CN109781912B - Method for measuring 29 auxiliary agent contents in pesticide preparation by gas chromatography-mass spectrometry - Google Patents
Method for measuring 29 auxiliary agent contents in pesticide preparation by gas chromatography-mass spectrometry Download PDFInfo
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Abstract
The invention relates to a method for determining the content of 29 auxiliary agents in a pesticide preparation by adopting a gas chromatography-mass spectrometer, belonging to the technical field of pesticide quality detection. The method for measuring the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry comprises the following steps: (1) preparing a reference substance solution; (2) preparing a sample solution; (3) preparing a blank solution; (4) and (5) GC-MS detection. The invention can simultaneously carry out high-throughput screening and accurate quantification on 29 auxiliary agents which are difficult to be simultaneously detected in the pesticide preparation. The detection efficiency is greatly improved. The method has the obvious advantages of simple operation, rapidness, accuracy, high sensitivity, good repeatability and the like, can quickly detect the content of the auxiliary agent to be forbidden in the pesticide preparation, provides reliable technical support for production and quality supervision of the pesticide preparation, and effectively promotes the sustainable development of the pesticide industry.
Description
Technical Field
The invention relates to a method for determining the content of 29 auxiliary agents in a pesticide preparation by adopting a gas chromatography-mass spectrometer, belonging to the technical field of pesticide quality detection.
Background
As is well known, an agricultural chemical adjuvant is a general term for adjuvants used in the processing and application of agricultural chemical preparations, other than an active ingredient of agricultural chemicals. Almost all chemically synthesized pesticide raw materials cannot be directly used, and can be processed into a pesticide preparation with practical use value by adding various auxiliary substances.
At present, more than 3000 kinds of conventionally used pesticide adjuvants are available, including surfactants, solvents, synergists, dispersants, stickers, stabilizers and the like, which account for a large proportion of pesticide preparations, from a few percent to ninety-ten percent, and although the pesticide adjuvants themselves have no biological activity and play an important role in reducing the dosage of pesticides, improving the biological activity of active ingredients of pesticides, improving the safety of pesticides to crops, reducing environmental pollution, improving economic benefits and the like, more and more researches show that the adjuvants considered as "inert" may be more toxic than the regulated pesticide active ingredients. Toxicity research of more than 2000 auxiliary agents by the United states environmental protection agency discovers that 26% of the auxiliary agents have serious health risks of carcinogenicity, teratogenicity, mutagenicity, endocrine disrupting effect, propagation damage, neurotoxicity and the like. In view of this, countries or regions of the european union, the united states, canada, australia, libaran, indonesia, etc. have successively developed strict regulatory provisions or standards for pesticide adjuvants. Since the pesticide registration management is carried out in continental areas of China, the management of effective components of pesticides is always emphasized, the safety research and management of auxiliaries are just started, although 9 types of auxiliaries such as 1, 4-benzenediol, di (2-ethylhexyl) phthalate, di (2-ethylhexyl) adipate and the like are forbidden and 75 types of auxiliaries such as acetonitrile, 1,2, 3-benzotriazole, benzene, ethylene glycol monobutyl ether, 1-butoxyethoxy-2-propanol, benzyl butyl phthalate, epoxy butane and the like are limited by 9 types of auxiliaries such as acetonitrile, 1,2, 3-benzotriazole, benzene, ethylene glycol monobutyl ether, 1-butoxyethoxy-2-propanol and the like in the pesticide emulsifiable concentrate issued in 2015 7 months by the pesticide institute of ministry of agriculture, ministry of agriculture and industry, only the harmful solvent limit in the pesticide emulsifiable concentrate recommended standard HG/T4576 and 2013 in the chemical industry is used for limiting the harmful solvent in the pesticide emulsifiable concentrate, The method is characterized in that limited values are set for 7 harmful solvents such as toluene, xylene, ethylbenzene, methanol, N-dimethylformamide, naphthalene and the like, while the current 'pesticide standard specification standard' in Taiwan province of China stipulates the limited standards of 44 auxiliaries such as xylene, aniline, benzene, carbon tetrachloride, trichloromethane, tetrachloroethylene and the like in finished pesticides, namely, at present, many auxiliaries commonly used in pesticide production in continental areas of China still lack related management regulations or limited standards, and serious supervision holes and supervision blanks exist.
