CN102749404A - Method for detecting N-methyl carbamate pesticide residues - Google Patents
Method for detecting N-methyl carbamate pesticide residues Download PDFInfo
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- CN102749404A CN102749404A CN2012102497522A CN201210249752A CN102749404A CN 102749404 A CN102749404 A CN 102749404A CN 2012102497522 A CN2012102497522 A CN 2012102497522A CN 201210249752 A CN201210249752 A CN 201210249752A CN 102749404 A CN102749404 A CN 102749404A
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- methyl carbamate
- carbamate pesticide
- pesticide residue
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Abstract
The invention discloses a method for detecting N-methyl carbamate pesticide residues. The method includes treating a water sample by means of extracting solid in advance; preparing a series of mixed methanol standard solutions of the N-methyl carbamate pesticide residues; analyzing the standard solutions by an ultra-fast chromatographic ultraviolet detector, and drawing a standard curve by using mass concentrations of the standard solutions as horizontal coordinates and peak areas of the standard solutions as vertical coordinates to obtain a standard curvilinear regression equation; and analyzing the water sample to be analyzed by the ultra-fast chromatographic ultraviolet detector and respectively computing mass concentrations of the N-methyl carbamate pesticide residues in the water sample to be analyzed according to the peak areas. By the aid of the method, a gap in the technology for detecting the N-methyl carbamate pesticide residues in environmental water is filled, mass concentrations of trace metolcarb, isoprocarb, diethofencarb and fenobucarb can be obtained simultaneously by one-step detection, and the method has the advantages of simplicity, capability of saving time, sensitivity and high efficiency. In addition, the ultra-fast liquid chromatographic ultraviolet detection method is universal and is popularized and applied easily.
Description
Technical field
The present invention relates to by means of the chemistry of measuring material or physical property is tested or the method for amalyzing substances, specifically, relate to detect in the environmental analysis field method of N-methyl carbamate pesticide residue thing.
Background technology
N-methyl carbamate class agricultural chemicals is widely used in desinsection, weeding, the sterilization of various crops in agricultural production, cause the pesticide residue that contains trace in environment water, food, crop and the animal feed.In new " state environment protecting standard " [HJ478-2009] that formulates, " drinking water sanitary standard " [GB/T5750.9-2006], " water environment quality standard " standards such as [GB3838-2002], all be not directed to the analyzing detecting method of N-methyl carbamate pesticide residue thing.
MTMC, Mobucin, the mould prestige of second and Bassa are the big and four kinds of slower compounds of degraded of N-methyl carbamate class pesticide poisoning property.Their residue not only parent has stronger biologically active, and toxicity and persistence that the product after hydrolysis, photodissociation or biodegradation has are stronger than parent.When enrichment, amplification through food chain, when being absorbed by the body,, cause nerve conduction to be obstructed with the physiologically active of acetylcholine esterase inhibition, cause neural paralysis even death, serious threat human beings'health safety.
MTMC, Mobucin, the mould prestige of second and the residual quantity of Bassa agricultural chemicals in environment are very low, and exist simultaneously with the residues of pesticides of other kind, cause the numerous difficulties of this type of Detecting Pesticide of trace.The sample pretreatment technology is an important means that solves this difficult problem, and at present, the preconditioning technique of MTMC, Mobucin, the mould prestige of second and Bassa pesticide residue mainly is liquid-liquid technique, solid phase extraction techniques etc.Traditional liquid-liquid technique complex operation step, and need to consume a large amount of reagent.Solid phase extraction techniques relies on characteristics such as its solvent consumption is few, efficient quick to replace traditional liquid-liquid technique gradually, is widely used in the analyzing and testing of trace amount environment sample.But it is sorry that traditional solid phase extraction techniques exists still when being applied to the analysis of trace MTMC in the environment, Mobucin, the mould prestige of second and Bassa that sensitivity is not enough, the recovery is low etc.So setting up the solid phase extraction techniques that is suitable for trace MTMC, Mobucin, the mould prestige of second and Bassa residues of pesticides has very important significance.
