CN103115977A - Method for rapidly detecting phosphorus hydride residue in tobaccos and tobacco products - Google Patents
Method for rapidly detecting phosphorus hydride residue in tobaccos and tobacco products Download PDFInfo
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Abstract
The invention provides a method for rapidly detecting phosphorus hydride residue in tobaccos and tobacco products. According to the method, in a sealed container and at a certain temperature, when the phosphorus hydride in a sample achieves a balance between gas phase and substrate, the gas phase part is introduced into a gas chromatography/mass spectrometer to separate and identify so as to detect the content of phosphorus hydride in the sample. By adopting the headspace sampling manner, the method not only facilitates the feeding but also can reduce the damage to the experimenter caused by phosphorus hydride; by adopting the gas chromatography-mass spectrometry, the requirements on the normal temperature of a feed port and the temperature of a column box are approached, and thus both the repeatability and the accuracy of the phosphorus detection are greater than that of the gas chromatography. The method is used for the detection of phosphorus hydride residue in tobaccos and tobacco products, is convenient, accurate and fast for operation, and has relatively high practical value.
Description
Technical field
The present invention relates to a kind of residual method of hydrogen phosphide in Fast Measurement tobacco and tobacco product.
Background technology
Along with the signature of " Framework Convention on Tobacco Control " with come into force, the pressure of " smoking is with healthy " that tobacco business faces is further strengthened, the 9th " control of tobacco product composition " in pact impels signtory power to make the control regime of tobacco product security aspect with the tenth " regulation that tobacco product discloses ", and more strictly limits the burst size of harmful ingredients in flue gas.As one of contracting party, China recent years has also progressively been strengthened scientific research and the technological development of tobacco monopoly commodities, and has formulated the detection method of some chemical properties and the requirement of limiting the quantity of.
Hydrogen phosphide (PH
3) be used for the control tobacco-plant pest-insect history of existing nearly 50 years as a kind of fumigant, domestic and international utilization at present is by aluminum phosphate (AIP) at most, the most widely thereby the rear hydrolysis generation of suction hydrogen phosphide is killed the insect in tobacco, and the method insecticidal effect is good.Because hydrogen phosphide is that extremely toxic substance is arranged, easily remain in closely knit tobacco in stifling process.The people contacts hydrogen phosphide and easily causes serium inorganic phosphorus to increase, and affects the eubolism of body, may cause neurasthenia syndrome and respiratory tract and alimentary canal to stimulate disease etc.
The existing the whole bag of tricks of measuring hydrogen phosphide respectively has relative merits, and detector tube method, Test paper method, electrochemical sensing method, ammonium molybdate method and chromatography were all once appeared in the newspapers and be used for measuring the phosphine gas that warehouse fumigant desinsection produces.Compare with electrochemical sensing method, ammonium molybdate method and chromatography, detector tube method and the operation of Test paper method are comparatively easy, but degree of accuracy and less stable, only can be as analyzing qualitatively.In the air of overhead, gas chromatography determination lake, trace hydrogen phosphide precision is good, also has the vapor-phase chromatography of reporting to can be used for measuring in red phosphorus storage process through moisture and the hydrogen phosphide that produces.Although the chromatography upper limit of detection is lower, operate more complicatedly, testing result is comparatively accurately, stability is strong, the phosphine gas in can the quantitative test environment.
Along with the concern of people to tobacco consumption safety, in tobacco and tobacco sample, the accurate detection of residual Phosphine content is the needs that improve the residual System Construction of tobacco agriculture, also will become the important step of evaluating cigarette quality safety.Yet relevant document is less, therefore in the urgent need to studying and set up relevant detection method, to realize the quantitative test to the residual hydrogen phosphide in tobacco and tobacco sample, for the safety cigarette evaluation provides scientific basis.
Summary of the invention
Problem for prior art exists the invention provides a kind of residual method of hydrogen phosphide in Fast Measurement tobacco and tobacco product.This assay method is easy and simple to handle, accurate, quick, and selectivity is good, has stronger practical value.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of residual method of hydrogen phosphide in Fast Measurement tobacco and tobacco product is characterized in that: the object that the method detects is that in tobacco and tobacco product, hydrogen phosphide is residual; At first take appropriate sample in the head space bottle, so headspace sampling, vapor-phase chromatography is separated, and mass detector detects, and qualitative with retention time, external standard method is quantitative.
