CN101846660B - Determination method of trace furadan - Google Patents
Determination method of trace furadan Download PDFInfo
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- CN101846660B CN101846660B CN 201010176402 CN201010176402A CN101846660B CN 101846660 B CN101846660 B CN 101846660B CN 201010176402 CN201010176402 CN 201010176402 CN 201010176402 A CN201010176402 A CN 201010176402A CN 101846660 B CN101846660 B CN 101846660B
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Abstract
The invention discloses a determination method of trace furadan, comprising the following step of: preparing a standard series carbinol solution of furadan, obtaining a regression equation of standard curve by the high performance liquid chromatography and fluorescence method; infiltrating and eluting the solid phase extraction device, collecting the water sample to be analyzed for enrichment, eluting by eluant and collecting the eluant, drying to constant volume; performing the chromatographic analysis to the preprocessing sample by the high performance liquid chromatography and fluorescence method, and calculating the concentration of furadan in water according to the regression equation of standard curve. The invention can solve the problems of poor sensitivity and low recovery rate for the determination of trace furadan in the environment by applying the existing technique, meanwhile overcome the disadvantages of complex operation process, high requirement to the analysts and high operation cost in the determination method of furadan by using existing determination method.
Description
Technical field
The present invention relates to a kind ofly by means of the chemistry of measuring material or physical property is tested or the method for amalyzing substances, specifically, relate to a kind of red method of trace furans of measuring in the environmental analysis field.
Background technology
Furans red (Carbofuran) is a kind of high malicious carbamate insecticides, and it is widely used in cereal crops, thereby causes the red residue of the furans that possibly contain trace in environment water, food, crop and the animal feed, serious threat human beings'health safety.
Because the residual quantity of furans pellet in environment is lower, often is low to moderate μ g/L
-1Even ng/L
-1Level, this has brought difficulty with regard to giving the red detection of trace furans.The sample pretreatment technology is to solve the important means that trace analysis detects, and at present, the red preconditioning technique of furans mainly contains liquid-liquid extraction method, solid phase extraction 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 red analysis of trace furans in the environment that sensitivity is not enough, the recovery is low etc.Therefore set up be suitable for the trace furans red detect efficient, fast, preprocess method that the recovery is high has very important significance.
In addition, the red detection method of furans mainly comprises vapor-phase chromatography (GC), gas phase-mass spectrometry method (GC-MS), high performance liquid chromatogram-mass spectrometry method (LC-MS), post-column derivation high performance liquid chromatography fluorescence detection, high performance liquid chromatography-uv detection method (LC-UV) etc.Because the thermal stability of furans pellet is strong, the temperature that causes GC to analyze is higher, and working time is longer; And MS is high to instrument requirement, is difficult for promoting; Post-column derivation high performance liquid chromatography fluorescence detection needs after chromatographic column, to increase the equipment of deriving automatically, complex operation; Conventional UV detector sensitivity is not high.Therefore, quick, easy, the economic red detection method ten minutes of furans necessity of development.
In new " drinking water sanitary standard " [GB/T 5750.9 2006,369-372] of formulating, the red analytical approach of furans is that sample separates with liquid chromatography after liquid-liquid extraction concentrates, and carries out post column derivatization again, detects with fluorescence detector.The sample pretreatment process of this method is loaded down with trivial details, and consumption of organic solvent is big; The post-column derivation reaction requires special derivative reagent and equipment, and has certain interference with the change of elution time and fluorescence intensity.
Summary of the invention
The technical matters that the present invention will solve provides a kind of sensitivity, quick, reliable, the economic red assay method of trace furans that is used for, and can solve prior art and be applied to the problem that existing sensitivity was not enough, the recovery is low when the trace furans is red in the environment detected; Overcome the red detection method operation steps complicacy of existing furans simultaneously, the analyst required shortcomings such as height, operation cost height.