The method that generally is used at present to separate and detects N-methyl carbamate pesticide residue thing mainly comprises vapor-phase chromatography, gas phase-mass spectrometry method, high performance liquid chromatogram-mass spectrometry method, post-column derivation high performance liquid chromatography fluorescence detection etc.But vapor-phase chromatography and post-column derivation high performance liquid chromatography fluorescence detection all need be derived to determinand, complex operation, and the derivating agent that uses generally has toxicity, and instrument is expensive simultaneously; Though mass spectrometry is sensitive, fast, high to instrument requirement, be difficult for popularization.
Summary of the invention
What the present invention will solve is the technical matters that does not have the specific aim analyzing detecting method in the prior art; A kind of N-methyl carbamate pesticide residue object detecting method is provided; Utilize SPE-hypervelocity liquid chromatography ultraviolet detection; Effectively eliminate the interference of impurity in the environment water, can detect the content of MTMC, Mobucin, the mould prestige of second and four kinds of N-methyl carbamates of Bassa pesticide residue thing simultaneously, apace.
In order to solve the problems of the technologies described above, the present invention is achieved through following technical scheme:
A kind of N-methyl carbamate pesticide residue object detecting method, said N-methyl carbamate pesticide residue thing comprises MTMC, Mobucin, the mould prestige of second and Bassa, this method is carried out according to following steps:
A. soak into and the activation solid phase extraction column with methyl alcohol, ultrapure water successively, subsequent use;
B. get water sample to be analyzed with 1 ~ 5mLmin
-1Appearance on the speed through the solid phase extraction column enrichment, treats that water sample all exhausts the back and uses ultrapure water drip washing;
C. at the dry solid phase extraction column of vacuum lower pumping;
D. use 1 ~ 7mL eluant, eluent with 1 ~ 5mLmin
-1Speed wash-out solid phase extraction column, and collect eluent;
E. behind nitrogen drying eluent under 20 ~ 55 ℃ of conditions, methanol constant volume;
F. prepare N-methyl carbamate pesticide residue system row and mix the methyl alcohol standard solution;
G. the N-methyl carbamate pesticide residue system row that adopt hypervelocity liquid chromatography UV-detector analytical procedure (f) to be prepared mix the methyl alcohol standard solution; With its mass concentration is that horizontal ordinate, peak area are ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately;
H. the water sample to be analyzed that adopts hypervelocity liquid chromatography UV-detector analytical procedure (e) to obtain;
I. the mould prestige of MTMC, Mobucin, second and the Bassa peak area separately that obtain according to step (h); Utilize step (g) gained MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately, calculate the mass concentration of MTMC in the water sample to be analyzed, Mobucin, the mould prestige of second and Bassa respectively;
Wherein, Hypervelocity liquid chromatography ultraviolet detection condition in step (g) and the step (h) is following: the C18 chromatographic column; Sampling volume is 5 ~ 10 μ L, and the volume ratio of mobile phase methanol-ultrapure water is 40:60 ~ 90:10, and the flow velocity of mobile phase methanol-ultrapure water is 0.5 ~ 1.5mLmin
-1, column temperature is 20 ~ 50 ℃, the ultraviolet detection wavelength is 200 ~ 340nm.
Solid phase extraction column in said step (a) to the step (d) is selected from vinylpyrrolidone-divinylbenzene polymer pillar (Oasis HLB pillar), C18 pillar or amino pillar.The upward appearance speed of water sample to be analyzed is 3mLmin in the said step (b)
-1
Eluant, eluent in the said step (d) is selected from methyl alcohol/acetonitrile that methyl alcohol, methylene chloride or volume are 1:1.
Eluant, eluent consumption in the said step (d) is 5mL.
Elution speed in the said step (d) is 3mLmin
-1
The volume ratio of mobile phase methanol-ultrapure water is 70:30 in said step (g) and the step (h).