Further, concrete steps are as follows:
1) sample pre-treatments: take tobacco or the tobacco product sample of 0.5g～1g, be placed in the head space bottle of 10mL or 20mL, sealing is placed in the head-space sampler sample introduction;
2) head-space sampler condition: 35 ℃～40 ℃ of furnace temperature; 35 ℃～40 ℃ of sampling probe temperature; 35 ℃～40 ℃ of transmission line temperature; Sample bottle heating duration of oscillation 10～12.5min; Sample bottle 2.0min pressing time; Sample injection time 0.1～0.25min; Pull out pin time 0.5min; Then entering gas chromatography separates;
3) gas chromatography separation condition: employing chromatographic column Elite-624 capillary column (60 m * 320um * 1.8um); 35 ℃～40 ℃ of injector temperatures; Column oven heating schedule: first keep 3min under the initial temperature of 40 ℃, then be warming up to 180 ℃ by 40 ℃/min and keep 0.5min; Carrier gas: helium, purity 99.999%; Carrier gas flux 2mL/min; Split ratio 2:1～5:1; Shunting gas enters Mass Spectrometer Method.
Further, the Mass Spectrometer Method condition: 230 ℃ of transmission line temperature, 210 ℃ of ion source temperatures, detector voltage 380V, detecting pattern SIR, detecting the fragment karyoplasmic ratio is 31,32,33,34, quantitatively the fragment karyoplasmic ratio is 34 or 33.
Further, the tail gas that gives off after split ratio 2:1～5:1 shunting adopts potassium permanganate to absorb.
Further, the treatment step of described tail gas is: tail gas enters in the wash bottle that liquor potassic permanganate is housed after cushioning empty bottle through first, through the second buffering empty bottle, enters the wash bottle that ultrapure water is housed afterwards.
After adopting technique scheme, usefulness of the present invention is:
Compare with existing method, the method adopts the mode of headspace sampling not only to facilitate sample introduction but also can reduce hydrogen phosphide to experimenter's harm; Adopt the gas chromatography mass spectrometry method to measure, near injection port and the post case temperature requirement of room temperature, the reappearance and the accuracy that make phosphorus measure all are better than vapor-phase chromatography.The method is used for the mensuration of tobacco and tobacco sample hydrogen phosphide, and easy and simple to handle, accurate, quick, selectivity is good, has stronger practical value.
Description of drawings
Figure l is the processing procedure schematic diagram of shunting tail gas in the present invention;
Fig. 2 is hydrogen phosphide SRI figure (retention time is peak, 3.26min place, is followed successively by from top to bottom the leading ion fragment 31,32,33,34 of hydrogen phosphide) in sample in the present invention;
Fig. 3 is that (because the head space equilibrium temperature is not high, the volatile component of offal sample is less, and the relative molecular mass of hydrogen phosphide is less for typical sample chromatographic fractionation figure in the present invention, go out the peak very fast, peak shape is fine, and retention time is the 3.26min left and right, and other Interference Peaks is not arranged.）；
Fig. 4 is PH in the present invention
3Series standard gas linear graph;
Embodiment
A kind of residual method of hydrogen phosphide in Fast Measurement tobacco and tobacco product has comprised that headspace sampling, chromatographic resolution detect.Take appropriate sample in the head space bottle, headspace sampling, vapor-phase chromatography is separated, and mass detector detects.Qualitative with retention time, external standard method is quantitative.
The preferred embodiment of the present invention is as follows:
Embodiment 1:
Sample pre-treatments: take 0.5g tobacco or tobacco product sample, be placed in the head space bottle of 20mL, sealing is placed in the head-space sampler sample introduction.
Head-space sampler condition: 35 ℃ of furnace temperature; 35 ℃ of sampling probe temperature; 35 ℃ of transmission line temperature; Sample bottle heating duration of oscillation 10min; Sample bottle 2.0min pressing time; Sample injection time 0.1min; Pull out pin time 0.5min; Then entering gas chromatography separates.
Chromatographic separation condition: chromatographic column: the Elite-624 capillary column (60 m * 320um * 1.8um); 35 ℃ of injector temperatures; Column oven heating schedule: first keep 3min under the initial temperature of 40 ℃, then be warming up to 180 ℃ by 40 ℃/min and keep 0.5min; Carrier gas: helium, purity 99.999%; Carrier gas flux 2mL/min; Split ratio 2:1; Shunting gas enters Mass Spectrometer Method.The tail gas that gives off after split ratio 2:1 shunting adopts potassium permanganate to absorb.As shown in Figure 1, the treatment step of described tail gas is: tail gas is through take first this bottle of buffering empty bottle 1(as empty bottle) after enter in the first wash bottle 2 that acid permanganate soln is housed.In the first wash bottle 2, hydrogen phosphide is phosphoric acid by the potassium permanganate of strong oxidizing property.Afterwards, be empty bottle through first this bottle of buffering empty bottle 3(), enter the second wash bottle 4 that ultrapure water is housed, will remove through the hydrogen chloride gas that may take out of in the tail gas of the first wash bottle 2, prevent secondary pollution.
