CN109781912A - With the method for 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations - Google Patents
With the method for 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations Download PDFInfo
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Abstract
The present invention relates to a kind of methods using 29 kinds of auxiliary agent contents in gas chromatograph-mass spectrometer (GC-MS) measurement pesticidal preparations, belong to pesticide quality detection technique field.Method with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations of the invention includes: that (1) reference substance solution is prepared；(2) preparation of sample solution；(3) preparation of blank solution；(4) GC-MS is detected.The present invention can carry out high flux examination and accurate quantification to the auxiliary agent that 29 kinds of difficulties detect simultaneously in pesticidal preparations simultaneously.Substantially increase detection efficiency.With easy to operate, quick, accurate, high sensitivity and the remarkable advantages such as reproducible, it can quickly detect and intend limiting used additives content in pesticidal preparations, robust techniques support is provided for the production of pesticidal preparations and quality monitoring, effectively pushes the sustainable development of pesticide industry.
Description
Technical field
The present invention relates to a kind of sides using 29 kinds of auxiliary agent contents in gas chromatograph-mass spectrometer (GC-MS) measurement pesticidal preparations
Method belongs to pesticide quality detection technique field.
Background technique
It is well known that insecticides adjuvant is other in addition to pesticide active ingredient used in Pesticide formulation and application
The general name of adminicle.Since nearly all chemically synthesized pesticide original medicine all not directly uses, it is necessary to all kinds of auxiliary by adding
The pesticidal preparations with actual use value can be processed by helping substance.
Currently, conventional use of insecticides adjuvant kind is more than 3000 kinds, including surfactant, solvent, synergist, point
Powder, sticker, stabilizer etc., proportion is very big in pesticidal preparations, differs from a few percent to nineties percent,
Although insecticides adjuvant itself is reducing pesticide dosage, the bioactivity for improving pesticide active ingredient, is improving without bioactivity
Pesticide to the safety of crop, reducing environmental pollution, increase economic efficiency etc. all plays a significant role, but more and more
Studies have shown that the auxiliary agent that these are considered as 'inertia' may be more toxic than the pesticide activity component supervised.Environmental Protection in America
Affix one's name to and the toxicity research of more than 2000 auxiliary agents found, wherein 26% auxiliary agent itself have carcinogenicity, teratogenesis, mutagenicity,
The serious health risks such as endocrine, reproductive injury, neurotoxicity.In consideration of it, European Union, the U.S., Canada, the big benefit of Australia
Stringent administrative provisions or standard are put into effect to insecticides adjuvant in succession in the countries such as Asia, Lebanon, Indonesia.China mainland
Area has laid particular emphasis on always the management to pesticide active ingredient, to the safety research of auxiliary agent since carrying out agriculture chemical registration management
It just starts to walk with management, although former the Institute for the Control of Agrochemicals of the Ministry of Agriculture,PRC has also issued in July, 2015, " insecticides adjuvant is limited with name
It is single " (exposure draft), intend to 1, 4-benzenediol, phthalic acid two (2- ethyl hexyl) ester, adipic acid two (2- ethyl hexyl) ester
Disabling and acetonitrile, l, 2,3 triazole, benzene, butyl glycol ether, 1- Butoxyethoxy -2- propyl alcohol, neighbour are carried out Deng 9 analog assistants
75 analog assistants such as phthalic acid benzyl butyl ester, epoxy butane are limited the use of, but still not yet formal appearance so far, and only chemical industry pushes away
Recommend standard HG/T 4576-2013 " in emulsifiable concentrates for agricultural chemicals hazardous solvent limit the quantity " to benzene,toluene,xylene in emulsifiable concentrates for agricultural chemicals, ethylbenzene,
7 kinds of hazardous solvents such as methanol, n,N-Dimethylformamide, naphthalene set Limited Doses, and existing " the pesticide standard rule in Taiwan Province, China
Lattice criterion " then define 44 kinds of auxiliary agents such as dimethylbenzene in finished pesticide, aniline, benzene, carbon tetrachloride, chloroform, tetrachloro-ethylene
Limitation benchmark, i other words still still there are much relevant pipes of common auxiliary agent shortage in pesticide producing in China mainland area at present
Reason regulation or limit standard, there are serious supervision loophole and supervision blank, these toxic auxiliary agents are full during the applications of pesticide
Portion enters environment, and remains in the circulatory systems such as atmospheric thermodynamics, hydrosphere for a long time, not only causes serious environmental pollution, but also
Safety of human and livestock is seriously endangered, toxic action is not less than even much larger than pesticide active ingredient itself.
