CN104764839A - Method for determining a variety of pesticide residues in health products by using gas chromatograph-mass spectrometer - Google Patents

Abstract

The present invention discloses a method for determining a variety of pesticide residues in health products by using a gas chromatograph-mass spectrometer. The method comprises: (1) weighing 10 g of a sample to be detected, and extracting with acetonitrile to obtain an extraction solution; (2) loading the extraction solution onto an Envi-18 column, washing with acetonitrile, collecting, and concentrating for spare; and (3) adding anhydrous sodium sulfate to an Envi-Carb column, connecting the lower part of the column and the top part of a Sep-Pak NH2 column to obtain a serially connected column, washing the serially connected column with an acetonitrile-toluene mixed solution, loading the concentrated solution obtained in the step (2) onto the serially connected column, washing the concentration bottle with the acetonitrile-toluene mixed solution, transferring the washing solution into the serially connected column, connecting a liquid storage device on the serially connected column, washing the serially connected column with the acetonitrile-toluene mixed solution, collecting all effluents, concentrating, adding n-hexane, carrying out rotary concentration, uniformly mixing, and determining by using gas chromatography-mass spectrometry. The method of the present invention has characteristics of good reproducibility, high accuracy, simple pretreatment, and no requirement of expensive extraction equipment.

Description

A kind of gas chromatograph-mass spectrometer that utilizes measures the method that in health products, Multiple Pesticides is residual

Technical field

The present invention relates to a kind of gas chromatograph-mass spectrometer that utilizes and measure the method that in health products, Multiple Pesticides is residual.

Background technology

China is the big country of pesticide producing and use, and in agricultural production, a large amount of agricultural chemicals is used, and the general toxicity of agricultural chemicals is higher and be easily attached to the position such as leaf, flower, fruit of plant; Agricultural chemicals good stability simultaneously, wherein benzene hexachloride, D.D.T. (dichloro-diphenyl-trichloroethane) can reach more than 60 years by stable existence in soil; The toxicity of organic chlorine agriculture chemicals is very big, has been put into the agricultural chemicals category prohibitted the use at present.Organophosphorus insecticide can enter human body through alimentary canal, respiratory tract and intact skin and mucous membrane, enter agricultural chemicals in body through oxidation and hydrolysis, suppress the activity of cholinesterase, make it lose the effect of hydrolysis of acetylcholine, cause CNS regulation function disorderly, cause stupor even dead.Organo-chlorine pesticide can disturb the process such as synthesis, release, transhipment, metabolism of human normal secretion, affects internal system and destroys the stable of organismic internal environment, cause canceration.

In recent years, along with the development of society, scientific research personnel has invented increasing pesticide new variety, also has increasing agricultural chemicals to be put into forbidding scope simultaneously, no matter be organophosphorus, organochlorine or pyrethrin pesticide, have a large amount of kinds to forbid producing and using.But due to the residue problem in supervision problem or soil and water quality, the agricultural chemicals of forbidding kind, also at the living safety threatening people, allows the pesticide species used also to there is the problem of Use out of range and Use overrun simultaneously.The makings multi-pesticide residue detection method that current China routine adopts is the mensuration > standard of 475 kinds of agricultural chemicals and related chemicals residual quantity in GB/T19649-2006< Cereals, but wherein there is processing mode complexity, expensive extraction equipment need be adopted, be unfavorable for applying.Health products are different from cereal crops simultaneously, and its constituent has very large difference, adopt the method for GB/T19649-2006 to extract sample, obviously not too applicable, therefore need a kind of detection method simple to operate badly for health food.

Summary of the invention

The object of the invention is to overcome the deficiencies in the prior art, provide a kind of pre-treatment simple, favorable reproducibility, what accuracy rate was high utilizes gas chromatograph-mass spectrometer to measure the method that in health products, Multiple Pesticides is residual.