At present, no national or industrial standard specially aiming at the content detection of the auxiliary agent in the pesticide preparation exists at home and abroad, only HG/T4576-2013 'Limit of harmful solvent in pesticide emulsifiable solution' sets up a matched detection technology for 7 limited harmful solvents such as benzene, toluene, xylene, ethylbenzene, methanol, N-dimethylformamide, naphthalene and the like in the emulsifiable solution preparation, relates to a gas chromatography detection method, the detection method comprises a gas chromatography, a liquid chromatography and a gas chromatography-mass spectrometry, wherein the coverage parameters mainly comprise more than 40 types of methanol, propylene oxide, carbon disulfide, carbon dichloride, 1, 2-dichloroethylene, acetonitrile, carbon tetrachloride and the like, and dozens of common additives such as normal hexane, methyl isobutyl ketone, butyl methacrylate, phenol, hydroquinone and the like lack corresponding detection technical methods.
The method is to establish a detection technical method for the remaining 30 auxiliary agents to be forbidden to be used in the pesticide preparation as soon as possible by referring to a list of the auxiliary agents to be forbidden to be used (a survey of comments) published by the agricultural chemical examination of the ministry of agriculture, not only can effectively fill the technical blank in the supervision field of the auxiliary agents to be forbidden to be used in the production of pesticides and provide powerful technical support for the final appearance and implementation of the list of the auxiliary agents to be forbidden to be used in the production of pesticides in China, but also has important practical significance for ensuring the safe production of agriculture in China, reducing the important potential safety hazard of agricultural products, maintaining the health and safety of consumers, protecting the ecological environment where the agricultural products live and promoting the sustainable and healthy development of the pesticide industry in China.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a method for measuring the content of commonly used additives in a pesticide preparation by using a gas chromatography-mass spectrometer, and the method can be used for rapidly measuring the content of 29 additives in the pesticide preparation.
In order to solve the first technical problem, the method for measuring the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry comprises the following steps:
(1) preparing a reference substance solution: weighing 29 auxiliary agents, dissolving the auxiliary agents by using methanol to prepare a series of reference substance solutions with different mass concentrations, wherein the reference substance solution contains 29 auxiliary agents;
(2) preparing a sample solution: weighing a pesticide sample to be detected, uniformly mixing the pesticide sample to be detected with methanol, and diluting with the methanol to obtain a sample solution to be detected;
(3) preparing a blank solution: carrying out the following step (2) except for weighing the sample;
(4) and (3) GC-MS detection: respectively injecting the series of reference substance working solutions in the step (1) and the blank solution in the step (3) into GC-MS, selecting ion monitoring, and carrying out regression analysis on the corresponding concentration of each auxiliary agent by using the quantitative ion peak area after blank deduction to obtain a standard working curve; injecting the sample solution to be detected in the step (2) into GC-MS under the same conditions, selecting ions for monitoring, obtaining the quantitative ion peak area of each auxiliary agent in the sample after blank deduction, substituting the quantitative ion peak area into a standard working curve, and obtaining the content of each auxiliary agent in the sample.
Further, the step (1) is as follows: dissolving 29 auxiliaries by using methanol to prepare mixed reference substance solutions of which the mass concentration of each auxiliary is 5000.0mg/L, accurately sucking the mixed reference substance solutions, and gradually diluting the mixed reference substance solutions by using methanol to form a series of reference substance solutions with different mass concentrations.
Preferably, in the method for measuring the content of the 29 auxiliary agents in the pesticide preparation by using the gas chromatography-mass spectrometry, the dilution factor in the step (2) is 100 times.
Preferably, the mixing in step (2) is vortex oscillation.
Preferably, the time of the vortex oscillation is 3 min.