Currently, both at home and abroad without specifically for the country of auxiliary agent content detection or professional standard, only HG/ in pesticidal preparations
T4576-2013 " hazardous solvent is limited the quantity in emulsifiable concentrates for agricultural chemicals " is to benzene,toluene,xylene, ethylbenzene, methanol, N in cream preparation, N- bis-
7 kinds of hazardous solvents of limiting such as methylformamide, naphthalene have formulated mating detection technique, and being related to detection method is gas chromatography, and
In relation in pesticidal preparations auxiliary agent detect document report it is also less, be related to detection method have gas chromatography, liquid chromatography and
Gas chromatography-mass spectrography, covering parameter is mainly methanol, propylene oxide, carbon disulfide, carbon dichloride, 1,2-dichloroethene, second
Nitrile, carbon tetrachloride etc. more than 40 still has n-hexane, hexone, butyl methacrylate, phenol, hydroquinone etc.
Tens of kinds of usual auxiliaries lack corresponding detection technique method.
With reference to " insecticides adjuvant is limited with list " (exposure draft) that former the Institute for the Control of Agrochemicals of the Ministry of Agriculture,PRC issues, establish as early as possible
The remaining nearly 30 kinds quasi- detection technique methods for limiting used additives are extremely urgent in pesticidal preparations, and it is raw not only can effectively to fill up pesticide
Partially intend limiting the technological gap of used additives supervision area in production, be China " insecticides adjuvant is limited with list " final appearance and
Implement and strong technical support be provided, and for ensure China's secure agricultural production, reduce agricultural product major safety risks,
The ecological environment and push the sustainable health hair of China's pesticide industry that maintenance consumer's health safety, protection are depended on for existence
Exhibition all has important realistic meaning.
Summary of the invention
The invention solves first technical problem be to provide it is a kind of using gas chromatograph-mass spectrometer (GC-MS) measure pesticide
The method of usual auxiliaries content in preparation, this method can quickly measure 29 kinds of auxiliary agent contents in pesticidal preparations.
In order to solve the first technical problem mentioned above, of the invention to be helped with 29 kinds in Gas Chromatography-Mass Spectrometry pesticidal preparations
The method of agent content includes:
(1) reference substance solution is prepared: weighing 29 kinds of auxiliary agents, the dissolution of auxiliary agent methanol is configured to serial different quality concentration
Reference substance solution, 29 kinds of auxiliary agents are contained in the reference substance solution；
(2) preparation of sample solution: weighing pesticide sample to be measured, and pesticide sample to be measured be uniformly mixed with methanol, then
Testing sample solution is obtained with methanol dilution；
(3) it the preparation of blank solution: in addition to not weighing sample, is carried out according to step (2)；
(4) GC-MS is detected: the blank solution in the control series product working solution and step (3) in step (1) is distinguished
GC-MS is injected, Salbutamol Selected Ion Monitoring returns its respective concentration to deduct the quota ion peak area of each auxiliary agent after blank
Analysis, obtains standard working curve；The testing sample solution in step (2) is injected into GC-MS under the same conditions, selects ion
Monitoring obtains deducting the quota ion peak area of each auxiliary agent in sample after blank, substitutes into standard working curve, acquire each in sample
The content of auxiliary agent.
Further, step (1) are as follows: be by the mass concentration that 29 kinds of auxiliary agent methanol dissolutions are configured to each auxiliary agent
The mixed reference substance solution of 5000.0mg/L, then the mixed reference substance solution is accurately drawn, it is diluted to series step by step with methanol
The reference substance solution of different quality concentration.
Preferably, the method with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations, step (2) institute
Stating diluted multiple is 100 times.