The flow velocity of mobile phase methanol-ultrapure water is 0.5mLmin in said step (g) and the step (h)
-1
Column temperature in said step (g) and the step (h) is 40 ℃.
Ultraviolet detection wavelength in said step (g) and the step (h) is 284nm.
The invention has the beneficial effects as follows:
The invention provides a kind of SPE and combine, the method for trace MTMC, Mobucin, the mould prestige of second and four kinds of N-methyl carbamates of Bassa pesticide residue thing in the testing environment water body with the ultra-violet analysis of hypervelocity liquid chromatography.This method can realize detecting in MTMC, Mobucin, the mould prestige of second and four kinds of N-methyl carbamates of the Bassa pesticide residue thing in 7min, and the range of linearity is 0.01 ~ 1000mgL
-1Related coefficient is 0.9982 ~ 0.9998; Detect and be limited to 0.049 ~ 1.6 μ g L
-1The relative standard deviation of appearance time and peak area is respectively between 0.001% ~ 0.01% and 0.1% ~ 0.6%; The method recovery is 91.3% ~ 107%, and relative standard deviation is 1.52% ~ 4.86%.
The present invention has filled up the blank of N-methyl carbamate pesticide residue quality testing survey technology in the environment water, can obtain the mass concentration of trace MTMC, Mobucin, the mould prestige of second and Bassa through disposable detection simultaneously.The solid phase extraction sample preconditioning technique is economy, safety, environmental protection not only, and can effectively remove the interference of impurity to detecting in the environment water, and sensitivity, the recovery are further strengthened; Simultaneously, hypervelocity liquid chromatography ultraviolet detection method need not add derivating agent, and detection saves time more, sensitivity, easy, and the instrument popularity rate is high, is easy to apply.
Embodiment
Following examples can make those skilled in the art more comprehensively understand the present invention, but do not limit the present invention in any way.Following examples are all used Agilent1200 RRLC hypervelocity liquid chromatograph, the configuration UV-detector; Agilent36 position solid-phase extraction device, the HSC-24B Nitrogen evaporator.
Embodiment 1
The water sample pre-service: soak into and activation C18 solid phase extraction column with 5mL methyl alcohol, 5mL ultrapure water successively, subsequent use.Get water sample to be analyzed with 1mLmin
-1On the speed appearance, through the enrichment of C18 solid phase extraction column, water sample all exhaust the back with the drip washing of 3mL ultrapure water, the dry 30min that under vacuum, continues to bleed then, with 1mL methyl alcohol with 1mLmin
-1Speed wash-out C18 solid phase extraction column, and collect eluent.After nitrogen dries up eluent under 20 ℃ of conditions, to 1.0mL, treat stratographic analysis with methanol constant volume.
The preparation of N-methyl carbamate pesticide residue thing standard serial solution: difference weighing 0.00100g MTMC, Mobucin, the mould prestige of second and Bassa solid sample, to 1mL, compound concentration is respectively 1000mgL with methanol constant volume
-1MTMC, Mobucin, the mould prestige of second and Bassa standard are mixed and are used liquid, and stepwise dilution becomes that concentration is respectively 500,250,125,62.5,31.25,15.63,7.82,1.0mgL then
-1The standard series mixed solution of MTMC, Mobucin, the mould prestige of second and Bassa, to be measured behind 0.45 μ m membrane filtration.
Adopt hypervelocity liquid chromatography UV-detector that the standard series mixed solution is analyzed; With MTMC, Mobucin, the mould prestige of second and Bassa peak area separately is that ordinate, mass concentration are horizontal ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately respectively.The testing conditions of choosing is: the C18 chromatographic column; Sampling volume 5.0 μ L; Mobile phase methanol-ultrapure water volume ratio 40:60; Mobile phase methanol-ultrapure water flow velocity 0.5mLmin
-120 ℃ of column temperatures; The detection wavelength is 200nm.