The Mass Spectrometer Method condition: 230 ℃ of transmission line temperature, 210 ℃ of ion source temperatures, detector voltage 380V, detecting pattern SIR, detecting the fragment karyoplasmic ratio is 31,32,33,34, its SIR schemes as shown in Figure 2, quantitatively fragment karyoplasmic ratio 34.
The sample chromatogram separation graph as shown in Figure 3, because the head space equilibrium temperature is not high, the volatile component of offal sample is less, and the relative molecular mass of hydrogen phosphide is less, goes out the peak very fast, peak shape is fine, retention time is the 3.26min left and right, and other Interference Peaks is not arranged.
Embodiment 2:
Adopt the method that 15 sheet cigarette samples are detected
Take approximately 0.8g sheet cigarette sample, be placed in the head space bottle of 20mL, sealing is placed in the head-space sampler sample introduction.
Head-space sampler condition: 40 ℃ of furnace temperature; 40 ℃ of sampling probe temperature; 40 ℃ of transmission line temperature; Sample bottle heating duration of oscillation 12.5min; Sample bottle 2.0min pressing time; Sample injection time 0.2min; Pull out pin time 0.5min; Then entering gas chromatography separates.
Chromatographic separation condition: chromatographic column: the Elite-624 capillary column (60 m * 320um * 1.8um); 35 ℃ of injector temperatures; Column oven heating schedule: first keep 3min under the initial temperature of 40 ℃, then be warming up to 180 ℃ by 40 ℃/min and keep 0.5min; Carrier gas: helium, purity 99.999%; Carrier gas flux 2mL/min; Split ratio 3:1; Shunting gas enters Mass Spectrometer Method.The tail gas that gives off after split ratio 3:1 shunting adopts potassium permanganate to absorb.The treatment step of described tail gas see Fig. 1 and embodiment one described.
The Mass Spectrometer Method condition: 230 ℃ of transmission line temperature, 210 ℃ of ion source temperatures, detector voltage 380V, detecting pattern SIR, detecting the fragment karyoplasmic ratio is 31,32,33,34, quantitatively the fragment karyoplasmic ratio is 34.
Typical curve: accurately take phosphatization aluminium flake 1.0000 g, be placed in the airtight triangular flask of 1000 mL, add water 10.0 mL, shake triangular flask and make its react completely (more than 6h), draw the air-tight bottle of top tank air 1.0mL injection 20 mL in triangular flask, as PH
3Standard is stocked gas, and demarcates with the ammonium molybdate colourimetry.Difference sample introduction 2.5,5.0,10.0,25.0,50.0ug/L PH
3Calibrating gas is measured, result as shown in Figure 4, PH
3Chromatographic peak area and PH
3Concentration presents linear relationship preferably, and the range of linearity is 2.5～50.0ug/L.
Sheet cigarette sample detection result is as shown in table 1, and sample segment detects, and content is between 0.0123～0.0521 ug/g.
Table 1 a cigarette sample detection result
Embodiment 3:
Adopt the method that 15 cigarette samples are detected
Take 1.0 cigarette samples, be placed in the head space bottle of 20mL, sealing is placed in the head-space sampler sample introduction.
Head-space sampler condition: 38 ℃ of furnace temperature; 38 ℃ of sampling probe temperature; 38 ℃ of transmission line temperature; Sample bottle heating duration of oscillation 12.0min; Sample bottle 2.0min pressing time; Sample injection time 0.25min; Pull out pin time 0.5min; Then entering gas chromatography separates.
Chromatographic separation condition: chromatographic column: the Elite-624 capillary column (60 m * 320um * 1.8um); 40 ℃ of injector temperatures; Column oven heating schedule: first keep 3min under the initial temperature of 40 ℃, then be warming up to 180 ℃ by 40 ℃/min and keep 0.5min; Carrier gas: helium, purity 99.999%; Carrier gas flux 2mL/min; Split ratio 2:1; Shunting gas enters Mass Spectrometer Method.The tail gas that gives off after split ratio 2:1 shunting adopts potassium permanganate to absorb.The treatment step of described tail gas see Fig. 1 and embodiment one described.
The Mass Spectrometer Method condition: 230 ℃ of transmission line temperature, 210 ℃ of ion source temperatures, detector voltage 380V, detecting pattern SIR, detecting the fragment karyoplasmic ratio is 31,32,33,34, quantitatively the fragment karyoplasmic ratio is 34.