Preferably, step (2) is described is uniformly mixed as vortex oscillation.
Preferably, the time of the vortex oscillation is 3min.
Further, 29 kinds of auxiliary agents are as follows: n-hexane, hexone, butyl methacrylate, phenol, N-
Methyl pyrrolidone, hydroquinone, methylene chloride, nitromethane, methyl methacrylate, nitroethane, o-cresol, to first
Phenol, 2-Pyrrolidone, diphenyl ether, repefral, benzotriazole, diacetylmonoxime, diethylene glycol monomethyl ether, diethyl two
Alcohol butyl ether, diisooctyl adipate, methyl-n-butyl ketone, isopropylidene acetone, isophorone, 1- ethyl-2-pyrrolidone, metacresol, 4-
Bis- (2- ethylhexyl) esters of chloro- 3,5- xylenol, BBP(Butyl Benzyl Phthalate, diethylene glycol ether, phthalic acid.
Preferably, the step (2) are as follows: accurately weigh 1g pesticide sample in 100mL volumetric flask, 50mL methanol whirlpool is added
Mechanical shaking extraction 2min is revolved, methanol constant volume to scale mixes, and draws 5mL extracting solution and is centrifuged 5min under 8000r/min, takes supernatant
Liquid crosses 0.22 μm of nylon leaching film.
It is accurately weighed described in step (2) and is accurate to 0.001g.
Preferably, the chromatographic column of the GC-MS are as follows: Agilent VF-1701MS capillary chromatographic column.
Preferably, the methanol is Chromatographic Pure Methanol, mass fraction w >=99.9% of methanol.
Preferably, the chromatographic condition that the GC-MS measurement uses are as follows: injector temperature: 260 DEG C；Temperature program: 30 DEG C of guarantors
Hold 2min, be warming up to 40 DEG C with 3 DEG C/min, keep 2min, then 5 DEG C/min is warming up to 130 DEG C, keep 3min, then with 20 DEG C/
Min is warming up to 200 DEG C, is finally warming up to 270 DEG C with 60 DEG C/min, keeps 20min；Sample introduction mode: split sampling, split ratio
50:1；Sample volume: 1 μ L；Carrier gas: helium, purity >=99.999%；Column flow rate: 1.0mL/min；
The mass spectrographic condition are as follows: ionization mode: EI；Ionizing energy: 70eV；Ion source temperature: 230 DEG C；Quadrupole rod temperature
Degree: 150 DEG C, interface temperature: 270 DEG C, solvent delay: 5.5min；Scanning mode: Salbutamol Selected Ion Monitoring mode.
Preferably, the average recovery of standard addition of the method is 89.1%~109.7%, relative standard deviation 1.1%
~4.6%, detection is limited to 1.3~131.7mg/kg, is quantitatively limited to 4.4~439.1mg/kg.
Detection limit of the present invention refers to minimum concentration when method can measure the substance.Quantitative limit of the present invention refers to
Method energy accurate quantitative analysis goes out concentration minimum when the substance.
The utility model has the advantages that
(1) method of the invention efficiently solves 29 kinds of auxiliary agents of art methods and coexists into vulnerable to other in pesticidal preparations
Divide the problem of interfering and causing false positive or false recessive result, while realizing and limiting used additives progress height to quasi- in pesticidal preparations
The ability of the accurate qualitatively screening of flux and accurate quantification detection.
(2) method of the invention cooperates Agilent VF-1701MS middle polarity capillary chromatographic column, can meet simultaneously
The good separation of Polar adjuvants and nonpolar auxiliary agent, realizes the quick detection of 29 kinds of auxiliary agents, substantially increases detection type and inspection
Survey efficiency.
(3) present invention has easy to operate, quick, accurate, high sensitivity and the remarkable advantages such as reproducible, can quickly examine
It surveys and intends limiting used additives content in pesticidal preparations, provide robust techniques support for the production of pesticidal preparations and quality monitoring, effectively
Push the sustainable development of pesticide industry.