Under identical condition, detect the water sample to be analyzed of above-mentioned processing; According to MTMC, Mobucin, the mould prestige of second and Bassa peak area separately; Utilize MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately accordingly, calculate the mass concentration of MTMC in the water sample, Mobucin, the mould prestige of second and Bassa respectively.
The analytical characteristic amount of MTMC, Mobucin, the mould prestige of second and Bassa: the related coefficient 0.9992 ~ 0.9996 of MTMC, Mobucin, the mould prestige of second and Bassa; Detect and be limited to 0.049 ~ 1.53 μ g L
-1The relative standard deviation of appearance time and peak area is respectively at 0.001% ~ 0.01% and 0.1% ~ 0.6%; The method recovery is 92.7% ~ 103%, and relative standard deviation is 1.30% ~ 3.75%.
Embodiment 2
The water sample pre-service: soak into and activation Oasis HLB solid phase extraction column with 5mL methyl alcohol, 5mL ultrapure water successively, subsequent use.Get water sample to be analyzed with 2mLmin
-1On the speed appearance, through the enrichment of Oasis HLB solid phase extraction column, water sample all exhaust the back with the drip washing of 3mL ultrapure water, the dry 30min that under vacuum, continues to bleed then, with 3mL methyl alcohol/acetonitrile (V/V)=1/1 with 2mLmin
-1Speed wash-out Oasis HLB solid phase extraction column, and collect eluent.After nitrogen dries up eluent under 30 ℃ of conditions, to 1.0mL, treat stratographic analysis with methanol constant volume.
The preparation of N-methyl carbamate pesticide residue thing standard serial solution: difference weighing 0.00100g MTMC, Mobucin, the mould prestige of second and Bassa solid sample, to 1mL, compound concentration is respectively 1000mgL with methanol constant volume
-1MTMC, Mobucin, the mould prestige of second and Bassa standard are mixed and are used liquid, and stepwise dilution becomes that concentration is respectively 500,250,125,62.5,31.25,15.63,7.82,1.0mgL then
-1The standard series mixed solution of MTMC, Mobucin, the mould prestige of second and Bassa, to be measured behind 0.45 μ m membrane filtration.
Adopt hypervelocity liquid chromatography UV-detector that the standard series mixed solution is analyzed; With MTMC, Mobucin, the mould prestige of second and Bassa peak area separately is that ordinate, mass concentration are horizontal ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately respectively.The testing conditions of choosing is: the C18 chromatographic column; Sampling volume 6.0 μ L; Mobile phase methanol-ultrapure water volume ratio 50:50; Mobile phase methanol-ultrapure water flow velocity 0.8mLmin
-125 ℃ of column temperatures; The detection wavelength is 254nm.
Under identical condition, detect the water sample to be analyzed of above-mentioned processing; According to MTMC, Mobucin, the mould prestige of second and Bassa peak area separately; Utilize MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately accordingly, calculate the mass concentration of MTMC in the water sample, Mobucin, the mould prestige of second and Bassa respectively.
The analytical characteristic amount of MTMC, Mobucin, the mould prestige of second and Bassa: the related coefficient 0.9982 ~ 0.9992 of MTMC, Mobucin, the mould prestige of second and Bassa; Detect and be limited to 0.058 ~ 1.45 μ g L
-1The relative standard deviation of appearance time and peak area is respectively at 0.002% ~ 0.009% and 0.1% ~ 0.5%; The method recovery is 95.8% ~ 104%, and relative standard deviation is 1.52% ~ 3.28%.
Embodiment 3
The water sample pre-service: soak into 5mL methyl alcohol, 5mL ultrapure water successively and the amino solid phase extraction column of activation, subsequent use.Get water sample to be analyzed with 3mLmin
-1On the speed appearance, through amino solid phase extraction column enrichment, water sample all exhaust the back with the drip washing of 3mL ultrapure water, the dry 30min that under vacuum, continues to bleed then, with 4mL methyl alcohol/acetonitrile (V/V)=1/1 with 3mLmin
-1The amino solid phase extraction column of speed wash-out, and collect eluent.After nitrogen dries up eluent under 40 ℃ of conditions, to 1.0mL, treat stratographic analysis with methanol constant volume.