Further, the 29 auxiliary agents are: n-hexane, methyl isobutyl ketone, butyl methacrylate, phenol, N-methyl pyrrolidone, hydroquinone, dichloromethane, nitromethane, methyl methacrylate, nitroethane, o-cresol, p-cresol, 2-pyrrolidone, diphenyl ether, dimethyl phthalate, benzotriazole, butanone oxime, diethylene glycol monomethyl ether, diethylene glycol butyl ether, diisooctyl adipate, 2-hexanone, mesityl oxide, isophorone, 1-ethyl-2-pyrrolidone, m-cresol, 4-chloro-3, 5-dimethylphenol, butylbenzyl phthalate, diethylene glycol ethyl ether, bis (2-ethylhexyl) phthalate.
Preferably, the step (2) is: accurately weighing 1g of pesticide sample into a 100mL volumetric flask, adding 50mL of methanol, performing vortex oscillation extraction for 2min, fixing the volume of the methanol to a scale, uniformly mixing, sucking 5mL of extracting solution, centrifuging for 5min at 8000r/min, and taking supernatant to pass through a 0.22 mu m nylon filter membrane.
Accurately weighing the powder in the step (2) to be accurate to 0.001 g.
Preferably, the GC-MS column is: agilent VF-1701MS capillary chromatography column.
Preferably, the methanol is chromatographic pure methanol, and the mass fraction w of the methanol is more than or equal to 99.9%.
Preferably, the GC-MS assay uses chromatographic conditions: sample inlet temperature: 260 ℃; temperature rising procedure: maintaining at 30 deg.C for 2min, heating to 40 deg.C at 3 deg.C/min for 2min, heating to 130 deg.C at 5 deg.C/min for 3min, heating to 200 deg.C at 20 deg.C/min, and heating to 270 deg.C at 60 deg.C/min for 20 min; sample introduction mode: split-flow sample injection, split ratio 50: 1; sample introduction amount: 1 mu L of the solution; carrier gas: helium with purity more than or equal to 99.999%; the column flow rate is 1.0 mL/min;
the conditions of the mass spectrum are as follows: an ionization mode: EI; ionization energy: 70 eV; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃, interface temperature: 270 ℃, solvent retardation: 5.5 min; the scanning mode is as follows: an ion monitoring mode is selected.
Preferably, the average standard addition recovery rate of the method is 89.1-109.7%, the relative standard deviation is 1.1-4.6%, the detection limit is 1.3-131.7 mg/kg, and the quantification limit is 4.4-439.1 mg/kg.
The detection limit of the present invention refers to the lowest concentration at which the method can detect the substance. The limit of quantitation described herein refers to the lowest concentration at which the method can accurately determine the substance.
Has the advantages that:
(1) the method effectively solves the problem that 29 auxiliary agents in the prior art are easily interfered by other coexisting components in the pesticide preparation to cause false positive or false recessive results, and simultaneously realizes the capability of carrying out high-flux accurate qualitative screening and accurate quantitative detection on the auxiliary agent to be forbidden in the pesticide preparation.
(2) The method provided by the invention is matched with an Agilent VF-1701MS medium-polarity capillary chromatographic column, so that good separation of polar auxiliary agents and non-polar auxiliary agents can be simultaneously met, the rapid detection of 29 auxiliary agents is realized, and the detection type and the detection efficiency are greatly improved.
(3) The method has the obvious advantages of simple operation, rapidness, accuracy, high sensitivity, good repeatability and the like, can quickly detect the content of the auxiliary agent to be forbidden in the pesticide preparation, provides reliable technical support for production and quality supervision of the pesticide preparation, and effectively promotes the sustainable development of the pesticide industry.
(4) The average standard addition recovery rate of 29 auxiliaries is 89.1-109.7 percent, the relative standard deviation is 1.1-4.6 percent, the detection limit is 1.3-131.7 mg/kg, the quantification limit is 4.4-439.1 mg/kg, and the requirement is far lower than the related limit requirement of a list for pesticide auxiliary forbidden limit (survey of comments) issued by the pesticide verification of the ministry of agriculture, and the requirement of production and quality supervision of pesticide preparations can be well met.
