CN101498692A - Method for measuring pesticide residue quantity in leather - Google Patents
Method for measuring pesticide residue quantity in leather Download PDFInfo
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- CN101498692A CN101498692A CNA2008100541632A CN200810054163A CN101498692A CN 101498692 A CN101498692 A CN 101498692A CN A2008100541632 A CNA2008100541632 A CN A2008100541632A CN 200810054163 A CN200810054163 A CN 200810054163A CN 101498692 A CN101498692 A CN 101498692A
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Abstract
The invention relates to a combined gas chromatography mass spectrometry measuring method for measuring the pesticide residue in leather, which belongs to the field of analytical chemistry. The method adopts normal hexane and acetonitrile to perform ultrasonic extraction to a leather sample and separates and purifies the sample extracting solution by various means such as liquid-liquid extraction, gel permeation chromatograph, adsorbent chromatography column, solidoid extraction column, and the like by aiming to the characteristics that the leather sample has high oil content, the residual processing assistant is complex, and the like, and the pesticide residue of the processed sample extracting solution is measured by the combined gas chromatography mass spectrometry. The invention has the advantages of high selectivity, wide range of application and low detectability, realizes the measurement of the pesticide residue in the leather, creates a new thought for the measurement of the pesticide residue in the leather and fills in a gap for the measurement of the pesticide residue.
Description
Technical field
The invention belongs to the analytical chemistry field, relate to the method that gas chromatography-mass spectrography is measured persticide residue in the leather.Be specifically related to by normal hexane and acetonitrile ultrasonic Extraction leather sample, with the agricultural chemicals in liquid-liquid extraction, gel permeation chromatography (GPC), adsorbent chromatography post, solid-phase extraction column (SPE post) the isolation of purified sample extracting solution, GC-MS(gas chromatography-mass spectrography) is measured its content.
Background technology
Agricultural chemicals is widely used in agricultural production and the commercial production, and when its pesticide-germicide of performance went out the evil effect, agricultural chemicals also became one of important pollutant.In the daily life in food and the daily necessities residual agricultural chemicals invade human body by modes such as alimentary canal, respiratory tract and skin contacts, thereby people's health is caused damage.Different agricultural chemicals has different harm to human body, and organic chlorine agriculture chemicals easily produces slow poisoning; Organophosphorus and carbamate chemicals for agriculture easily produce acute poisoning, serious sometimes threat to life.
Along with understanding and the attention of people to pollution by pesticides, growing to the detection demand of persticide residue, its detected object relates to food, agricultural product, textile, Chinese herbal medicine etc.During leather was produced, agricultural chemicals used as the sterilization and insect prevention agent.And residue in agricultural chemicals in the leather and fur products, and by the skin contact, human body being damaged, this situation has caused the concern of some large-scale garment manufacturers, and has proposed the relevant detection demand.Yet detecting for the persticide residue in the leather does not at present also have perfect relatively method, does not more have standard method to follow.Through experiment repeatedly, the present invention has determined to be directed to the gas chromatography-mass spectrum detection method of agricultural chemicals residual in the leather, has filled up this blank of persticide residue detection range.
Summary of the invention
The invention provides a kind of GC-MS(gas chromatography-mass spectrography) and measure the method for persticide residue in the leather.Agricultural chemicals residual in the leather sample is through normal hexane and acetonitrile ultrasonic Extraction, and extract uses gas chromatograph-mass spectrometer (GCMS) that pesticide concentration is detected after multiple purification method purification separation.
1. extract and purify
A. extract:
A. take by weighing the 2g-10g leather sample that mixes in the 150mL beaker;
B. add the 30mL-100mL normal hexane, behind the abundant mixing, ultrasonic 50min-100min in 30 ℃ of-60 ℃ of water-baths, extract is filtered in the 250mL separating funnel through filter paper;
C. add the 30mL-100mL acetonitrile in the sample residue, ultrasonic 50min-100min in 30 ℃ of-60 ℃ of water-baths merges acetonitrile in separating funnel;
B. purify:
A. liquid-liquid extraction
The separating funnel 20min-50min that vibrates on oscillator is transferred to acetonitrile layer in the flat bottom flask, and normal hexane extracts 2-4 time with the vibration of 20mL-50mL acetonitrile respectively mutually again, the 30min-50min that at every turn vibrates, and the merging acetonitrile is in flat bottom flask;
The acetonitrile extract that merges concentrates near doing on Rotary Evaporators, add cyclohexane and ethyl acetate (1:1) solution of 5mL-15mL, concentrates the nearly back of doing once more and is settled to 10mL with cyclohexane and ethyl acetate (1:1) solution.