The preparation of N-methyl carbamate pesticide residue thing standard serial solution: difference weighing 0.00100g MTMC, Mobucin, the mould prestige of second and Bassa solid sample, to 1mL, compound concentration is respectively 1000mgL with methanol constant volume
-1MTMC, Mobucin, the mould prestige of second and Bassa standard are mixed and are used liquid, and stepwise dilution becomes that concentration is respectively 500,250,125,62.5,31.25,15.63,7.82,1.0mgL then
-1The standard series mixed solution of MTMC, Mobucin, the mould prestige of second and Bassa, to be measured behind 0.45 μ m membrane filtration.
Adopt hypervelocity liquid chromatography UV-detector that the standard series mixed solution is analyzed; With MTMC, Mobucin, the mould prestige of second and Bassa peak area separately is that ordinate, mass concentration are horizontal ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately respectively.The testing conditions of choosing is: the C18 chromatographic column; Sampling volume 7.0 μ L; Mobile phase methanol-ultrapure water volume ratio 60:40; Mobile phase methanol-ultrapure water flow velocity 1.0mLmin
-130 ℃ of column temperatures; The detection wavelength is 284nm.
Under identical condition, detect the water sample to be analyzed of above-mentioned processing; According to MTMC, Mobucin, the mould prestige of second and Bassa peak area separately; Utilize MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately accordingly, calculate the mass concentration of MTMC in the water sample, Mobucin, the mould prestige of second and Bassa respectively.
The analytical characteristic amount of MTMC, Mobucin, the mould prestige of second and Bassa: the related coefficient 0.9991 ~ 0.9998 of MTMC, Mobucin, the mould prestige of second and Bassa; Detect and be limited to 0.050 ~ 1.60 μ g L
-1The relative standard deviation of appearance time and peak area is respectively at 0.002% ~ 0.008% and 0.1% ~ 0.6%; The method recovery is 91.3% ~ 105%, and relative standard deviation is 1.45% ~ 4.86%.
Embodiment 4
The water sample pre-service: soak into and activation C18 solid phase extraction column with 5mL methyl alcohol, 5mL ultrapure water successively, subsequent use.Get water sample to be analyzed with 4mLmin
-1On the speed appearance, through the enrichment of C18 solid phase extraction column, water sample all exhaust the back with the drip washing of 3mL ultrapure water, the dry 30min that under vacuum, continues to bleed then, with the 5mL methylene chloride with 4mLmin
-1Speed wash-out C18 solid phase extraction column, and collect eluent.After nitrogen dries up eluent under 50 ℃ of conditions, to 1.0mL, treat stratographic analysis with methanol constant volume.
The preparation of N-methyl carbamate pesticide residue thing standard serial solution: difference weighing 0.00100g MTMC, Mobucin, the mould prestige of second and Bassa solid sample, to 1mL, compound concentration is respectively 1000mgL with methanol constant volume
-1MTMC, Mobucin, the mould prestige of second and Bassa standard are mixed and are used liquid, and stepwise dilution becomes that concentration is respectively 500,250,125,62.5,31.25,15.63,7.82,1.0mgL then
-1The standard series mixed solution of MTMC, Mobucin, the mould prestige of second and Bassa, to be measured behind 0.45 μ m membrane filtration.
Adopt hypervelocity liquid chromatography UV-detector that the standard series mixed solution is analyzed; With MTMC, Mobucin, the mould prestige of second and Bassa peak area separately is that ordinate, mass concentration are horizontal ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately respectively.The testing conditions of choosing is: the C18 chromatographic column; Sampling volume 8.0 μ L; Mobile phase methanol-ultrapure water volume ratio 70:30; Mobile phase methanol-ultrapure water flow velocity 1.2mLmin
-140 ℃ of column temperatures; The detection wavelength is 320nm.