Drawings
FIG. 129 is a graph of selective ion monitoring of adjuvants;
FIG. 2 shows that the abamectin (5% missible oil) has the detected content of n-hexane of 2.84g/100g and p-cresol of 0.08g/100 g;
FIG. 3 shows that N-methyl pyrrolidone with a content of 15.65g/100g is detected by prochloraz (450g/L missible oil);
FIG. 4 Cyhalothrin (5.10% emulsifiable concentrate) detected dichloromethane with a content of 2.35g/100 g;
FIG. 5 Total ion current chromatogram for 29 auxiliaries from comparative example 1;
FIG. 6 Total ion current chromatogram of 29 adjuvants in comparative example 2.
Detailed Description
In order to solve the first technical problem, the method for determining the content of 29 additives in the pesticide preparation by using the gas chromatography-mass spectrometer comprises the following steps:
the method comprises the following specific steps:
(1) preparing a reference substance solution: accurately weighing 29 auxiliary agent reference substances (accurate to 0.01mg) in the same volumetric flask, dissolving with chromatographic pure methanol to prepare mixed reference substance solution with the mass concentration of each auxiliary agent of 5000.0mg/L, storing at 4 ℃ and having the validity period of 1 month. Accurately sucking a proper amount of mixed reference substance solution, gradually diluting with chromatographic pure methanol to obtain series of reference substance working solutions with different mass concentrations, and preparing for use.
(2) Preparing a sample solution: weighing 1g of pesticide sample (accurate to 0.001g) in a 100mL volumetric flask, adding 50mL of methanol, performing vortex oscillation extraction for 3min, fixing the volume of the methanol to a scale, uniformly mixing, sucking 5mL of extracting solution, centrifuging at 8000r/min for 5min, taking supernate, passing through a 0.22 mu m nylon filter membrane, and adjusting the dilution factor according to the content of an auxiliary agent in the sample when performing GC-MS analysis.
(3) Preparing a blank solution: except that the sample was not weighed, the procedure was as in step (2).
(4) Respectively injecting the series of reference substance working solutions in the step (1) and the blank solution in the step (3) into GC-MS, selecting ion monitoring, and carrying out regression analysis on the corresponding concentration of each auxiliary agent by using the quantitative ion peak area after blank deduction to obtain a standard working curve; injecting the sample solution to be detected in the step (2) into GC-MS under the same conditions, selecting ions for monitoring, obtaining the quantitative ion peak area of each auxiliary agent in the sample after blank deduction, substituting the quantitative ion peak area into a standard working curve, and obtaining the content of each auxiliary agent in the sample.
The mass fraction w of the chromatographic pure methanol used as the extraction and dilution solvent is more than or equal to 99.9 percent.
29 auxiliary agents which are simultaneously detected are N-hexane, methyl isobutyl ketone, butyl methacrylate, phenol, N-methylpyrrolidone, hydroquinone, dichloromethane, nitromethane, methyl methacrylate, nitroethane, o-cresol, p-cresol, 2-pyrrolidone, diphenyl ether, dimethyl phthalate, benzotriazole, butanone oxime, diethylene glycol monomethyl ether, diethylene glycol butyl ether, diisooctyl adipate, 2-hexanone, mesityl oxide, isophorone, 1-ethyl-2-pyrrolidone, m-cresol, 4-chloro-3, 5-dimethylphenol, butyl benzyl phthalate, diethylene glycol ethyl ether and bis (2-ethylhexyl) phthalate.
The chromatographic conditions in the GC-MS measurement are as follows: a chromatographic column: AgiLent VF-1701MS capillary chromatography column, 60m x 0.25mm x 0.25 μm; sample inlet temperature: 260 ℃; temperature rising procedure: maintaining at 30 deg.C for 2min, heating to 40 deg.C at 3 deg.C/min for 2min, heating to 130 deg.C at 5 deg.C/min for 3min, heating to 200 deg.C at 20 deg.C/min, and heating to 270 deg.C at 60 deg.C/min for 20 min; sample introduction mode: split-flow sample injection, split ratio 50: 1; sample introduction amount: 1 mu L of the solution; carrier gas: helium with purity more than or equal to 99.999%; column flow rate: 1.0 mL/min.