(4) the average recovery of standard addition that this method measures 29 kinds of auxiliary agents is 89.1%~109.7%, and relative standard deviation is
1.1%~4.6%, detection is limited to 1.3~131.7mg/kg, 4.4~439.1mg/kg is quantitatively limited to, well below the former Ministry of Agriculture
The related limitation requirement of " insecticides adjuvant is limited with list " (exposure draft) of agriculture chemical examination institution's publication, can meet well
The needs of pesticidal preparations production and quality monitoring.
Detailed description of the invention
The Salbutamol Selected Ion Monitoring figure of 29 kinds of auxiliary agents of Fig. 1；
Fig. 2 avermectin (5% missible oil) detects the n-hexane that content is 2.84g/100g and the paracresol of 0.08g/100g；
Fig. 3 Prochloraz (450g/L missible oil) detects the N-Methyl pyrrolidone that content is 15.65g/100g；
Fig. 4 cyfloxylate (5.10% missible oil) detects the methylene chloride that content is 2.35g/100g；
The total ion chromatogram of 29 kinds of auxiliary agents in Fig. 5 comparative example 1；
The total ion chromatogram of 29 kinds of auxiliary agents in Fig. 6 comparative example 2.
Specific embodiment
In order to solve the first technical problem mentioned above, a kind of use gas chromatograph-mass spectrometer (GC-MS) of the invention measures pesticide
29 kinds of auxiliary agent content methods are as follows in preparation:
Specific step is as follows:
(1) 29 kinds of auxiliary agent reference substance (being accurate to 0.01mg) Yu Tongyi volumetric flasks the preparation of reference substance solution: are accurately weighed
In, the mixed reference substance solution that each auxiliary agent mass concentration is 5000.0mg/L is prepared with Chromatographic Pure Methanol dissolution, is protected at 4 DEG C
It deposits, validity period 1 month.Suitable mixed reference substance solution is accurately drawn, it is dense to be diluted to different quality step by step with Chromatographic Pure Methanol
The control series product working solution of degree, it is ready-to-use.
(2) preparation of sample solution: weighing 1g pesticide sample (being accurate to 0.001g) in 100mL volumetric flask, is added
50mL methanol vortex oscillation extracts 3min, and methanol constant volume to scale mixes, and draws 5mL extracting solution and is centrifuged under 8000r/min
5min takes supernatant to cross 0.22 μm of nylon leaching film, analyzes to GC-MS, according to the content appropriate adjustment dilution times of auxiliary agent in sample
Number.
(3) it the preparation of blank solution: in addition to not weighing sample, is carried out according to step (2).
(4) blank solution in the control series product working solution and step (3) in step (1) is injected separately into GC-MS,
Salbutamol Selected Ion Monitoring carries out regression analysis to its respective concentration to deduct the quota ion peak area of each auxiliary agent after blank, obtains
Standard working curve；The testing sample solution in step (2) is injected into GC-MS under the same conditions, Salbutamol Selected Ion Monitoring obtains
The quota ion peak area for deducting each auxiliary agent in sample after blank, substitutes into standard working curve, acquires containing for each auxiliary agent in sample
Amount.
Mass fraction w >=99.9% used for extracting retarder thinner Chromatographic Pure Methanol of the invention.
29 kinds of auxiliary agents of detection are n-hexane, hexone, butyl methacrylate, phenol, N- methyl simultaneously
Pyrrolidones, hydroquinone, methylene chloride, nitromethane, methyl methacrylate, nitroethane, o-cresol, paracresol, 2-
Pyrrolidones, diphenyl ether, repefral, benzotriazole, diacetylmonoxime, diethylene glycol monomethyl ether, diethylene glycol fourth
Ether, diisooctyl adipate, methyl-n-butyl ketone, isopropylidene acetone, isophorone, 1- ethyl-2-pyrrolidone, metacresol, 4- chloro- 3,
Bis- (2- ethylhexyl) esters of 5- xylenol, BBP(Butyl Benzyl Phthalate, diethylene glycol ether, phthalic acid.