Under identical condition, detect the water sample to be analyzed of above-mentioned processing; According to MTMC, Mobucin, the mould prestige of second and Bassa peak area separately; Utilize MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately accordingly, calculate the mass concentration of MTMC in the water sample, Mobucin, the mould prestige of second and Bassa respectively.
The analytical characteristic amount of MTMC, Mobucin, the mould prestige of second and Bassa: the related coefficient 0.9993 ~ 0.9997 of MTMC, Mobucin, the mould prestige of second and Bassa; Detect and be limited to 0.049 ~ 1.48 μ g L
-1The relative standard deviation of appearance time and peak area is respectively at 0.001% ~ 0.007% and 0.2% ~ 0.5%; The method recovery is 92.8% ~ 99.5%, and relative standard deviation is 1.32% ~ 3.38%.
Embodiment 5
The water sample pre-service: soak into and activation Oasis HLB solid phase extraction column with 5mL methyl alcohol, 5mL ultrapure water successively, subsequent use.Get water sample to be analyzed with 5mLmin
-1On the speed appearance, through the enrichment of Oasis HLB solid phase extraction column, water sample all exhaust the back with the drip washing of 3mL ultrapure water, the dry 30min that under vacuum, continues to bleed then, with the 7mL methylene chloride with 5mLmin
-1Speed wash-out Oasis HLB solid phase extraction column, and collect eluent.After nitrogen dries up eluent under 55 ℃ of conditions, to 1.0mL, treat stratographic analysis with methanol constant volume.
The preparation of N-methyl carbamate pesticide residue thing standard serial solution: difference weighing 0.00100g MTMC, Mobucin, the mould prestige of second and Bassa solid sample, to 1mL, compound concentration is respectively 1000mgL with methanol constant volume
-1MTMC, Mobucin, the mould prestige of second and Bassa standard are mixed and are used liquid, and stepwise dilution becomes that concentration is respectively 500,250,125,62.5,31.25,15.63,7.82,1.0mgL then
-1The standard series mixed solution of MTMC, Mobucin, the mould prestige of second and Bassa, to be measured behind 0.45 μ m membrane filtration.
Adopt hypervelocity liquid chromatography UV-detector that the standard series mixed solution is analyzed; With MTMC, Mobucin, the mould prestige of second and Bassa peak area separately is that ordinate, mass concentration are horizontal ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately respectively.The testing conditions of choosing is: the C18 chromatographic column; Sampling volume 10.0 μ L; Mobile phase methanol-ultrapure water volume ratio 90:10; Mobile phase methanol-ultrapure water flow velocity 1.5mLmin
-150 ℃ of column temperatures; The detection wavelength is 340nm.
Under identical condition, detect the water sample to be analyzed of above-mentioned processing; According to MTMC, Mobucin, the mould prestige of second and Bassa peak area separately; Utilize MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately accordingly, calculate the mass concentration of MTMC in the water sample, Mobucin, the mould prestige of second and Bassa respectively.
The analytical characteristic amount of MTMC, Mobucin, the mould prestige of second and Bassa: the related coefficient 0.9989 ~ 0.9996 of MTMC, Mobucin, the mould prestige of second and Bassa; Detect and be limited to 0.052 ~ 1.59 μ g L
-1The relative standard deviation of appearance time and peak area is respectively at 0.001% ~ 0.009% and 0.1% ~ 0.6%; The method recovery is 93.6% ~ 107%, and relative standard deviation is 1.51% ~ 3.85%.
The experiment proof; Combine with hypervelocity liquid chromatography ultraviolet detection through SPE; The data result that N-methyl carbamate pesticide residue object detecting method of the present invention obtains under the optimization experiment condition; Can be applied to the mould prestige of MTMC, Mobucin, second and the detection of Bassa in the environment water,, be easy to apply for analyzing fast, simultaneously of MTMC, Mobucin, the mould prestige of second and Bassa in the environment water provides feasible.