In order to solve the problems of the technologies described above, the present invention is achieved through following technical scheme:
The assay method that a kind of trace furans is red, this method is carried out according to following steps:
(1) the red standard series methanol solution of preparation furans is used the high performance liquid chromatography fluorescence spectrometry, and concentration and the peak area drawing standard curve red according to furans, obtains the typical curve regression equation;
(2) methyl alcohol-ultrapure water soaks into the drip washing solid-phase extraction device, gets water sample to be analyzed with 1～5mLmin
-1Speed is carried out example enrichment, and 1～7mL eluant, eluent is with 1～3mLmin
-1Speed drip washing is also collected eluent, 20～55 ℃ of dry leacheates of inert gas, methanol constant volume;
(3) under the test condition identical with step (1), adopt the high performance liquid chromatography fluorescence method that the sample that step (2) obtains is carried out stratographic analysis, go out the red concentration of furans in the water sample to be analyzed according to step (1) gained typical curve regression equation calculation.
High performance liquid chromatography fluoroscopic examination condition in said step (1) and the step (3) is: C18 chromatographic column, sampling volume are 5～10 μ L, and moving phase is that volume ratio is methyl alcohol-ultrapure water of 40: 60～65: 35, and flow velocity is 0.5～1.5mLmin
-1, 20～40 ℃ of column temperatures, fluorescence exciting wavelength are 285nm, emission wavelength is 320nm.
Technical scheme as further qualification:
The volume ratio of said mobile phase methanol-ultrapure water is 50: 50.
The flow velocity of said moving phase is 1mLmin
-1
Said column temperature is 35 ℃.
Enrichment speed in the said step (2) is 3mLmin
-1
Eluant, eluent is tetrahydrofuran, methyl alcohol or ethyl acetate in the said step (2).
The consumption of eluant, eluent is 5mL in the said step (2).
The elution speed of eluant, eluent is 3mLmin in the said step (2)
-1
The invention has the beneficial effects as follows:
The invention provides a kind of SPE combines with the high performance liquid chromatography fluorescence analysis and detects the red method of trace furans; Compare with the drinking water standard method; This method has obtained several essential condition: adopt the method for SPE to replace the liquid-liquid extraction mode that sample is carried out pre-treatment, water sample enrichment speed to be analyzed is 1～5mLmin
-1, leacheate preferably adopts tetrahydrofuran in the sample pretreatment process, and its consumption is in 1.0～7.0mL scope, and drip washing speed is 1～3mLmin
-1The testing conditions of high performance liquid chromatography fluorescence analysis is that sampling volume 5～10 μ L, mobile phase methanol-ultrapure water volume ratio are 40: 60～65: 35, flow velocity 0.5～1.5mLmin
-1, 20～40 ℃ of column temperatures, fluorescence exciting wavelength 285nm, emission wavelength 320nm, and The effect equation of linear regression, related coefficient and the range of linearity.The detection limit of furans pellet is by 0.125 μ g L
-1Be reduced to 3ng L
-1, reduced by 1～2 one magnitude; The order of magnitude of the range of linearity expands to 1000 by 100; Relative standard deviation is reduced to 1.1%～4.2% from 4.6%～8.9%; The recovery rises to 94.3%～99.7% by 81.0%～120%.In sum, the present invention can obtain better precision and recovery of standard addition, and is highly sensitive, and step is simple to operation, and saved expense.
Embodiment
Through concrete embodiment the present invention is made further detailed description below:
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 Agilent 1200 RRLC high performance liquid chromatographs; 12 solid-phase extraction devices of Agilent, C18 solid phase extraction column (500mg/3mL); The HSC-24B Nitrogen evaporator; Chromatographic column is Eclipse XDB C18 (150mm * 4.6mm * 5 μ m).
Embodiment 1
The preparation of the red standard serial solution of furans: pipette 200mgL
-1The red standard reserving solution 12.5mL of furans in the 25mL volumetric flask, methanol constant volume, compound concentration is 100mgL
-1The red standard of furans is used liquid, then stepwise dilution be 50.0,10.0,5.0,1.0,0.5,0.1,0.05mgL
-1Standard serial solution, to be measured behind 0.45 μ m membrane filtration.
Sample pretreatment: soak into and four SPE C18 of drip washing pillar with 5mL methyl alcohol, 5mL ultrapure water successively, activation is subsequent use.Get the 200mL water sample, add 5,10,15 μ gL respectively
-1The red standard of furans is used liquid, with 1mLmin
-1Speed after the enrichment of C18 pillar, with 1mL methyl alcohol with 1mLmin
-1Speed drip washing solid phase extraction column, and collect leacheate.Under 20 ℃ of conditions, after argon gas dries up, to 1.0mL, treat stratographic analysis with methanol constant volume.