Technical scheme of the present invention is summarized as follows:

Utilize gas chromatograph-mass spectrometer to measure the method that in health products, Multiple Pesticides is residual, comprise the steps:

(1) take 10g testing sample, be accurate to 0.01g, extract 3min with 10ml acetonitrile, standing separation, obtains extract;

(2) by extract by having used the Envi-18 post of 10mL acetonitrile prewashing, and with 15mL acetonitrile Xian Di Envi-18 post, collection extract and cleansing solution are in concentrated bottle, and evaporator is concentrated into 1mL, for subsequent use;

(3) add in Envi-Carb post is highly the anhydrous sodium sulfate of 2cm. Envi-Carb post bottom is connected with Sep-Pak NH2 column top and obtains columns in series, wash columns in series with 4mL acetonitrile-methylbenzene mixed liquor; The concentrate that step (2) obtains is crossed columns in series, with 6mL acetonitrile-methylbenzene mixed liquor washing concentrating bottle, and cleansing solution is moved in columns in series; Columns in series connects 50mL liquid reservoir, more past with 25mL acetonitrile-methylbenzene mixed liquor washing series connection, collect all effluents, in 40 DEG C of water-baths, spin concentration is to about 0.5mL, and add 2.5mL normal hexane, last spin concentration is to 1mL, mixing, fixed with gas chromatography-mass spectrum side; Acetonitrile and the toluene of described acetonitrile-methylbenzene mixed liquor to be volume ratio be 3:1 are mixed;

Makings condition:

Chromatographic column: DB-1701 (30m × 0.25mm × 0.25 μm) quartz capillary column;

Chromatogram column temperature: 40 DEG C keep 1min, then with 30 DEG C/min temperature programme to 130 DEG C, then are warming up to 250 DEG C with 5 DEG C/min, then are warming up to 300 DEG C with 10 DEG C/min, keep 5 minutes;

Carrier gas: nitrogen, purity >=99.999%, flow velocity 1.2ml/min;

Injector temperature: 290 DEG C;

Sample size: 1 μ L;

Input mode: Splitless injecting-Sample, opens diverting valve and dottle pin blow down valve after 1.5min;

Electron bombardment ionization source: 70eV;

Ion source temperature: 230 DEG C;

GC-MS interface temperature: 280 DEG C.

Advantage of the present invention: favorable reproducibility, accuracy rate is high; Pre-treatment is simple, without the need to the extraction equipment of costliness.

Accompanying drawing explanation

Fig. 1 is the residual total ion current figure of agriculture.

Embodiment

The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.Below in conjunction with specific embodiment, the invention will be further described.

Embodiment 1

Utilize gas chromatograph-mass spectrometer to measure the method that in health products, Multiple Pesticides is residual, comprise the steps:

(1) take 10g testing sample (certain tea processing factory produce tealeaves, lot number: 20131001), is accurate to 0.01g, with 10ml acetonitrile extract 3min, standing separation, obtains extract;

(2) by extract by having used the Envi-18 post of 10mL acetonitrile prewashing, and with 15mL acetonitrile Xian Di Envi-18 post, collection extract and cleansing solution are in concentrated bottle, and evaporator is concentrated into 1mL, for subsequent use;

(3) add in Envi-Carb post is highly the anhydrous sodium sulfate of 2cm. Envi-Carb post bottom is connected with Sep-Pak NH2 column top and obtains columns in series, wash columns in series with 4mL acetonitrile-methylbenzene mixed liquor; The concentrate that step (2) obtains is crossed columns in series, with 6mL acetonitrile-methylbenzene mixed liquor washing concentrating bottle, and cleansing solution is moved in columns in series; Columns in series connects 50mL liquid reservoir, more past with 25mL acetonitrile-methylbenzene mixed liquor washing series connection, collect all effluents, in 40 DEG C of water-baths, spin concentration is to about 0.5mL, and add 2.5mL normal hexane, last spin concentration is to 1mL, mixing, fixed with gas chromatography-mass spectrum side; Acetonitrile and the toluene of described acetonitrile-methylbenzene mixed liquor to be volume ratio be 3:1 are mixed;

Makings condition:

Chromatographic column: DB-1701 (30m × 0.25mm × 0.25 μm) quartz capillary column;

Chromatogram column temperature: 40 DEG C keep 1min, then with 30 DEG C/min temperature programme to 130 DEG C, then are warming up to 250 DEG C with 5 DEG C/min, then are warming up to 300 DEG C with 10 DEG C/min, keep 5 minutes;

Carrier gas: nitrogen, purity >=99.999%, flow velocity 1.2ml/min;

Injector temperature: 290 DEG C;

Sample size: 1 μ L;

Input mode: Splitless injecting-Sample, opens diverting valve and dottle pin blow down valve after 1.5min;

Electron bombardment ionization source: 70eV;

Ion source temperature: 230 DEG C;

GC-MS interface temperature: 280 DEG C.