Typical curve: accurately take phosphatization aluminium flake 1.0000 g, be placed in the airtight triangular flask of 1000 mL, add water 10.0 mL, shake triangular flask and make its react completely (more than 6h), draw the air-tight bottle of top tank air 1.0mL injection 20 mL in triangular flask, as PH
3Standard is stocked gas, and demarcates with the ammonium molybdate colourimetry.Difference sample introduction 2.5,5.0,10.0,25.0,50.0ug/L PH
3Calibrating gas is measured, result as shown in Figure 4, PH
3Chromatographic peak area and PH
3Concentration presents linear relationship preferably, and the range of linearity is 2.5～50.0ug/L.
It is as shown in table 2 that the cigarette product detect result, detects in sample segment, and content is between 0.0028～0.0089 ug/g.
Table 2 cigarette sample testing result
Claims (5)
1. the residual method of hydrogen phosphide in a Fast Measurement tobacco and tobacco product, it is characterized in that: the object that the method detects is that in tobacco and tobacco product, hydrogen phosphide is residual; At first take appropriate sample in the head space bottle, so headspace sampling, vapor-phase chromatography is separated, and mass detector detects, and qualitative with retention time, external standard method is quantitative.
2. according to the residual method of hydrogen phosphide in a kind of Fast Measurement tobacco claimed in claim 1 and tobacco product, it is characterized in that: concrete steps are as follows:
1) sample pre-treatments: take tobacco or the tobacco product sample of 0.5g～1g, be placed in the head space bottle of 10mL or 20mL, sealing is placed in the head-space sampler sample introduction;
2) head-space sampler condition: 35 ℃～40 ℃ of furnace temperature; 35 ℃～40 ℃ of sampling probe temperature; 35 ℃～40 ℃ of transmission line temperature; Sample bottle heating duration of oscillation 10～12.5min; Sample bottle 2.0min pressing time; Sample injection time 0.1～0.25min; Pull out pin time 0.5min; Then entering gas chromatography separates;
3) gas chromatography separation condition: employing chromatographic column Elite-624 capillary column (60 m * 320um * 1.8um); 35 ℃～40 ℃ of injector temperatures; Column oven heating schedule: first keep 3min under the initial temperature of 40 ℃, then be warming up to 180 ℃ by 40 ℃/min and keep 0.5min; Carrier gas: helium, purity 99.999%; Carrier gas flux 2mL/min; Split ratio 2:1～5:1; Shunting gas enters Mass Spectrometer Method.
3. in accordance with the method for claim 2, in it is characterized in that: the Mass Spectrometer Method condition: 230 ℃ of transmission line temperature, 210 ℃ of ion source temperatures, detector voltage 380V, detecting pattern SIR, detecting the fragment karyoplasmic ratio is 31,32,33,34, quantitatively the fragment karyoplasmic ratio is 34 or 33.
4. as the residual method of hydrogen phosphide in claim 2,3 described a kind of Fast Measurement tobaccos and tobacco product, it is characterized in that: the tail gas that gives off after split ratio 2:1～5:1 shunting adopts potassium permanganate to absorb.
5. the residual method of hydrogen phosphide in a kind of Fast Measurement tobacco as claimed in claim 4 and tobacco product, it is characterized in that: the treatment step of described tail gas is: tail gas enters in the wash bottle that liquor potassic permanganate is housed after cushioning empty bottle through first, through the second buffering empty bottle, enter the wash bottle that ultrapure water is housed afterwards.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103728406A (en) * | 2014-01-03 | 2014-04-16 | 浙江中烟工业有限责任公司 | Method for measuring residual phosphine in tobacco and tobacco products based on pulse flame photometric detector |
| CN105758813A (en) * | 2016-04-22 | 2016-07-13 | 广西中烟工业有限责任公司 | Method for determining phosphate in cigarette paper |
| CN106370762A (en) * | 2016-11-18 | 2017-02-01 | 司法部司法鉴定科学技术研究所 | Test method of phosphine |
| CN111808739A (en) * | 2020-04-12 | 2020-10-23 | 中国科学院武汉植物园 | Anaerobic bottle quantitative isobaric oxygen removal device and method for biological culture |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103728406A (en) * | 2014-01-03 | 2014-04-16 | 浙江中烟工业有限责任公司 | Method for measuring residual phosphine in tobacco and tobacco products based on pulse flame photometric detector |
| CN105758813A (en) * | 2016-04-22 | 2016-07-13 | 广西中烟工业有限责任公司 | Method for determining phosphate in cigarette paper |
| CN106370762A (en) * | 2016-11-18 | 2017-02-01 | 司法部司法鉴定科学技术研究所 | Test method of phosphine |
| CN111808739A (en) * | 2020-04-12 | 2020-10-23 | 中国科学院武汉植物园 | Anaerobic bottle quantitative isobaric oxygen removal device and method for biological culture |
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