Chromatographic condition when GC-MS is measured are as follows: chromatographic column: AgiLent VF-1701MS capillary chromatographic column, 60m ×
0.25mm×0.25μm；Injector temperature: 260 DEG C；Temperature program: 30 DEG C of holding 2min are warming up to 40 DEG C with 3 DEG C/min, protect
2min is held, then 5 DEG C/min is warming up to 130 DEG C, 3min is kept, then be warming up to 200 DEG C with 20 DEG C/min, finally with 60 DEG C/min
270 DEG C are warming up to, 20min is kept；Sample introduction mode: split sampling, split ratio 50:1；Sample volume: 1 μ L；Carrier gas: helium, purity
>=99.999%；Column flow rate: 1.0mL/min.
The Mass Spectrometry Conditions of use are as follows: ionization mode: EI；Ionizing energy: 70eV；Ion source temperature: 230 DEG C；Quadrupole rod temperature
Degree: 150 DEG C, interface temperature: 270 DEG C, solvent delay: 5.5min；Scanning mode: Salbutamol Selected Ion Monitoring mode.
The retention time and Salbutamol Selected Ion Monitoring parameter of 29 kinds of auxiliary agents are shown in Table 1.
The retention time and Salbutamol Selected Ion Monitoring parameter of 1 29 kinds of auxiliary agents of table
When GC-MS is measured, helped if auxiliary agent chromatographic peak retention time is corresponding to reference substance solution in sample after deduction blank
Agent retention time is consistent, and in the sample mass spectrum after background correction, selected ion occurs, and it is quantitative from
It is sub with the abundance of qualitative ion than the abundance of ions with reference substance solution than consistent, it may be assumed that relative abundance > 50%, allow ±
10% deviation；Relative abundance allows ± 15% deviation between 20%~50%；Relative abundance permits between 10%~20%
Perhaps ± 20% deviation；Relative abundance≤10% allows ± 50% deviation, then can determine whether that there are this auxiliary agents in sample；If above-mentioned
Two conditions cannot meet simultaneously, then judgement does not contain this kind of auxiliary agent.
The range of linearity, linear equation, related coefficient, detection limit, quantitative limit, average recovery rate and the phase of 2 29 kinds of auxiliary agents of table
To standard deviation
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
1. instrument and equipment
Agilent 7890B-5977B type gas chromatograph-mass spectrometer (GC-MS)；Eppendorf 5810R type high speed freeze from
Scheming；Sartorius BP 211D type electronic balance；XW-80A type eddy mixer.
2. material and reagent
Auxiliary agent reference substance: n-hexane, hexone, butyl methacrylate, phenol, N-Methyl pyrrolidone,
Hydroquinone (analyzes pure, Chengdu Cologne Chemical Company)；Methylene chloride, nitromethane, methyl methacrylate, nitre
Base ethane, o-cresol, paracresol, 2-Pyrrolidone, diphenyl ether, repefral, benzotriazole (analysis it is pure, at
City Ke Long chemical reagent factory)；Diacetylmonoxime, diethylene glycol monomethyl ether, butyl, diisooctyl adipate (analysis it is pure,
Shanghai Aladdin biochemical technology limited liability company)；Methyl-n-butyl ketone, isopropylidene acetone, isophorone, 1- ethyl-2-pyrrolidone,
Metacresol, 4-chloro-3,5-dimethylphenol, BBP(Butyl Benzyl Phthalate (analyze pure, the limited public affairs of Shanghai Mike's woods biochemical technology
Department)；Diethylene glycol ether (analysis is pure, and fine chemistry industry research institute is recovered in Tianjin)；Bis- (2- ethylhexyl) esters of phthalic acid
(analysis is pure, uncommon love (Shanghai) the chemical conversion industry Development Co., Ltd of ladder).
Reagent: Chromatographic Pure Methanol is purchased from Sigma-Aldrich.
Sample: commercially available pesticidal preparations A --- avermectin (5% missible oil).