Testing result is in table 1 and Fig. 1.

Significantly can find out that in 14, tested pesticide composition can be effectively separated in same sampling system by table 1 with Fig. 1, can quantitatively calculate.

Table 1

Sequence number	Test item	Retention time	m/z
				1	Dieldrite	23.49	277,380,345
2	5a,6,9,9a-hexahydro-6,9-methano-2,4	21.51	265,339
				3	Parathion	19.73	186,235,263
4	Chlopyrifos	19.43	258,286
				5	Thimet	14.05	121,231,153
6	DDVP	6.54	185,220
				7	Parathion-methyl	18.03	233,246,200
8	Etrimfos	16.48	181,277
				9	Diazinon	15.82	179,137
10	Pirimiphos-methyl	18.74	276,305
				11	Quinalphos	21.41	298,157
12	Entex	19.73	169,153
				13	Malathion	19.23	158,143
14	Fenifrothion	18.96	260,247

Table 2 two kinds of method contrast testing results

Sequence number	Test item	Testing result of the present invention (ppm)	GB (GB/T19649-2006) testing result (ppm)
				1	Dieldrite	0.1	0.1
2	5a,6,9,9a-hexahydro-6,9-methano-2,4	0.02	0.02
				3	Parathion	0.003	0.003
4	Chlopyrifos	Do not detect	Do not detect
				5	Thimet	Do not detect	Do not detect
6	DDVP	Do not detect	Do not detect
				7	Parathion-methyl	Do not detect	Do not detect
8	Etrimfos	0.003	0.003
				9	Diazinon	0.001	0.001
10	Pirimiphos-methyl	0.004	0.004
				11	Quinalphos	0.003	0.003
12	Entex	Do not detect	Do not detect
				13	Malathion	Do not detect	Do not detect
14	Fenifrothion	Do not detect	Do not detect

Claims (1)

1. utilize gas chromatograph-mass spectrometer to measure the method that in health products, Multiple Pesticides is residual, it is characterized in that comprising the steps:

(1) take 10g testing sample, be accurate to 0.01g, extract 3min with 10ml acetonitrile, standing separation, obtains extract;

(2) by extract by having used the Envi-18 post of 10mL acetonitrile prewashing, and with 15mL acetonitrile Xian Di Envi-18 post, collection extract and cleansing solution are in concentrated bottle, and evaporator is concentrated into 1mL, for subsequent use;

(3) add in Envi-Carb post is highly the anhydrous sodium sulfate of 2cm. Envi-Carb post bottom is connected with Sep-Pak NH2 column top and obtains columns in series, wash columns in series with 4mL acetonitrile-methylbenzene mixed liquor; The concentrate that step (2) obtains is crossed columns in series, with 6mL acetonitrile-methylbenzene mixed liquor washing concentrating bottle, and cleansing solution is moved in columns in series; Columns in series connects 50mL liquid reservoir, more past with 25mL acetonitrile-methylbenzene mixed liquor washing series connection, collect all effluents, in 40 DEG C of water-baths, spin concentration is to about 0.5mL, and add 2.5mL normal hexane, last spin concentration is to 1mL, mixing, fixed with gas chromatography-mass spectrum side; Acetonitrile and the toluene of described acetonitrile-methylbenzene mixed liquor to be volume ratio be 3:1 are mixed;

Makings condition:

Chromatographic column: DB-1701 (30m × 0.25mm × 0.25 μm) quartz capillary column;

Chromatogram column temperature: 40 DEG C keep 1min, then with 30 DEG C/min temperature programme to 130 DEG C, then are warming up to 250 DEG C with 5 DEG C/min, then are warming up to 300 DEG C with 10 DEG C/min, keep 5 minutes;

Carrier gas: nitrogen, purity >=99.999%, flow velocity 1.2ml/min;

Injector temperature: 290 DEG C;

Sample size: 1 μ L;

Input mode: Splitless injecting-Sample, opens diverting valve and dottle pin blow down valve after 1.5min;

Electron bombardment ionization source: 70eV;

Ion source temperature: 230 DEG C;

GC-MS interface temperature: 280 DEG C.