High performance liquid chromatography fluoroscopic examination condition: adopt liquid chromatograph; Eclipse XDB C18 chromatographic column; Sampling volume 5.0 μ L; Mobile phase methanol-ultrapure water volume ratio 40: 60; Flow velocity 0.5mLmin
-120 ℃ of column temperatures; Fluorescence exciting wavelength 285nm, emission wavelength 320nm.
Use the red standard serial solution of high performance liquid chromatography fluorescence spectrometry furans under these conditions, and concentration and the peak area drawing standard curve red according to furans, the typical curve regression equation obtained; Under identical test condition, the sample after the SPE is carried out stratographic analysis, carry out qualitative analysis according to appearance time, peak area carries out quantitative test to trace furans pellet, calculates the red concentration of furans in the water sample to be analyzed.
The analytical characteristic amount that furans is red: the red sample introduction 5.0 μ L of the trace furans after the processing obtain the typical curve regression equation by chem workstation, and calculate the correlation analysis characteristic quantity.The concentration of furans pellet is at 0.1～50.0mgL
-1Be favorable linearity with peak area in the scope, linear equation is y=2.983x-0.2799 (R
2=0.9999), and to obtain the red concentration limit of furans according to 3 times of signal to noise ratio (S/N ratio)s be 30ngL
-1To 2.5mgL
-1Red continuous 6 sample introductions of furans, the relative standard deviation of appearance time and peak area is respectively 1.6% and 4.2%, and the red average recovery rate of furans is 95.7%～98.4%.
Embodiment 2
Except that the sample pretreatment condition was different with high performance liquid chromatography fluoroscopic examination condition, other steps were all identical with embodiment 1.
Sample pretreatment: soak into and four SPE C18 of drip washing pillar with 5mL methyl alcohol, 5mL ultrapure water successively, activation is subsequent use.Get the 200mL water sample, add 5,10,15 μ gL respectively
-1The red standard of furans is used liquid, with 2mLmin
-1Speed after the enrichment of C18 pillar, with 3mL ethyl acetate with 2mLmin
-1Speed drip washing solid phase extraction column, and collect leacheate.Under 30 ℃ of conditions, after argon gas dries up, to 1.0mL, carry out stratographic analysis with methanol constant volume.
High performance liquid chromatography fluoroscopic examination condition: adopt liquid chromatograph; Eclipse XDB C18 chromatographic column; Sampling volume 6.0 μ L; Mobile phase methanol-ultrapure water volume ratio 55: 45; Flow velocity 0.8mLmin
-125 ℃ of column temperatures; Fluorescence exciting wavelength 285nm, emission wavelength 320nm.
The analytical characteristic amount that furans is red: the red sample introduction 6.0 μ L of the trace furans after the processing obtain the typical curve regression equation by chem workstation, and calculate the correlation analysis characteristic quantity.The concentration of furans pellet is at 0.1～50.0mgL
-1Be favorable linearity with peak area in the scope, linear equation is y=3.018x-0.1639 (R
2=0.9999), and to obtain the red concentration limit of furans according to 3 times of signal to noise ratio (S/N ratio)s be 10ngL
-1To 2.5mgL
-1Red continuous 6 sample introductions of furans, the relative standard deviation of appearance time and peak area is respectively 1.9% and 3.3%, and the red average recovery rate of furans is 94.3%～96.2%.
Embodiment 3
Except that the sample pretreatment condition was different with high performance liquid chromatography fluoroscopic examination condition, other steps were all identical with embodiment 1.
Sample pretreatment: soak into and four C18 pillars of drip washing SPE with 5mL methyl alcohol, 5mL ultrapure water successively, activation is subsequent use.Get the 200mL water sample, add 5,10,15 μ gL respectively
-1The red standard of furans is used liquid, with 3mLmin
-1Speed after the enrichment of C18 pillar, with the 4mL tetrahydrofuran with 2mLmin
-1Speed drip washing solid phase extraction column, and collect leacheate.Under 35 ℃ of conditions, after argon gas dries up, to 1.0mL, carry out stratographic analysis with methanol constant volume.