3. the preparation of reference substance solution: accurately weighing 29 kinds of auxiliary agent reference substance (being accurate to 0.01mg) Yu Tongyi volumetric flasks
In, the mixed reference substance solution that each auxiliary agent mass concentration is each about 5000.0mg/L is prepared with Chromatographic Pure Methanol dissolution, at 4 DEG C
It saves, validity period 1 month.Suitable mixed reference substance solution is accurately drawn, is diluted to each auxiliary agent matter step by step with Chromatographic Pure Methanol
Amount concentration is the control series product of 6.25mg/L, 12.5mg/L, 25mg/L, 50mg/L, 100mg/L, 200mg/L, 400mg/L
Solution, it is ready-to-use.
4. sample pre-treatments:
1g pesticide sample (being accurate to 0.001g) is weighed in 100mL volumetric flask, 50mL methanol vortex oscillation is added and extracts
3min, methanol constant volume to scale mix, and draw 5mL extracting solution and are centrifuged 5min under 8000r/min, supernatant is taken to cross 0.22 μm
Nylon leaching film obtains the sample analyzed to GC-MS.
5. blank test:
In addition to not weighing sample, carried out according to above-mentioned steps 4.
6. measuring method:
Prepared control series product working solution and blank solution are injected separately into GC-MS, Salbutamol Selected Ion Monitoring, with button
Except the quota ion peak area of auxiliary agent each after blank carries out regression analysis to its respective concentration, standard working curve is obtained；In phase
Testing sample solution is injected into GC-MS under the conditions of, Salbutamol Selected Ion Monitoring obtains deducting after blank quantifying for each auxiliary agent in sample
Ion peak areas, substitutes into standard working curve, and the content for acquiring each auxiliary agent in sample is shown in Table 3.
The testing result of each auxiliary agent in 3 sample A of table
In GC-MS measurement, the chromatographic condition of use are as follows: chromatographic column: AgiLent VF-1701MS capillary chromatographic column,
60m×0.25mm×0.25μm；Injector temperature: 260 DEG C；Temperature program: 30 DEG C of holding 2min are warming up to 40 with 3 DEG C/min
DEG C, 2min is kept, then 5 DEG C/min is warming up to 130 DEG C, 3min is kept, then be warming up to 200 DEG C with 20 DEG C/min, finally with 60
DEG C/min is warming up to 270 DEG C, keep 20min；Sample introduction mode: split sampling, split ratio 50:1；Sample volume: 1 μ L；Carrier gas: helium
Gas, purity >=99.999%；Column flow rate: 1.0mL/min.
The Mass Spectrometry Conditions of use are as follows: ionization mode: EI；Ionizing energy: 70eV；Ion source temperature: 230 DEG C；Quadrupole rod temperature
Degree: 150 DEG C, interface temperature: 270 DEG C, solvent delay: 5.5min；Scanning mode: Salbutamol Selected Ion Monitoring mode.
The retention time and Salbutamol Selected Ion Monitoring parameter of 29 kinds of auxiliary agents are shown in Table 1.
When GC-MS is measured, helped if auxiliary agent chromatographic peak retention time is corresponding to reference substance solution in sample after deduction blank
Agent retention time is consistent, and in the sample mass spectrum after background correction, selected ion occurs, and it is quantitative from
It is sub with the abundance of qualitative ion than the abundance of ions with reference substance solution than consistent, it may be assumed that relative abundance > 50%, allow ±
10% deviation；Relative abundance allows ± 15% deviation between 20%~50%；Relative abundance permits between 10%~20%
Perhaps ± 20% deviation；Relative abundance≤10% allows ± 50% deviation, then can determine whether that there are this auxiliary agents in sample；If above-mentioned
Two conditions cannot meet simultaneously, then judgement does not contain this kind of auxiliary agent.
Embodiment 2
Select another pesticidal preparations sample B, it is similar to Example 1, it is unique unlike: it is (accurate to weigh 1g pesticide sample
To 0.001g) in 100mL volumetric flask, 50mL methanol vortex oscillation is added and extracts 3min, methanol constant volume to scale mixes, and inhales
It takes 5mL extracting solution to be centrifuged 5min under 8000r/min, takes supernatant 1mL in 10mL volumetric flask, be settled to Chromatographic Pure Methanol
Scale mixes, and crosses 0.22 μm of nylon leaching film, analyzes to GC-MS.
The content for measuring each auxiliary agent in sample B is shown in Table 4.