The mass spectrometry conditions used were: an ionization mode: EI; ionization energy: 70 eV; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃, interface temperature: 270 ℃, solvent retardation: 5.5 min; the scanning mode is as follows: an ion monitoring mode is selected.
The retention times and the selective ion monitoring parameters for the 29 auxiliaries are shown in table 1.
Table 129 retention time and selected ion monitoring parameters for the adjuvants
When in GC-MS measurement, if the retention time of the auxiliary agent chromatographic peak in the sample after blank deduction is consistent with the retention time of the corresponding auxiliary agent in the reference solution, and in the sample mass spectrogram after background deduction, selected ions all appear, and the abundance ratio of the quantitative ions and the qualitative ions is consistent with the abundance ratio of the ions in the reference solution, namely: relative abundance > 50%, allowing ± 10% deviation; the relative abundance is between 20% and 50%, and the deviation of +/-15% is allowed; the relative abundance is between 10% and 20%, and the deviation of +/-20% is allowed; the relative abundance is less than or equal to 10 percent, and the deviation of +/-50 percent is allowed, so that the auxiliary agent can be judged to exist in the sample; if the two conditions cannot be simultaneously met, judging that the auxiliary agent is not contained.
TABLE 229 linear ranges, linear equations, correlation coefficients, detection limits, quantitation limits, average recovery and relative standard deviations for the adjuvants
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
1. Apparatus and device
Agilent 7890B-5977B gas chromatography-mass spectrometer; an Eppendorf 5810R type high speed refrigerated centrifuge; sartorius model BP 211D electronic balance; XW-80A vortex mixer.
2. Materials and reagents
Auxiliary agent reference substance: n-hexane, methyl isobutyl ketone, butyl methacrylate, phenol, N-methylpyrrolidone, hydroquinone (analytically pure, metropolis chemicals ltd); dichloromethane, nitromethane, methyl methacrylate, nitroethane, o-cresol, p-cresol, 2-pyrrolidone, diphenyl ether, dimethyl phthalate, and benzotriazole (analytically pure, Chengdong chemical reagent factory); butanone oxime, diethylene glycol monomethyl ether, diethylene glycol butyl ether, diisooctyl adipate (analytical grade, Shanghai Arlatin Biochemical science Co., Ltd.); 2-hexanone, mesityl oxide, isophorone, 1-ethyl-2-pyrrolidone, m-cresol, 4-chloro-3, 5-dimethylphenol, butyl benzyl phthalate (analytical purity, Shanghai Michelin Biochemical technology Ltd.); diethylene glycol ethyl ether (analytically pure, shinny fine chemical research institute, Tianjin); bis (2-ethylhexyl) phthalate (analytically pure, Toshiei (Shanghai) chemical industries, Ltd.).
Reagent: chromatographically pure methanol, available from Sigma-Aldrich, USA.
Sample preparation: commercial pesticide preparation A-avermectin (5% emulsifiable concentrate).
3. Preparing a reference substance solution: accurately weighing 29 auxiliary agent reference substances (accurate to 0.01mg) in the same volumetric flask, dissolving with chromatographic pure methanol to prepare mixed reference substance solution with the mass concentration of each auxiliary agent of about 5000.0mg/L, storing at 4 ℃ and having the validity period of 1 month. Accurately sucking a proper amount of mixed reference substance solution, gradually diluting with chromatographic pure methanol to obtain series reference substance solutions with the mass concentrations of all the auxiliary agents of 6.25mg/L, 12.5mg/L, 25mg/L, 50mg/L, 100mg/L, 200mg/L and 400mg/L, and preparing for use.