High performance liquid chromatography fluoroscopic examination condition: adopt liquid chromatograph; Eclipse XDB C18 chromatographic column; Sampling volume 8.0 μ L; Mobile phase methanol-ultrapure water volume ratio 50: 50; Flow velocity 1.0mLmin
-130 ℃ of column temperatures; Fluorescence exciting wavelength 285nm, emission wavelength 320nm.
The analytical characteristic amount that furans is red: the red sample introduction 8.0 μ L of the trace furans after the processing obtain the typical curve regression equation by chem workstation, and calculate the correlation analysis characteristic quantity.The concentration of furans pellet is at 0.05～50.0mgL
-1Be favorable linearity with peak area in the scope, linear equation is y=3.000x-0.2993 (R
2=0.9999), and to obtain the red concentration limit of furans according to 3 times of signal to noise ratio (S/N ratio)s be 3ngL
-1To 0.5mgL
-1Red continuous 6 sample introductions of furans, the relative standard deviation of appearance time and peak area is respectively 1.1% and 3.8%, and the red average recovery rate of furans is 96.3%～99.7%.
Embodiment 4
Except that the sample pretreatment condition was different with high performance liquid chromatography fluoroscopic examination condition, other steps were all identical with embodiment 1.
Sample pretreatment: soak into and four C18 pillars of drip washing SPE with 5mL methyl alcohol, 5mL ultrapure water successively, activation is subsequent use.Get the 200mL water sample, add 5,10,15 μ gL respectively
-1The red standard of furans is used liquid, with 4mLmin
-1Speed after the enrichment of C18 pillar, with the 5mL tetrahydrofuran with 3mLmin
-1Speed drip washing solid phase extraction column, and collect leacheate.Under 45 ℃ of conditions, after argon gas dries up, to 1.0mL, carry out stratographic analysis with methanol constant volume.
High performance liquid chromatography fluoroscopic examination condition: adopt liquid chromatograph; Eclipse XDB C18 chromatographic column; Sampling volume 9.0 μ L; Mobile phase methanol-ultrapure water volume ratio 60: 40; Flow velocity 1.2mLmin
-135 ℃ of column temperatures; Fluorescence exciting wavelength 285nm, emission wavelength 320nm.
The analytical characteristic amount that furans is red: the red sample introduction 9.0 μ L of the trace furans after the processing obtain the typical curve regression equation by chem workstation, and calculate the correlation analysis characteristic quantity.The concentration of furans pellet is at 0.05～50.0mgL
-1Be favorable linearity with peak area in the scope, linear equation is y=3.012x-0.2871 (R
2=0.9999), and to obtain the red concentration limit of furans according to 3 times of signal to noise ratio (S/N ratio)s be 3.2ngL
-1To 0.5mgL
-1Red continuous 6 sample introductions of furans, the relative standard deviation of appearance time and peak area is respectively 1.1% and 3.4%, and the red average recovery rate of furans is 95.1%～99.5%.
Embodiment 5
Except that the sample pretreatment condition was different with high performance liquid chromatography fluoroscopic examination condition, other steps were all identical with embodiment 1.
Sample pretreatment: soak into and four C18 pillars of drip washing SPE with 5mL methyl alcohol, 5mL ultrapure water successively, activation is subsequent use.Get the 200mL water sample, add 5,10,15 μ gL respectively
-1The red standard of furans is used liquid, with 5mLmin
-1Speed after the enrichment of C18 pillar, with the 7mL tetrahydrofuran with 3mLmin
-1Speed drip washing solid phase extraction column, and collect leacheate.Under 55 ℃ of conditions, after argon gas dries up, to 1.0mL, carry out stratographic analysis with methanol constant volume.
High performance liquid chromatography fluoroscopic examination condition: adopt liquid chromatograph; Eclipse XDB C18 chromatographic column; Sampling volume 10.0 μ L; Mobile phase methanol-ultrapure water volume ratio 65: 35; Flow velocity 1.5mLmin
-140 ℃ of column temperatures; Fluorescence exciting wavelength 285nm, emission wavelength 320nm.