Although top combination is described the preferred embodiments of the present invention; But the present invention is not limited to above-mentioned embodiment, and above-mentioned embodiment only is schematically, is not restrictive; Those of ordinary skill in the art is under enlightenment of the present invention; Not breaking away under the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, these all belong within protection scope of the present invention.
Claims (10)
1. a N-methyl carbamate pesticide residue object detecting method is characterized in that, said N-methyl carbamate pesticide residue thing comprises MTMC, Mobucin, the mould prestige of second and Bassa, and this method is carried out according to following steps:
A. soak into and the activation solid phase extraction column with methyl alcohol, ultrapure water successively, subsequent use;
B. get water sample to be analyzed with 1 ~ 5mLmin
-1Appearance on the speed through the solid phase extraction column enrichment, treats that water sample all exhausts the back and uses ultrapure water drip washing;
C. at the dry solid phase extraction column of vacuum lower pumping;
D. use 1 ~ 7mL eluant, eluent with 1 ~ 5mLmin
-1Speed wash-out solid phase extraction column, and collect eluent;
E. behind nitrogen drying eluent under 20 ~ 55 ℃ of conditions, methanol constant volume;
F. prepare N-methyl carbamate pesticide residue system row and mix the methyl alcohol standard solution;
G. the N-methyl carbamate pesticide residue system row that adopt hypervelocity liquid chromatography UV-detector analytical procedure (f) to be prepared mix the methyl alcohol standard solution; With its mass concentration is that horizontal ordinate, peak area are ordinate drawing standard curve, obtains MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately;
H. the water sample to be analyzed that adopts hypervelocity liquid chromatography UV-detector analytical procedure (e) to obtain;
I. the mould prestige of MTMC, Mobucin, second and the Bassa peak area separately that obtain according to step (h); Utilize step (g) gained MTMC, Mobucin, the mould prestige of second and Bassa typical curve regression equation separately, calculate the mass concentration of MTMC in the water sample to be analyzed, Mobucin, the mould prestige of second and Bassa respectively;
Wherein, Hypervelocity liquid chromatography ultraviolet detection condition in step (g) and the step (h) is following: the C18 chromatographic column; Sampling volume is 5 ~ 10 μ L, and the volume ratio of mobile phase methanol-ultrapure water is 40:60 ~ 90:10, and the flow velocity of mobile phase methanol-ultrapure water is 0.5～1.5mLmin
-1, column temperature is 20 ~ 50 ℃, the ultraviolet detection wavelength is 200 ~ 340nm.
2. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1; It is characterized in that the solid phase extraction column in said step (a) to the step (d) is selected from vinylpyrrolidone-divinylbenzene polymer pillar, C18 pillar or amino pillar.
3. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that, the upward appearance speed of water sample to be analyzed is 3mLmin in the said step (b)
-1
4. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that the eluant, eluent in the said step (d) is selected from methyl alcohol/acetonitrile that methyl alcohol, methylene chloride or volume are 1:1.
5. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that the eluant, eluent consumption in the said step (d) is 5mL.
6. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that the elution speed in the said step (d) is 3mLmin
-1
7. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that, the volume ratio of mobile phase methanol-ultrapure water is 70:30 in said step (g) and the step (h).
8. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that, the flow velocity of mobile phase methanol-ultrapure water is 0.5mLmin in said step (g) and the step (h)
-1
9. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that the column temperature in said step (g) and the step (h) is 40 ℃.