4. Sample pretreatment:
weighing 1g of pesticide sample (accurate to 0.001g) into a 100mL volumetric flask, adding 50mL of methanol, performing vortex oscillation extraction for 3min, fixing the volume of the methanol to a scale, uniformly mixing, absorbing 5mL of extracting solution, centrifuging for 5min at 8000r/min, taking supernate, and filtering with a 0.22 mu m nylon filter membrane to obtain a sample to be analyzed by GC-MS.
5. Blank test:
except that the sample was not weighed, the procedure was as described in step 4 above.
6. The determination method comprises the following steps:
respectively injecting the prepared series of reference substance working solutions and blank solutions into GC-MS, selecting ions for monitoring, and carrying out regression analysis on the corresponding concentrations of the auxiliary agents by using the quantitative ion peak areas of the auxiliary agents after blank deduction to obtain a standard working curve; injecting the sample solution to be tested into GC-MS under the same conditions, selecting ions for monitoring, obtaining the quantitative ion peak area of each auxiliary agent in the sample after blank deduction, substituting the quantitative ion peak area into a standard working curve, and obtaining the content of each auxiliary agent in the sample, wherein the content is shown in table 3.
TABLE 3 test results for each auxiliary in sample A
In the case of GC-MS measurement, the chromatographic conditions used were: a chromatographic column: AgiLent VF-1701MS capillary chromatography column, 60m x 0.25mm x 0.25 μm; sample inlet temperature: 260 ℃; temperature rising procedure: maintaining at 30 deg.C for 2min, heating to 40 deg.C at 3 deg.C/min for 2min, heating to 130 deg.C at 5 deg.C/min for 3min, heating to 200 deg.C at 20 deg.C/min, and heating to 270 deg.C at 60 deg.C/min for 20 min; sample introduction mode: split-flow sample injection, split ratio 50: 1; sample introduction amount: 1 mu L of the solution; carrier gas: helium with purity more than or equal to 99.999%; column flow rate: 1.0 mL/min.
The mass spectrometry conditions used were: an ionization mode: EI; ionization energy: 70 eV; ion source temperature: 230 ℃; quadrupole rod temperature: 150 ℃, interface temperature: 270 ℃, solvent retardation: 5.5 min; the scanning mode is as follows: an ion monitoring mode is selected.
The retention times and the selective ion monitoring parameters for the 29 auxiliaries are shown in table 1.
When in GC-MS measurement, if the retention time of the auxiliary agent chromatographic peak in the sample after blank deduction is consistent with the retention time of the corresponding auxiliary agent in the reference solution, and in the sample mass spectrogram after background deduction, selected ions all appear, and the abundance ratio of the quantitative ions and the qualitative ions is consistent with the abundance ratio of the ions in the reference solution, namely: relative abundance > 50%, allowing ± 10% deviation; the relative abundance is between 20% and 50%, and the deviation of +/-15% is allowed; the relative abundance is between 10% and 20%, and the deviation of +/-20% is allowed; the relative abundance is less than or equal to 10 percent, and the deviation of +/-50 percent is allowed, so that the auxiliary agent can be judged to exist in the sample; if the two conditions cannot be simultaneously met, judging that the auxiliary agent is not contained.
Example 2
Another pesticide formulation sample B was selected, similar to example 1, with the only difference that: weighing 1g of pesticide sample (accurate to 0.001g) into a 100mL volumetric flask, adding 50mL of methanol, performing vortex oscillation extraction for 3min, fixing the volume of the methanol to a scale, uniformly mixing, absorbing 5mL of extracting solution, centrifuging for 5min at 8000r/min, taking 1mL of supernatant into a 10mL volumetric flask, fixing the volume of the supernatant to the scale by using chromatographic pure methanol, uniformly mixing, passing through a 0.22 mu m nylon filter membrane, and performing GC-MS analysis.
The amounts of the various adjuvants measured in sample B are shown in Table 4.
TABLE 4 test results for each auxiliary in sample B
Example 3
Another pesticide formulation sample C was selected as described in example 1 and the measured amounts of each adjuvant in the sample are shown in table 5.
