en) * | 2016-04-06 | 2016-08-31 | 浙江中烟工业有限责任公司 | GC-MS/MS analytical method for organo-chlorine pesticide residuals in particulate matters of main stream smoke of cigarette |
| CN105891362B (en) * | 2016-04-06 | 2018-08-24 | 浙江中烟工业有限责任公司 | The remaining GC-MS/MS analysis methods of Multiple Pesticides in a kind of cigarette mainstream smoke condensate |
| CN105911156B (en) * | 2016-04-06 | 2018-08-24 | 浙江中烟工业有限责任公司 | The GC-MS/MS analysis methods of Organochlorine Pesticide Residues in a kind of cigarette mainstream smoke condensate |
| CN105891362A (en) * | 2016-04-06 | 2016-08-24 | 浙江中烟工业有限责任公司 | GC-MS/MS method for analyzing multiple types of pesticide residues in cigarette main stream smoke grain phase substances |
| CN107389808A (en) * | 2017-06-28 | 2017-11-24 | 防城港市质量技术监督局 | The detection method of vegetable pesticide residue |
| CN107490651A (en) * | 2017-10-16 | 2017-12-19 | 花锦 | Pyrethroid pesticide remained detection method in a kind of asparagus and its product |
| CN110927368A (en) * | 2019-11-28 | 2020-03-27 | 中国农业大学 | Method for detecting residual pesticide in closed environment of agricultural product logistics |
| CN110927368B (en) * | 2019-11-28 | 2020-11-17 | 中国农业大学 | Method for detecting residual pesticide in closed environment of agricultural product logistics |
| CN111289677A (en) * | 2020-03-31 | 2020-06-16 | 中国烟草总公司郑州烟草研究院 | Method for measuring spicy components in main stream smoke of cigarette |
| CN111289677B (en) * | 2020-03-31 | 2023-04-14 | 中国烟草总公司郑州烟草研究院 | Method for measuring spicy components in main stream smoke of cigarette |
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