B.GPC purifies
The sample extracting solution that is settled to 10mL is filtered into GPC sample introduction bottle through 0.45 μ m pin type filtrator, used Bio-Beads, the chromatographic column of S-X3 (200-400 order) is carried out GPC and is purified.Collect liquid and be transferred in the flat bottom flask, rotary evaporation is done near, adds the 10mL normal hexane, and rotary evaporation is done near once more;
The GPC purification condition:
Acquisition time: 20min-32min
Sampling volume: 5mL
Moving phase: cyclohexane and ethyl acetate (1:1) solution
Flow velocity: 5mL/min
C. chromatographic column purifies
The preparation of chromatographic column:
Adopt the wet-filling method, in glass chromatography column, add the high anhydrous sodium sulfate of 0.5cm-1.5cm with the hexane solution that contains 0.2%-0.8% acetone, the 10g-20g florisil silica, 10g-20g silica gel, the top adds the high anhydrous sodium sulfate of about 0.5cm-1.5cm again, strike reality, with the hexane solution 10mL-30mL activation pillar that contains 0.2%-0.8% acetone, standby.
Last sample and drip washing:
Flat bottom flask with among the about 5mL-10mL washing of the hexane solution that the contains 0.2%-0.8% acetone b is transferred to solution in the chromatographic column for preparing, and the hexane solution 20mL-30mL drip washing with containing 0.2%-0.8% acetone discards leacheate.Add the hexane solution 100mL-150mL drip washing chromatographic column that contains 10%-20% acetone again, collect leacheate in flat bottom flask, be concentrated near doing;
The d.SPE column purification
The hexane solution activation graphitized carbon pillar that contains 20%-30% acetone with 5mL-10mL, to be transferred to pillar through the sample solution that chromatographic column purifies and concentrated, the normal hexane drip washing pillar that contains 20%-30% acetone with 5mL-15mL, collect leacheate, concentrate the nearly back adding 5mL-10mL normal hexane of doing and be concentrated near doing again, be settled to 1mL with normal hexane, analyze with GC-MS.
2. set the GC-MS instrument parameter
The A.GC condition
Gas chromatograph: Thermo DSQ II
Chromatographic column: HP-5MS capillary column 0.25mm * 30m * 0.25 μ m
Injector temperature: 250 ℃-300 ℃
Transmission line temperature: 250 ℃-300 ℃
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction pattern: split sampling not
Sampling volume: 1 μ L
Temperature programme:
Initial temperature is 100 ℃, and the programming rate with 8 ℃/min behind the maintenance 2min rises to 250 ℃.250 ℃ keep 5min after, rise to 320 ℃ with the speed of 15 ℃/min, keep 5min.
B. mass spectrum condition
Detector temperature: 250 ℃-300 ℃
Ion source temperature: 250 ℃-300 ℃
Ionization mode: EI
Acquisition mode: SIM pattern
The present invention is directed to grease, dyestuff and various auxiliary agent in the leather sample provide multiple purification separation method, it is characterized in that liquid-liquid extraction, GPC, adsorbent chromatography post, SPE decontaminating column purification and separation method unite use, the multiple leather of removing in the leather sample of grease, dye well is handled auxiliary agent.
The present invention adopts gas chromatography-mass spectrum logotype method, optimizing application heating schedule realized separating of impurity and determinand, effectively measured residual agricultural chemicals in the leather sample.
Specific embodiment
The detection of agricultural chemicals in the embodiment one pigskin sample
1. extract and purify
A. extract:
A. take by weighing the 5.0g sample that mixes in the 150mL beaker;
B. add the 50mL normal hexane, behind the abundant mixing, ultrasonic 60min in 50 ℃ of water-baths, extract is filtered in the 250mL separating funnel through filter paper;
C. add the 50mL acetonitrile in the sample residue, ultrasonic 60min in 50 ℃ of water-baths merges acetonitrile in separating funnel;
B. purify:
A. liquid-liquid extraction
The separating funnel 30min that vibrates on oscillator is transferred to acetonitrile layer in the flat bottom flask, and normal hexane extracts 2 times with the vibration of 30mL acetonitrile respectively mutually again, and the 40min that at every turn vibrates merges acetonitrile and also integrates with in the flat bottom flask mutually;
The acetonitrile extract that merges concentrates near doing on Rotary Evaporators, add cyclohexane and ethyl acetate (1:1) solution of 10mL, concentrates the nearly back of doing and is settled to 10mL with cyclohexane and ethyl acetate (1:1) solution.