10. a kind of N-methyl carbamate pesticide residue object detecting method according to claim 1 is characterized in that the ultraviolet detection wavelength in said step (g) and the step (h) is 284nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106383192A (en) * | 2016-11-09 | 2017-02-08 | 无锡艾科瑞思产品设计与研究有限公司 | Detection method of mobucin |
| CN107422048A (en) * | 2017-04-10 | 2017-12-01 | 中国水产科学研究院黑龙江水产研究所 | Water sample level Four bar flight time mass spectrum method for combined use is identified without standard items rapid screening |
| CN108445128A (en) * | 2018-03-01 | 2018-08-24 | 中国热带农业科学院农产品加工研究所 | A kind of method of carbamates determination of drug residues in birds, beasts and eggs |
| CN110068637A (en) * | 2019-03-28 | 2019-07-30 | 厦门泓益检测有限公司 | A kind of measuring method based on sumiewei residue in dynamic derived food |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1584557A (en) * | 2004-06-15 | 2005-02-23 | 厦门大学 | Rapid measuring method for residual carbamate pesticide weight in vegetables |
| WO2011081787A2 (en) * | 2009-12-15 | 2011-07-07 | Fmc Corporation | Sustained-release silica microcapsules |
| CN102336868A (en) * | 2010-07-21 | 2012-02-01 | 天津科技大学 | Preparation method of trace meta-tolyl-N-methylcarbamate-enriched molecular imprinting polymer |
-
2012
- 2012-07-18 CN CN201210249752.2A patent/CN102749404B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1584557A (en) * | 2004-06-15 | 2005-02-23 | 厦门大学 | Rapid measuring method for residual carbamate pesticide weight in vegetables |
| WO2011081787A2 (en) * | 2009-12-15 | 2011-07-07 | Fmc Corporation | Sustained-release silica microcapsules |
| CN102336868A (en) * | 2010-07-21 | 2012-02-01 | 天津科技大学 | Preparation method of trace meta-tolyl-N-methylcarbamate-enriched molecular imprinting polymer |
Non-Patent Citations (8)
| Title |
|---|
| KUN QIAN ET AL.: "Preparation and application of a molecularly imprinted polymer for the determination of trace metolcarb in food matrices by high performance liquid chromatography", 《JOURNAL OF SEPARATION SCIENCE》 * |
| YANG RU-ZHEN ET AL.: "Dispersive Solid-Phase Extraction Cleanup Combined with Accelerated Solvent Extraction for the Determination of Carb", 《J CHROMATOGR SCI》 * |
| 吴国旭等: "94种化合物高效液相色谱分析中紫外吸收波长的选择", 《农药》 * |
| 文君等: "高效液相色谱法同时测定蔬菜中5种氨基甲酸酯类农药", 《中国卫生检验杂志》 * |
| 王晓楠等: "水中氨基甲酸酯类农残前处理及色谱检测研究进展", 《化学分析计量》 * |
| 陈剑刚等: "高效液相色谱-质谱法分析测定水中氨基甲酸酯", 《分析化学》 * |
| 陈晓红等: "固相萃取-高效液相色谱柱后衍生法测定水中痕量N-甲基氨基甲酸酯", 《中国卫生检验杂志》 * |
| 黄志波等: "超高效液相色谱-质谱／质谱法测定叶菜中11种氨基甲酸酯农药残留", 《热带农业科学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106383192A (en) * | 2016-11-09 | 2017-02-08 | 无锡艾科瑞思产品设计与研究有限公司 | Detection method of mobucin |
| CN107422048A (en) * | 2017-04-10 | 2017-12-01 | 中国水产科学研究院黑龙江水产研究所 | Water sample level Four bar flight time mass spectrum method for combined use is identified without standard items rapid screening |
| CN108445128A (en) * | 2018-03-01 | 2018-08-24 | 中国热带农业科学院农产品加工研究所 | A kind of method of carbamates determination of drug residues in birds, beasts and eggs |
| CN108445128B (en) * | 2018-03-01 | 2020-05-26 | 中国热带农业科学院农产品加工研究所 | Method for measuring residual amount of carbamate drugs in eggs |
| CN110068637A (en) * | 2019-03-28 | 2019-07-30 | 厦门泓益检测有限公司 | A kind of measuring method based on sumiewei residue in dynamic derived food |
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| CN102749404B (en) | 2014-07-16 |
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