The analytical characteristic amount that furans is red: the red sample introduction 10.0 μ L of the trace furans after the processing obtain the typical curve regression equation by chem workstation, and calculate the correlation analysis characteristic quantity.The concentration of furans pellet is at 0.05～50.0mgL
-1Be favorable linearity with peak area in the scope, linear equation is y=3.050x-0.2749 (R
2=0.9999), and to obtain the red concentration limit of furans according to 3 times of signal to noise ratio (S/N ratio)s be 3.5ngL
-1To 0.5mgL
-1Red continuous 6 sample introductions of furans, the relative standard deviation of appearance time and peak area is respectively 1.2% and 2.6%, and the red average recovery rate of furans is 95.3%～98.1%.
The experiment proof; Through combining SPE and high performance liquid chromatography fluorescence chromatography (SPE-LC-FLD); The data result that the red assay method of this trace furans obtains under the optimization experiment condition, detection limit, the range of linearity and the recovery red with being applied to furans under the other technologies optimum condition compare, and detection limit has reduced by 1～2 one magnitude; The range of linearity has been expanded 1 one magnitude, and the recovery is better.Concrete data such as following table:
Although combine accompanying drawing that the preferred embodiments of the present invention are described above; 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 (8)
1. the red assay method of a trace furans is characterized in that this method is carried out according to following steps:
(1) the red standard series methanol solution of preparation furans is used the high performance liquid chromatography fluorescence spectrometry, and concentration and the peak area drawing standard curve red according to furans, obtains the typical curve regression equation;
(2) methyl alcohol-ultrapure water soaks into drip washing SPE C18 pillar, gets water sample to be analyzed with 1～5mLmin
-1Speed is carried out example enrichment, and 1～7mL eluant, eluent is with 1～3mLmin
-1Speed drip washing is also collected eluent, and wherein eluant, eluent is tetrahydrofuran, methyl alcohol or ethyl acetate, 20～55 ℃ of dry leacheates of inert gas, methanol constant volume;
(3) under the test condition identical with step (1), adopt the high performance liquid chromatography fluorescence method that the sample that step (2) obtains is carried out stratographic analysis, go out the red concentration of furans in the water sample to be analyzed according to step (1) gained typical curve regression equation calculation;
Wherein, the high performance liquid chromatography fluoroscopic examination condition in said step (1) and the step (3) is: C18 chromatographic column, moving phase are that volume ratio is methyl alcohol-ultrapure water of 40: 60～65: 35, and fluorescence exciting wavelength is 285nm, and emission wavelength is 320nm.
2. the red assay method of a kind of trace furans according to claim 1 is characterized in that the sampling volume of high performance liquid chromatography fluoroscopic examination is 5～10 μ L in said step (1) and the step (3), and flow velocity is 0.5～1.5mLmin
-1, 20～40 ℃ of column temperatures.
3. the red assay method of a kind of trace furans according to claim 1 is characterized in that the volume ratio of said mobile phase methanol-ultrapure water is 50: 50.
4. the red assay method of a kind of trace furans according to claim 1 is characterized in that the flow velocity of said moving phase is 1mLmin
-1
5. the red assay method of a kind of trace furans according to claim 1 is characterized in that said column temperature is 35 ℃.
6. according to the red assay method of each described a kind of trace furans in the claim 1 to 5, it is characterized in that the enrichment speed in the said step (2) is 3mLmin
-1
7. according to the red assay method of each described a kind of trace furans in the claim 1 to 5, it is characterized in that the consumption of eluant, eluent is 5mL in the said step (2).
8. according to the red assay method of each described a kind of trace furans in the claim 1 to 5, it is characterized in that the elution speed of eluant, eluent is 3mLmin in the said step (2)
-1
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| CN1632538A (en) * | 2003-12-25 | 2005-06-29 | 中国科学院大连化学物理研究所 | Fast detection method with high sensitivity for pesticide residue |
| CN101398414A (en) * | 2008-10-15 | 2009-04-01 | 上海市公安局刑事侦查总队 | Method for qualitatively screening 242 kinds of compounds by liquid phase chromatography-mass spectra at the same times |
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| CN1632538A (en) * | 2003-12-25 | 2005-06-29 | 中国科学院大连化学物理研究所 | Fast detection method with high sensitivity for pesticide residue |
| CN101398414A (en) * | 2008-10-15 | 2009-04-01 | 上海市公安局刑事侦查总队 | Method for qualitatively screening 242 kinds of compounds by liquid phase chromatography-mass spectra at the same times |
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