B.GPC purifies
The sample extracting solution that is settled to 10mL is filtered into GPC sample introduction bottle through 0.45 μ m pin type filtrator, carried out GPC and purify.Collect liquid and be transferred in the flat bottom flask, rotary evaporation is done near, adds the 10mL normal hexane, is evaporated near doing;
The GPC purification condition:
Acquisition time: 20min-32min
Sampling volume: 5mL
Moving phase: cyclohexane and ethyl acetate (1:1) solution
Flow velocity: 5mL/min
C. chromatographic column purifies
The preparation of chromatographic column:
Adopt the method for wet dress, in glass chromatography column, add the high anhydrous sodium sulfate of 1cm with the hexane solution that contains 0.5% acetone, add the 10g florisil silica, add 10g silica gel, the top adds the high anhydrous sodium sulfate of 1cm again, strike reality, with the hexane solution 20mL activation pillar that contains 0.5% acetone, standby.
Last sample and drip washing:
With the about 5mL washing of the hexane solution that contains 0.5% acetone flat bottom flask, solution is transferred in the chromatographic column for preparing, the hexane solution 25mL drip washing with containing 0.5% acetone discards leacheate.Add the hexane solution 110mL drip washing chromatographic column that contains 15% acetone again, collect leacheate in flat bottom flask, be concentrated near doing;
The d.SPE column purification
The hexane solution activation graphitized carbon pillar that contains 25% acetone with 5mL, to be transferred to pillar through the sample solution that chromatographic column purifies and oneself concentrates, the normal hexane drip washing pillar that contains 25% acetone with 10mL, collect leacheate, concentrate the nearly back adding 10mL normal hexane of doing and be concentrated near doing again, be settled to 1mL with normal hexane, analyze with GC-MS.
2. set the GC-MS instrument parameter
The A.GC condition
Gas chromatograph: Thermo DSQ II
Chromatographic column: HP-5MS capillary column 0.25mm * 30m * 0.25 μ m
Injector temperature: 250 ℃
Transmission line temperature: 280 ℃
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction pattern: be regardless of and flow to
Sampling volume: 1 μ L
Temperature programme:
| Programming rate (℃/min) | Temperature (℃) | Retention time (min) |
| 100 | 2 | |
| 8 | 250 | 5 |
| 15 | 320 | 5 |
B. mass spectrum condition
Detector temperature: 300 ℃
Ion source temperature: 250 ℃
Ionization mode: EI
Acquisition mode: SIM pattern
C. the characteristic ion of organophosphorus pesticide:
| Sequence number | The compound Chinese name | The compound English name | CAS No. | Select ion |
| 1 | Daconil M | Chlorothalonil | 1897-45-6 | 229，266，264，268 |
| 2 | N, N-dimethyl-N-phenyl-(N-fluorine dichloromethane sulfenyl)-sulfonamide | Dichlofluanid | 1085-98-9 | 123，167，224 |
| 3 | Phosphordithiic acid O, O-dimethyl-S (1,2-diethyl-ester group ethyl) ester | Malathion | 121-75-5 | 125，158，173 |
| 4 | O, O-diethyl-O-p-nitrophenyl ester | Parathion-ethyl | 56-38-2 | 291，139，155 |
| 5 | N-(dichloro fluorine first) sulfenyl N-p-methylphenyl N ', N '-dimethyl disulfide acid diamide | Tolyfluranid | 731-27-1 | 346，137，181，238 |
| 6 | α-six nitrogen sulphur ring | α-endosul fan | 959-98-8 | 339，241，265 |
| 7 | β-six nitrogen sulphur ring | β-endosulfan | 33213-65-9 | 339，241，265 |
| 8 | Chlordene-epoxy octahydro-two methylene naphthalene | Dieldrin | 60-57-1 | 345，380，237，79 |
| 9 | 1,1,2,2 pairs of (4-methoxyphenyl) ethane of 1-three chloro- | Methoxychl or | 72-43-5 | 227，228，153 |
| 10 | The dichloro-benzenes ether-ether | permethrin | 52645-53-1 | 183，163，127 |
3. qualitative and quantitative
A. qualitative
Retention time through sample peak and standard items peak is compared, and sample peak mass spectrogram and standard substance mass spectrogram are compared, and determines whether detect target compound in the sample.
