CN102221589A - Method for detecting residual quantity of pesticides in vegetable sample by utilizing liquid chromatogram-high resolution mass spectrometer - Google Patents
Method for detecting residual quantity of pesticides in vegetable sample by utilizing liquid chromatogram-high resolution mass spectrometer Download PDFInfo
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Abstract
The invention relates to a method for detecting the residual quantity of pesticides in a vegetable sample by utilizing a liquid chromatogram-high resolution mass spectrometer, which belongs to the technical field of a food safety detecting. The method provided by the invention comprises the following steps: 1) extracting the residual acetonitrile in the sample; 2) carrying out the dispersion solid-phase extraction and purification on a sample extraction solution; 3) detecting by utilizing the liquid chromatogram-high resolution mass spectrometer; and 4) analyzing the result. In the method provided by the invention, the quality accuracy of 27 pesticides is less than 1ppm; the detection limit is 0.01-0.05mg/kg; the addition recovery rate is 80-100%; and the relative standard deviation is less than 15%.
Description
Technical field
The invention belongs to the food safety detection technical field, be specifically related to the method that the liquid chromatography high resolution mass spectrum detects the many residual quantities of agricultural chemicals in the vegetable sample.
Background technology
Over nearly 20 years, agricultural chemicals is at proportion of crop planting and use increasingly extensively in producing, and it takes place, promotes growth, improves output and the effect that improves aspect the product quality is very significant reducing disease and pest, has become the indispensable material base of modern agriculture.But the use of agricultural chemicals can cause the delay of crop drug disposition undoubtedly or accumulate, and enters the human body and the ecosystem in residual mode.The abuse or illegally use the phenomenon of agricultural chemicals still to exist, its harm to the mankind and environment mainly is chronic, at a specified future date and cumulative, residues of pesticides in the agricultural product have become generally acknowledged agricultural and environmental problem, have been at present both at home and abroad pesticide research, the important content developing, use and manage to residual monitoring and control.
Now, the detection of persticide residue mainly contains vapor-phase chromatography, liquid phase chromatography, gas chromatography-mass spectrography and liquid chromatography-tandem mass spectrometry method in the vegetables.Vapor-phase chromatography and liquid phase chromatography mainly are to rely on chromatographic resolution, during at samples such as complex matrices such as leek, garlics, have certain difficulty on agricultural chemicals qualitative; Gas chromatography-mass spectrography and liquid chromatography-tandem mass spectrometry method mainly are to utilize the Low Resolution Mass Spectra detecting device, the fragment that produces by compound structure fracture or rearrangement carries out sample detection, but, when analyzing a plurality of compound at the same time, owing to be subjected to the influence of sweep velocity etc., the sensitivity meeting is a greater impact, and is higher to the chromatogram separation requirement.Yet, analyze the accurate mass number and the abundance of agricultural chemicals list isotope and heavy isotope according to the high resolution mass spectrum detecting device, and then easily the reliable element of supposition is formed, improved accuracy and the reliability of agricultural chemicals on qualitative and quantitative, avoided a chromatography and quadrupole rod Low Resolution Mass Spectra difficult problem high the chromatogram separation requirement.
Because residues of pesticides content in vegetables is extremely low, above-mentioned several method improves signal to noise ratio (S/N ratio) when detecting method generally has two kinds of approach, the one, set about from the specimen preparation link, utilize the whole bag of tricks to remove impurity and non-target compound as much as possible, the concentrating sample of maximum multiple, reduce and disturb, to reach the purpose of research, this method difficulty in practical operation is very big; Another kind of approach is the characteristic according to target compound, selects the specific detection device for use, reduces background interference as far as possible.And actual sample is given qualitative and is quantitatively brought very big influence because the difference of regional condition, the matrix of vegetables own when measuring, is subjected to non-target compound to disturb.
At present domestic less to the research of avoiding disturbing effect by the accurate mass number that extracts agricultural chemicals, many residual quantities of agricultural chemicals examination criteria concentrates on gas chromatography and the liquid chromatography-tandem mass spectrometry mostly in the agricultural product of having formulated, to the accurate mass number that uses high resolution mass spectrum to extract agricultural chemicals detect residues of pesticides, reducing to qualitative and quantitatively disturb aspect the difficult problem also not detecting industry and do not cause concern, only have patent to adopt gas chromatograph-high resolved flight time mass spectrum to detect carbazole compound in the crude oil in petrochemical industry.
Summary of the invention
Problem at the prior art existence, the objective of the invention is to design provides a kind of quick, easy, highly sensitive, and effectively reduces or eliminates the technical scheme of disturbing the liquid chromatography high resolution mass spectrum detection method of pesticide multi-residues amount from the complex matrices of vegetables.