The testing result of each auxiliary agent in 4 sample B of table
Embodiment 3
As described in Example 1, another pesticidal preparations sample C is selected, the content for measuring each auxiliary agent in sample is shown in Table 5.
The testing result of each auxiliary agent in 5 sample C of table
Comparative example 1
It is similar to Example 1, it is unique unlike: the chromatographic condition that GC-MS measurement uses are as follows: injector temperature: 260
DEG C, temperature program: 30 DEG C of holding 2min are warming up to 40 DEG C with 3 DEG C/min, keep 2min, and then 8 DEG C/min is warming up to 100 DEG C,
270 DEG C are warming up to 25 DEG C/min again, keeps 30min；Sample introduction mode: split sampling, split ratio 800:1；Sample volume: 1 μ L；It carries
Gas: helium, purity >=99.999%；Column flow rate: 1.0mL/min.
The Mass Spectrometry Conditions are as follows: ionization mode: EI；Ionizing energy: 70eV；Ion source temperature: 230 DEG C；Quadrupole rod temperature:
150 DEG C, interface temperature: 270 DEG C, solvent delay: 6.15min；Scanning mode: full scan, scanning range: 28~400u.
Comparative example 2
It is similar to Example 1, it is unique unlike: the chromatographic condition that GC-MS measurement uses are as follows: injector temperature: 260
DEG C, temperature program: 30 DEG C of holding 2min are warming up to 40 DEG C with 3 DEG C/min, keep 2min, and then 8 DEG C/min is warming up to 150 DEG C,
1min is kept, then is warming up to 200 DEG C with 20 DEG C/min, is finally warming up to 270 DEG C with 60 DEG C/min, keeps 35min；Sample introduction mould
Formula: split sampling, split ratio 500:1；Sample volume: 1 μ L；Carrier gas: helium, purity >=99.999%；Column flow rate: 1.0mL/min.
The Mass Spectrometry Conditions are as follows: ionization mode: EI；Ionizing energy: 70eV；Ion source temperature: 230 DEG C；Quadrupole rod temperature:
150 DEG C, interface temperature: 270 DEG C, solvent delay: 5min；Scanning mode: full scan, scanning range: 28~400u.
The testing result of pesticidal preparations A is shown in Table 6, table 7 respectively under the conditions of comparative example 1, comparative example 2.
Under the conditions of 6 comparative example 1 of table in sample A each auxiliary agent testing result
Under the conditions of 7 comparative example 2 of table in sample A each auxiliary agent testing result
The separation situation of 29 kinds of auxiliary agents is shown in Table shown in 8 and Fig. 5, Fig. 6 under the conditions of comparative example 1, comparative example 2, it will thus be seen that
Under other chromatographies and Mass Spectrometry Conditions such as comparative example 1, comparative example 2, the separating degree of 29 kinds of auxiliary agents is poor or even some compositions are basic
It cannot distinguish between, such as paracresol and metacresol, repefral and 4-chloro-3,5-dimethylphenol.
The retention time situation of 29 kinds of auxiliary agents under the conditions of 83 kinds of table
The retention time situation of 29 kinds of auxiliary agents under the conditions of 83 kinds of table
Claims (10)
1. with the method for 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations, which is characterized in that the method packet
It includes:
(1) reference substance solution is prepared: weighing 29 kinds of auxiliary agents, the dissolution of auxiliary agent methanol is configured to pair of serial different quality concentration
According to product solution, 29 kinds of auxiliary agents are contained in the reference substance solution；
(2) preparation of sample solution: pesticide sample to be measured is weighed, and pesticide sample to be measured is uniformly mixed with methanol, then use first
Alcohol dilutes to obtain testing sample solution；
(3) it the preparation of blank solution: in addition to not weighing sample, is carried out according to step (2)；
(4) GC-MS is detected: the blank solution in the control series product working solution and step (3) in step (1) is injected separately into
GC-MS, Salbutamol Selected Ion Monitoring return point to deduct the quota ion peak area of each auxiliary agent after blank to its respective concentration
Analysis, obtains standard working curve；The testing sample solution in step (2) is injected into GC-MS under the same conditions, selects ion prison
It surveys, obtains deducting the quota ion peak area of each auxiliary agent in sample after blank, substitute into standard working curve, acquire in sample and respectively help
The content of agent.