B. quantitative
Adopt the typical curve external standard method quantitative.
The detection of persticide residue in the embodiment two ox-hide samples
1. extract and purify
A. extract:
A. take by weighing the 3.0g sample that mixes in the 150mL beaker;
B. add the 40mL normal hexane, behind the abundant mixing, ultrasonic 80min in 60 ℃ of water-baths, extract is filtered in the 250mL separating funnel through filter paper;
C. add the 40mL acetonitrile in the sample residue, ultrasonic 80min in 60 ℃ of water-baths merges acetonitrile in separating funnel;
B. purify:
A. liquid-liquid extraction
The separating funnel 40min that vibrates on oscillator is transferred to acetonitrile layer in the flat bottom flask, and normal hexane extracts 3 times with the vibration of 30mL acetonitrile respectively mutually again, and the 30min that at every turn vibrates merges acetonitrile and also integrates with in the flat bottom flask mutually;
The acetonitrile extract that merges concentrates near doing on Rotary Evaporators, add cyclohexane and ethyl acetate (1:1) solution of 8mL, concentrates the nearly back of doing and is settled to 10mL with cyclohexane and ethyl acetate (1:1) solution.
B.GPC purifies
The sample extracting solution that is settled to 10mL is filtered into GPC sample introduction bottle through 0.45 μ m pin type filtrator, carried out GPC and purify.Collect liquid and be transferred in the flat bottom flask, rotary evaporation is done near, adds the 10mL normal hexane, is evaporated near doing;
The GPC purification condition:
Acquisition time: 20min-32min
Sampling volume: 5mL
Moving phase: cyclohexane and ethyl acetate (1:1) solution
Flow velocity: 5mL/min
C. chromatographic column purifies
The preparation of chromatographic column:
Adopt the method for wet dress, in glass chromatography column, add the high anhydrous sodium sulfate of 1cm with the hexane solution that contains 0.8% acetone, add 10 gram florisil silicas, add 10 gram silica gel, the top adds the high anhydrous sodium sulfate of 1cm again, strike reality, with the hexane solution 18mL activation pillar that contains 0.8% acetone, standby.
Last sample and drip washing:
With the about 5mL washing of the hexane solution that contains 0.8% acetone flat bottom flask, solution is transferred in the chromatographic column for preparing, the hexane solution 25mL drip washing with containing 0.8% acetone discards leacheate.Add the hexane solution 120mL drip washing chromatographic column that contains 18% acetone again, collect leacheate in flat bottom flask, be concentrated near doing;
The d.SPE column purification
The hexane solution activation graphitized carbon pillar that contains 20% acetone with 8mL, to be transferred to pillar through the sample solution that chromatographic column purifies and concentrated, the normal hexane drip washing pillar that contains 20% acetone with 15mL, collect leacheate, concentrate the nearly back adding 10mL normal hexane of doing and be concentrated near doing again, be settled to 1mL with normal hexane, analyze with GC-MS.
2. set the GC-MS instrument parameter
The A.GC condition
Gas chromatograph: Thermo DSQ II
Chromatographic column: HP-5MS capillary column 0.25mm * 30m * 0.25 μ m
Injector temperature: 280 ℃
Transmission line temperature: 300 ℃
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction pattern: split sampling not
Sampling volume: 1 μ L
Temperature programme:
| Programming rate (℃/min) | Temperature (℃) | Retention time (min) |
| 100 | 2 | |
| 8 | 250 | 5 |
| 15 | 320 | 5 |
B. mass spectrum condition
Detector temperature: 300 ℃
Ion source temperature: 250 ℃
Ionization mode: EI
Acquisition mode: SIM pattern
C. the characteristic ion of organophosphorus pesticide
| Sequence number | The compound Chinese name | The compound English name | CAS No. | Select ion |
| 1 | Daconil M | Chlorothalonil | 1897-45-6 | 229，266，264，268 |
| 2 | N, N-dimethyl-N-phenyl-(N-fluorine dichloromethane sulfenyl)-sulfonamide | Dichlofluanid | 1085-98-9 | 123，167，224 |
| 3 | Phosphordithiic acid O, O-dimethyl-S-(1,2-diethyl-ester group ethyl) ester | Malathion | 121-75-5 | 125，158，173 |
| 4 | O, O-diethyl-O-p-nitrophenyl ester | Parathion-ethyl | 56-38-2 | 291，139，155 |
| 5 | N-(dichloro fluorine first) sulfenyl-N-p-methylphenyl-N ', N '-dimethyl disulfide acid diamide | Tolyfluranid | 731-27-1 | 346，137，181，238 |
| 6 | α-six nitrogen sulphur ring | α-endosulfan | 959-98-8 | 339，241，265 |
| 7 | β-six nitrogen sulphur ring | β-endosulfan | 33213-65-9 | 339，241，265 |
| 8 | Chlordene-epoxy octahydro-two methylene naphthalene | Dieldrin | 60-57-1 | 345，380，237，79 |
| 9 | 1,1,1-three chloro-2, two (4-methoxyphenyl) ethane of 2- | Methoxychlor | 72-43-5 | 227，228，153 |
| 10 | The dichloro-benzenes ether-ether | permethrin | 52645-53-1 | 183，163，127 |
3. qualitative and quantitative
A. qualitative
Retention time through sample peak and standard items peak is compared, and sample peak mass spectrogram and standard substance mass spectrogram are compared, and determines whether detect target compound in the sample.