TABLE 5 test results for each auxiliary in sample C
Comparative example 1
Similar to example 1, the only difference is: the GC-MS measurement adopts the following chromatographic conditions: sample inlet temperature: 260 ℃, temperature rising program: maintaining at 30 deg.C for 2min, heating to 40 deg.C at 3 deg.C/min, maintaining for 2min, heating to 100 deg.C at 8 deg.C/min, heating to 270 deg.C at 25 deg.C/min, and maintaining for 30 min; sample introduction mode: split-flow sample injection, split-flow ratio 800: 1; sample introduction amount: 1 mu L of the solution; carrier gas: helium with purity more than or equal to 99.999%; column flow rate: 1.0 mL/min.
The mass spectrum conditions are as follows: an ionization mode: EI; ionization energy: 70 eV; ion source temperature: 230 ℃; quadrupole rod temperature: 150 ℃, interface temperature: 270 ℃, solvent retardation: 6.15 min; the scanning mode is as follows: full scan, scan range: 28-400 u.
Comparative example 2
Similar to example 1, the only difference is: the GC-MS measurement adopts the following chromatographic conditions: sample inlet temperature: 260 ℃, temperature rising program: maintaining at 30 deg.C for 2min, heating to 40 deg.C at 3 deg.C/min for 2min, heating to 150 deg.C at 8 deg.C/min for 1min, heating to 200 deg.C at 20 deg.C/min, heating to 270 deg.C at 60 deg.C/min, and maintaining for 35 min; sample introduction mode: split-flow sample injection, split ratio 500: 1; sample introduction amount: 1 mu L of the solution; carrier gas: helium with purity more than or equal to 99.999%; column flow rate: 1.0 mL/min.
The mass spectrum conditions are as follows: an ionization mode: EI; ionization energy: 70 eV; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃, interface temperature: 270 ℃, solvent retardation: 5 min; the scanning mode is as follows: full scan, scan range: 28-400 u.
The results of testing the pesticide preparation a under the conditions of comparative example 1 and comparative example 2 are shown in tables 6 and 7, respectively.
Table 6 results of testing each auxiliary agent in sample a under the conditions of comparative example 1
TABLE 7 test results of various additives in sample A under the conditions of comparative example 2
The separation of 29 auxiliaries under the conditions of comparative example 1 and comparative example 2 is shown in Table 8 and FIGS. 5 and 6, and it can be seen that: under other chromatographic and mass spectrometric conditions, such as comparative example 1, comparative example 2, 29 aids were poorly separated, and even some components could not be distinguished at all, such as p-cresol and m-cresol, dimethyl phthalate and 4-chloro-3, 5-dimethylphenol.
TABLE 83 Retention time profiles for 29 auxiliaries under the conditions
TABLE 83 Retention time of 29 auxiliaries under the conditions
Claims (8)
1. The method for determining the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry is characterized by comprising the following steps:
(1) preparing a reference substance solution: weighing 29 auxiliary agents, dissolving the auxiliary agents by using methanol to prepare a series of reference substance solutions with different mass concentrations, wherein the reference substance solution contains 29 auxiliary agents;
(2) preparing a sample solution: weighing a pesticide sample to be detected, uniformly mixing the pesticide sample to be detected with methanol, and diluting with the methanol to obtain a sample solution to be detected;
(3) preparing a blank solution: carrying out the following step (2) except for weighing the sample;
(4) and (3) GC-MS detection: injecting the series of reference substance working solutions in the step (1) and the blank solutions in the step (3) into GC-MS respectively, selecting ions for monitoring, and performing regression analysis on the corresponding concentrations of the auxiliary agents by using the quantitative ion peak areas of the auxiliary agents after blank deduction to obtain a standard working curve; injecting the sample solution to be detected in the step (2) into GC-MS under the same conditions, selecting ion monitoring to obtain the quantitative ion peak area of each auxiliary agent in the sample after blank deduction, substituting the quantitative ion peak area into a standard working curve, and obtaining the content of each auxiliary agent in the sample;