2. according to claim 1 with the method for 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations, feature
It is, step (1) are as follows: be the mixing of 5000.0mg/L by the mass concentration that 29 kinds of auxiliary agent methanol dissolutions are configured to each auxiliary agent
Reference substance solution, then the mixed reference substance solution is accurately drawn, it is diluted to pair of serial different quality concentration step by step with methanol
According to product solution.
3. the method according to claim 1 or claim 2 with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations,
It is characterized in that, step (2) the diluted multiple is 100 times.
4. any one side with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations according to claim 1~3
Method, which is characterized in that step (2) is described to be uniformly mixed as vortex oscillation；The time of the vortex oscillation is preferably 3min.
5. according to claim 4 with the method for 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations, feature
Be, 29 kinds of auxiliary agents are as follows: n-hexane, hexone, butyl methacrylate, phenol, N-Methyl pyrrolidone,
Hydroquinone, methylene chloride, nitromethane, methyl methacrylate, nitroethane, o-cresol, paracresol, 2-Pyrrolidone,
Diphenyl ether, repefral, benzotriazole, diacetylmonoxime, diethylene glycol monomethyl ether, butyl, adipic acid
The chloro- 3,5- dimethyl of di-isooctyl, methyl-n-butyl ketone, isopropylidene acetone, isophorone, 1- ethyl-2-pyrrolidone, metacresol, 4-
Bis- (2- ethylhexyl) esters of phenol, BBP(Butyl Benzyl Phthalate, diethylene glycol ether, phthalic acid.
6. any one side with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations according to claim 1~5
Method, which is characterized in that the step (2) are as follows: accurately weigh 1g pesticide sample in 100mL volumetric flask, 50mL methanol whirlpool is added
Mechanical shaking extraction 2min is revolved, methanol constant volume to scale mixes, and draws 5mL extracting solution and is centrifuged 5min under 8000r/min, takes supernatant
Liquid crosses 0.22 μm of nylon leaching film.
7. any one side with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations according to claim 1~6
Method, which is characterized in that the chromatographic column of the GC-MS are as follows: Agilent VF-1701 MS capillary chromatographic column.
8. according to claim 7 with the method for 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations, feature
It is, the methanol is Chromatographic Pure Methanol, mass fraction w >=99.9% of methanol.
9. any one side with 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations according to claim 1~8
Method, which is characterized in that the chromatographic condition that the GC-MS measurement uses are as follows: injector temperature: 260 DEG C；Temperature program: 30 DEG C of guarantors
Hold 2min, be warming up to 40 DEG C with 3 DEG C/min, keep 2min, then 5 DEG C/min is warming up to 130 DEG C, keep 3min, then with 20 DEG C/
Min is warming up to 200 DEG C, is finally warming up to 270 DEG C with 60 DEG C/min, keeps 20min；Sample introduction mode: split sampling, split ratio
50:1；Sample volume: 1 μ L；Carrier gas: helium, purity >=99.999%；Column flow rate: 1.0mL/min；
The mass spectrographic condition are as follows: ionization mode: EI；Ionizing energy: 70eV；Ion source temperature: 230 DEG C；Quadrupole rod temperature:
150 DEG C, interface temperature: 270 DEG C, solvent delay: 5.5min；Scanning mode: Salbutamol Selected Ion Monitoring mode.
10. any one of according to claim 1~9 29 kinds of auxiliary agent contents in Gas Chromatography-Mass Spectrometry pesticidal preparations
Method, which is characterized in that the average recovery of standard addition of the method is 89.1%~109.7%, relative standard deviation 1.1%
~4.6%, detection is limited to 1.3~131.7mg/kg, is quantitatively limited to 4.4~439.1mg/kg.
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| CN109374777A (en) * | 2018-12-14 | 2019-02-22 | 四川省农业科学院分析测试中心 | A kind of detection method of pesticide residues in vegetables medicine auxiliary agent |
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