B. quantitative
Adopt the typical curve external standard method quantitative.
The detection of persticide residue in embodiment three sheepskins
1. extract and purify
A. extract:
A. take by weighing the 5.0g sample that mixes in the 150mL beaker;
B. add the 50mL normal hexane, behind the abundant mixing, ultrasonic 60min in 50 ℃ of water-baths, extract is filtered in the 250mL separating funnel through filter paper;
C. add the 50mL acetonitrile in the sample residue, ultrasonic 60min in 50 ℃ of water-baths merges acetonitrile in separating funnel;
B. purify:
A. liquid-liquid extraction
The separating funnel 30min that vibrates on oscillator is transferred to acetonitrile layer in the flat bottom flask, and normal hexane extracts 3 times with the vibration of 30mL acetonitrile respectively mutually again, and the 40min that at every turn vibrates merges acetonitrile and also integrates with in the flat bottom flask mutually;
The acetonitrile extract that merges concentrates near doing on Rotary Evaporators, add cyclohexane and ethyl acetate (1:1) solution of 10mL, concentrates the nearly back of doing and is settled to 10mL with cyclohexane and ethyl acetate (1:1) solution.
B.GPC purifies
The sample extracting solution that is settled to 10mL is filtered into GPC sample introduction bottle through 0.45 μ m pin type filtrator, carried out GPC and purify.Collect liquid and be transferred in the flat bottom flask, rotary evaporation is done near, adds the 10mL normal hexane, is evaporated near doing;
The GPC purification condition:
Acquisition time: 20min-32min
Sampling volume: 5mL
Moving phase: cyclohexane and ethyl acetate (1:1) solution
Flow velocity: 5mL/min
C. chromatographic column purifies
The preparation of chromatographic column:
Adopt the method for wet dress, in glass chromatography column, add the high anhydrous sodium sulfate of 1cm with the hexane solution that contains 0.5% acetone, add 10 gram florisil silicas, add 10 gram silica gel, the top adds the high anhydrous sodium sulfate of 1cm again, strike reality, with the hexane solution 20mL activation pillar that contains 0.5% acetone, standby.
Last sample and drip washing:
With the about 5mL washing of the hexane solution that contains 0.5% acetone flat bottom flask, solution is transferred in the chromatographic column for preparing, the hexane solution 25mL drip washing with containing 0.5% acetone discards leacheate.Add the hexane solution 110mL drip washing chromatographic column that contains 15% acetone again, collect leacheate in flat bottom flask, be concentrated near doing;
The d.SPE column purification
The hexane solution activation graphitized carbon pillar that contains 25% acetone with 5mL, to be transferred to pillar through the sample solution that chromatographic column purifies and concentrated, the normal hexane drip washing pillar that contains 25% acetone with 10mL, collect leacheate, concentrate the nearly back adding 10mL normal hexane of doing and be concentrated near doing again, be settled to 1mL with normal hexane, analyze with GC-MS.