the 29 auxiliary agents are: n-hexane, methyl isobutyl ketone, butyl methacrylate, phenol, N-methyl pyrrolidone, hydroquinone, dichloromethane, nitromethane, methyl methacrylate, nitroethane, o-cresol, p-cresol, 2-pyrrolidone, diphenyl ether, dimethyl phthalate, benzotriazole, butanone oxime, diethylene glycol monomethyl ether, diethylene glycol butyl ether, diisooctyl adipate, 2-hexanone, mesityl oxide, isophorone, 1-ethyl-2-pyrrolidone, m-cresol, 4-chloro-3, 5-dimethylphenol, butyl benzyl phthalate, diethylene glycol ethyl ether, bis (2-ethylhexyl) phthalate;
the chromatographic column of the GC-MS is as follows: agilent VF-1701MS capillary chromatographic column;
the GC-MS determination adopts the following chromatographic conditions: sample inlet temperature: 260 ℃; temperature rising procedure: maintaining at 30 deg.C for 2min, heating to 40 deg.C at 3 deg.C/min for 2min, heating to 130 deg.C at 5 deg.C/min for 3min, heating to 200 deg.C at 20 deg.C/min, and heating to 270 deg.C at 60 deg.C/min for 20 min; sample introduction mode: split-flow sample injection, split ratio 50: 1; sample introduction amount: 1 mu L of the solution; carrier gas: helium with purity more than or equal to 99.999%; the column flow rate is 1.0 mL/min;
the conditions of the mass spectrum are as follows: an ionization mode: EI; ionization energy: 70 eV; ion source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃, interface temperature: 270 ℃, solvent retardation: 5.5 min; the scanning mode is as follows: an ion monitoring mode is selected.
2. The method for determining the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 1, wherein the step (1) is: dissolving 29 auxiliary agents by using methanol to prepare mixed reference substance solutions with the mass concentration of each auxiliary agent being 5000.0mg/L, accurately sucking the mixed reference substance solutions, and gradually diluting the mixed reference substance solutions by using methanol to form a series of reference substance solutions with different mass concentrations.
3. The method for determining the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 1 or 2, wherein the dilution factor in the step (2) is 100 times.
4. The method for determining the content of the 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 1 or 2, wherein the mixing in the step (2) is vortex oscillation.
5. The method for determining the content of the 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 4, wherein the time of the vortex oscillation is 3 min.
6. The method for determining the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 1 or 2, wherein the step (2) is: accurately weighing 1g of pesticide sample into a 100mL volumetric flask, adding 50mL of methanol, performing vortex oscillation extraction for 2min, fixing the volume of the methanol to a scale, uniformly mixing, sucking 5mL of extracting solution, centrifuging for 5min at 8000r/min, and taking supernatant to pass through a 0.22 mu m nylon filter membrane.
7. The method for determining the content of 29 auxiliaries in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 1, wherein the methanol is chromatographic pure methanol, and the mass fraction w of the methanol is not less than 99.9%.
8. The method for determining the content of 29 auxiliary agents in the pesticide preparation by using gas chromatography-mass spectrometry as claimed in claim 1 or 2, wherein the average normalized recovery rate is 89.1-109.7%, the relative standard deviation is 1.1-4.6%, the detection limit is 1.3-131.7 mg/kg, and the quantification limit is 4.4-439.1 mg/kg.
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| CN106596821A (en) * | 2016-12-12 | 2017-04-26 | 中国测试技术研究院 | Quick determination method of organic solvents in pesticide preparation |
| 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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| CN106596821A (en) * | 2016-12-12 | 2017-04-26 | 中国测试技术研究院 | Quick determination method of organic solvents in pesticide preparation |
| 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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| Determination of metalaxyl and identification of adjuvants in wettable powder pesticide technical formulas;Eva Pose-Juan et al.;《Anal Bioanal Chem》;20090205;第1535-1544页 * |
| 农药制剂中39种有机溶剂的气相色谱-质谱测定方法研究;唐祥凯 等;《中国测试》;20170228;第42-46页 * |
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