2. set the GC-MS instrument parameter
The A.GC condition
Gas chromatograph: Thermo DSQ II
Chromatographic column: HP-5MS capillary column 0.25mm * 30m * 0.25 μ m
Injector temperature: 250 ℃
Transmission line temperature: 280 ℃
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction pattern: split sampling not
Sampling volume: 1 μ L
Temperature programme:
| Programming rate (℃/min) | Temperature (℃) | Retention time (min) |
| 100 | 2 | |
| 8 | 250 | 5 |
| 15 | 320 | 5 |
B. mass spectrum condition
Detector temperature: 300 ℃
Ion source temperature: 250 ℃
Ionization mode: EI
Acquisition mode: SIM pattern
C. the characteristic ion of organophosphorus pesticide
| Sequence number | The compound Chinese name | The compound English name | CASNo. | Select ion |
| 1 | Daconil M | Chlorothalonil | 1897-45-6 | 229，266，264，268 |
| 2 | N, N-dimethyl-N-phenyl-(N-fluorine dichloromethane sulfenyl)-sulfonamide | Dichlofluanid | 1085-98-9 | 123，167，224 |
| 3 | Phosphordithiic acid O, O-dimethyl-S-(1,2-diethyl-ester group ethyl) ester | Malathion | 121-75-5 | 125，158，173 |
| 4 | O, O-diethyl-O-p-nitrophenyl ester | Parathion-ethyl | 56-38-2 | 291，139，155 |
| 5 | N-(dichloro fluorine first) sulfenyl-N-p-methylphenyl-N ', N '-dimethyl disulfide acid diamide | Tolyfluranid | 731-27-1 | 346，137，181，238 |
| 6 | α-six nitrogen sulphur ring | α-endosulfan | 959-98-8 | 339，241，265 |
| 7 | β-six nitrogen sulphur ring | β-endosulfan | 33213-65-9 | 339，241，265 |
| 8 | Chlordene-epoxy octahydro-two methylene naphthalene | Dieldrin | 60-57-1 | 345，380，237，79 |
| 9 | 1,1,1-three chloro-2, two (4-methoxyphenyl) ethane of 2- | Methoxychlor | 72-43-5 | 227，228，153 |
| 10 | The dichloro-benzenes ether-ether | permethrin | 52645-53-1 | 183，163，127 |
3. qualitative and quantitative
A. qualitative
Retention time through sample peak and standard items peak is compared, and sample peak mass spectrogram and standard substance mass spectrogram are compared, and determines whether detect target compound in the sample.
B. quantitative
Adopt the typical curve external standard method quantitative.
The detection of persticide residue in embodiment four buffs
1. extract and purify
A. extract:
A. take by weighing the 10.0g sample that mixes in the 150mL beaker;
B. add the 100mL normal hexane, behind the abundant mixing, ultrasonic 100min in 60 ℃ of water-baths, extract is filtered in the 250mL separating funnel through filter paper;
C. add the 100mL acetonitrile in the sample residue, ultrasonic 100min in 60 ℃ of water-baths merges acetonitrile in separating funnel;
B. purify:
A. liquid-liquid extraction
The separating funnel 50min that vibrates on oscillator is transferred to acetonitrile layer in the flat bottom flask, and normal hexane extracts 4 times with the vibration of 50mL acetonitrile respectively mutually again, and the 40min that at every turn vibrates merges acetonitrile and also integrates with in the flat bottom flask mutually;
The acetonitrile extract that merges concentrates near doing on Rotary Evaporators, add cyclohexane and ethyl acetate (1:1) solution of 15mL, concentrates the nearly back of doing and is settled to 10mL with cyclohexane and ethyl acetate (1:1) solution.
B.GPC purifies
The sample extracting solution that is settled to 10mL is filtered into GPC sample introduction bottle through 0.45 μ m pin type filtrator, carried out GPC and purify.Collect liquid and be transferred in the flat bottom flask, rotary evaporation is done near, adds the 10mL normal hexane, is evaporated near doing;
The GPC purification condition:
Acquisition time: 20min-32min
Sampling volume: 5mL
Moving phase: cyclohexane and ethyl acetate (1:1) solution
Flow velocity: 5mL/min
C. chromatographic column purifies
The preparation of chromatographic column:
Adopt the method for wet dress, in glass chromatography column, add the high anhydrous sodium sulfate of 1cm with the hexane solution that contains 0.5% acetone, add 10 gram florisil silicas, add 10 gram silica gel, the top adds the high anhydrous sodium sulfate of 1cm again, strike reality, with the hexane solution 20mL activation pillar that contains 0.5% acetone, standby.
Last sample and drip washing:
With the about 10mL washing of the hexane solution that contains 0.5% acetone flat bottom flask, solution is transferred in the chromatographic column for preparing, the hexane solution 30mL drip washing with containing 0.5% acetone discards leacheate.Add the hexane solution 150mL drip washing chromatographic column that contains 20% acetone again, collect leacheate in flat bottom flask, be concentrated near doing;
The d.SPE column purification
The hexane solution activation graphitized carbon pillar that contains 30% acetone with 10mL, to be transferred to pillar through the sample solution that chromatographic column purifies and concentrated, the normal hexane drip washing pillar that contains 30% acetone with 15mL, collect leacheate, concentrate the nearly back adding 10mL normal hexane of doing and be concentrated near doing again, be settled to 1mL with normal hexane, analyze with GC-MS.
2. set the GC-MS instrument parameter
The A.GC condition
Gas chromatograph: Thermo DSQ II
Chromatographic column: HP-5MS capillary column 0.25mm * 30m * 0.25 μ m
Injector temperature: 250 ℃
Transmission line temperature: 300 ℃
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction pattern: split sampling not
Sampling volume: 1 μ L
Temperature programme:
| Programming rate (℃/min) | Temperature (℃) | Retention time (min) |
| 100 | 2 | |
| 8 | 250 | 5 |
| 15 | 320 | 5 |
B. mass spectrum condition
Detector temperature: 300 ℃
Ion source temperature: 250 ℃
Ionization mode: EI
Acquisition mode: SIM pattern
C. the characteristic ion of organophosphorus pesticide:
| Sequence number | The compound Chinese name | The compound English name | CAS No. | Select ion |
| 1 | Daconil M | Chlorothalonil | 1897-45-6 | 229，266，264，268 |
| 2 | N, N-dimethyl-N-phenyl-(N-fluorine dichloromethane sulfenyl)-sulfonamide | Dichlofluanid | 1085-98-9 | 123，167，224 |
| 3 | Phosphordithiic acid O, O-dimethyl-S-(1,2-diethyl-ester group ethyl) ester | Malathion | 121-75-5 | 125，158，173 |
| 4 | O, O-diethyl-O-p-nitrophenyl ester | Parathion-ethyl | 56-38-2 | 291，139，155 |
| 5 | N-(dichloro fluorine first) sulfenyl-N-p-methylphenyl-N ', N '-dimethyl disulfide acid diamide | Tolyfluranid | 731-27-1 | 346，137，181，238 |
| 6 | α-six nitrogen sulphur ring | α-endosulfan | 959-98-8 | 339，241，265 |
| 7 | β-six nitrogen sulphur ring | β-endosulfan | 33213-65-9 | 339，241，265 |
| 8 | Chlordene-epoxy octahydro-two methylene naphthalene | Dieldrin | 60-57-1 | 345，380，237，79 |
| 9 | 1,1,1-three chloro-2, two (4-methoxyphenyl) ethane of 2- | Methoxychlor | 72-43-5 | 227，228，153 |
| 10 | The dichloro-benzenes ether-ether | permethrin | 52645-53-1 | 183，163，127 |
3. qualitative and quantitative
A. qualitative
Retention time through sample peak and standard items peak is compared, and sample peak mass spectrogram and standard substance mass spectrogram are compared, and determines whether detect target compound in the sample.
B. quantitative
Adopt the typical curve external standard method quantitative.
Claims (5)
1. a gas chromatography combined with mass spectrometry (GC-MS) is measured the method for persticide residue in the leather, it is characterized in that: to the leather sample through ultrasonic Extraction, adopt liquid-liquid extraction, gel permeation chromatography (GPC), adsorbent chromatography post, solid-phase extraction column (SPE post) to unite the method for use, residual agricultural chemicals in the isolation of purified extract, and use gas chromatograph-mass spectrometer (GCMS) to measure its content, wherein, said purification separation leather sample extracting solution middle peasant cartridge bag is drawn together following steps:
A. ultrasonic Extraction
Take by weighing leather sample that 2g-10g mixes in beaker, add the 30mL-100mL normal hexane, fully behind the mixing, ultrasonic 50min-100min in 30 ℃ of-60 ℃ of water-baths, extract is filtered in the separating funnel through filter paper, add the 30mL-100mL acetonitrile in the sample residue, ultrasonic 50min-100min in 30 ℃ of-60 ℃ of water-baths is incorporated in the separating funnel with acetonitrile normal hexane mutually mutually;
B. liquid-liquid extraction
The normal hexane and the acetonitrile extract of leather sample are transferred in the separating funnel, and the 20min-50min that on the separating funnel oscillator, vibrates, acetonitrile layer is transferred in the flat bottom flask, normal hexane extracts 2-4 time with the vibration of 20mL-50mL acetonitrile respectively mutually again, each vibration 30min-50min, merge acetonitrile mutually and in flat bottom flask, the acetonitrile extract that merges is after concentrating on the Rotary Evaporators, the cyclohexane and ethyl acetate (1:1) solution that add 5mL-15mL concentrate the back once more and are settled to 10mL with cyclohexane and ethyl acetate (1:1) solution;
C.GPC purifies
The sample extracting solution that is settled to 10mL is filtered into GPC sample introduction bottle with the pin type filtrator, carried out GPC and purify, collect liquid and be transferred in the flat bottom flask, after concentrating on the Rotary Evaporators, add the 10mL normal hexane, be evaporated to 0.1mL-0.5mL;
The GPC purification condition is:
Acquisition time: 20min-32min
Sampling volume: 5mL
Moving phase: cyclohexane and ethyl acetate (1:1) solution
Flow velocity: 5mL/min
D. adsorbent chromatography column purification
With the flat bottom flask in the hexane solution 5mL-10mL washing C step that contains 0.2%-0.8% acetone, solution is transferred in the chromatographic column for preparing, with the hexane solution 20mL-30mL drip washing that contains 0.2%-0.8% acetone, discard leacheate, again with the hexane solution 100mL-150mL drip washing chromatographic column that contains 10%-20% acetone, collect leacheate in flat bottom flask, on Rotary Evaporators, concentrate leacheate;
E.SPE purifies
The hexane solution activation SPE pillar that contains 20%-30% acetone with about 5mL-10mL, to be transferred to pillar through the sample solution that chromatographic column purifies and concentrated, the normal hexane drip washing pillar that contains 20%-30% acetone with 5mL-15mL, collect leacheate, concentrate the nearly back adding 5mL-10mL normal hexane of doing and be concentrated near doing again, be settled to 1mL with normal hexane;
F. gas chromatography-mass spectrography is measured extract, and wherein parameter is:
Chromatographic condition:
Injector temperature can be 250 ℃-300 ℃,
The following setting of heating schedule:
Initial temperature is 100 ℃, keeps that the programming rate with 8 ℃/min rises to 250 ℃ behind the 2min, 250 ℃ keep 5min after, rise to 320 ℃ with the speed of 15 ℃/min, keep 5min;
The mass spectrum condition:
Detector temperature: 250 ℃-300 ℃
Ion source temperature: 250 ℃-300 ℃
Ionization mode: EI
Acquisition mode: SIM pattern.
2. the method for claim 1 is characterized in that using in the GPC purification method packing material to be Bio-Beads, the chromatographic column of S-X3 (200-400 order).
3. the method for claim 1, it is characterized in that the chromatographic column filler in the adsorbent chromatography column purification is anhydrous sodium sulfate, florisil silica and silica gel, three kinds of filler layerings are filled separately, fill the high anhydrous sodium sulfate of 0.5cm-1.5cm successively, the 10g-20g florisil silica, 10g-20g silica gel, top add the high anhydrous sodium sulfate of 0.5cm-1.5cm again, and the hexane solution that contains 0.2%-0.8% acetone with 10mL-30mL activates.
4. the method for claim 1 is characterized in that SPE column purification pillar is the graphitized carbon pillar.
5. according to claim 1, it is characterized in that method detects at the gaschromatographic mass spectrometry of persticide residue in the leather, agricultural chemicals is: daconil M (Bravo, Chlorothalonil), N, N-dimethyl-N-phenyl-(N-fluorine dichloromethane sulfenyl)-sulfonamide (Euparen, Dichlofluanid), phosphordithiic acid O, O-dimethyl-S-(1,2-diethyl-ester group ethyl) ester (malathion, Malathion), O, and O-diethyl-O-p-nitrophenyl ester (ethyl parathion, Parathion-ethyl), N-(dichloro fluorine first) sulfenyl N p-methylphenyl-N ', N '-dimethyl disulfide acid diamide (Tolylfluanid, Tolyfluranid), α-six nitrogen sulphur ring (α-5a,6,9,9a-hexahydro-6,9-methano-2,4, α-endosulfan), β-six nitrogen sulphur ring (β-5a,6,9,9a-hexahydro-6,9-methano-2,4, β-endosulfan), chlordene-epoxy octahydro-two methylene naphthalene (dieldrite, Dieldrin), 1,1,1-three chloro-2, two (4-methoxyphenyl) ethane (methoxychlors of 2-, Methoxychlor), the dichloro-benzenes ether-ether (Permethrin, permethrin).
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