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that may further comprise the steps:
1) acetonitrile of residues of pesticides extracts in the sample
Take by weighing 25～50g vegetable sample, add 25～50ml acetonitrile, carrying out high speed dispersion handles, obtain the mixing homogenate solution formed by vegetables matrix, water and acetonitrile, in above-mentioned homogenate solution, add 15～25g complex salt reagent of saltouing, carry out high speed dispersion again and handle, carry out centrifugally operated, standing demix then;
2) the dispersion Solid-Phase Extraction of sample extraction solution purifies
Get 2～6ml upper strata acetonitrile, add 0.6～1.8g anhydrous magnesium sulfate, 0.05～0.2g N-propyl group-ethylenediamine (PSA) and 0.05～0.2gC respectively
18, the centrifuging and taking of vibrating again supernatant, supernatant are crossed the organic filter membrane of 0.22 μ m, promptly obtain sample solution;
3) use liquid chromatography-high-resolution mass spectrometer to detect
A) preparation of standard solution: accurately taking by weighing the standard items agricultural chemicals respectively, is acetone-toluene solution dissolving of 3:7 with volume ratio, is made into the standard inventory solution of 1.0mg/mL respectively, according to the response of each agricultural chemicals, becomes standard operation liquid with dilution in acetonitrile during use;
B) use liquid chromatography-high resolution mass spectroscope examination criteria working fluid and the sample solution after purifying: draw standard operation liquid and sample solution respectively by automatic sampler, inject liquid chromatography-high resolution mass spectroscope, residues of pesticides are separated through liquid-phase chromatographic column in the sample solution, and the high resolution mass spectrum full scan detects;
4) interpretation of result
The structure of database: with ToxID software establishment step 3) the compound molecule formula database information table of standard items agricultural chemicals in;
Qualitative and quantitative: the accurate mass number with the quasi-molecular ion peak of compound is qualitative ion and quota ion; Mass concentration X with standard operation liquid is a horizontal ordinate, and the peak area Y of quota ion is an ordinate, the drawing standard working curve, and it is quantitative with standard working curve sample to be carried out external standard method; Carry out qualitative with chromatographic peak retention time that occurs in the sample solution and qualitative ion (accurate mass number).
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that in the described step 1) that the complex salt reagent of saltouing is anhydrous magnesium sulfate and sodium chloride mix reagent, anhydrous magnesium sulfate and sodium chloride mass ratio 10:1 in anhydrous magnesium sulfate and the sodium chloride mix reagent.
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that in the described step 1) adding in the vegetable sample behind the acetonitrile homogenate 1～3min under dispersion machine medium speed 8000～12000 r/min, add the complex salt homogenate 0.5～2min under rotating speed 8000～12000 r/min that saltouts behind the reagent, at last centrifugal 4～6min under 3000～5000 rpm in hydro-extractor.
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that described step 2) at the middle and upper levels acetonitrile add anhydrous magnesium sulfate, N-propyl group-ethylenediamine (PSA) and C18,0.5～2min, centrifugal 2～4min under hydro-extractor 8 000～12 000 r/min then vibrate on the vortex oscillator.
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that the standard items agricultural chemicals is acephatemet, orthene, omethoate, Aldicarb sulfoxide, Azodrin, carbendazim, Aldicarb sulfone, probenazole, 3-hydroxyl carbofuran, Imidacloprid, Rogor, tricyclazole, Aphox, carbofuran, carbaryl, paclobutrazol, phonetic mould amine, triazolone, Hostathion, propiconazole, alachlor, Acetochlor, Difenoconazole, Quizalotop-ethyl, butachlor, pyridaben and Avermectin in the described step 3).
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that liquid phase chromatogram condition in the described step 3): chromatographic column: XDB-C18,1.8 μ m, 4.6 * 50mm; Moving phase: A is 5mM ammonium acetate+0.1% aqueous formic acid, and B is an acetonitrile; Gradient elution: 0～10min, 20%～90% B; 10～18min, 90%B; 18～18.1min, 90%～20% B; 18.1～25min, 20% B; Sample size: 5 μ L; Flow velocity: 0.3mL/min; Column temperature: 30 ℃;
Mass spectrum condition: mass analyzer: the mass analyzer that the accurate mass number can be provided; Scan pattern: positive ion-full scan pattern; Mass range: 100～1000; Resolution: 60000; Ion gun: electric spray ion source (ESI); Spray voltage: 4.5kV; Sheath atmospheric pressure: 45arb; Assist gas pressure power: 5arb.
Described liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that the qualitative, quantitative ion is the H+ and the NH4+ adduct of agricultural chemicals in the described step 4), and is the accurate mass number.
The present invention extracts in the vegetable sample behind the pesticide multi-residues, with disperseing solid phase extraction techniques to purify with acetonitrile reagent; After sample extraction, the complex salt that adds magnesium sulphate and sodium chloride is saltoutd, and guarantees to distribute to organic phase as acephatemet isopolarity agricultural chemicals; Disperse Solid-Phase Extraction to purify with magnesium sulphate, PSA, C18 composite material, when further removing water residual in the organic phase, in PSA and the C18 adsorption sample as chaff interferences such as sugar, fat; With full-automatic screening application software ToxID, the structure database is very convenient, only need in Excel typing pesticide name and molecular formula, automatically calculate the accurate mass number of H+, NH4+ or Na+ adduct, can be used for complicated substrate, simplify sample purification, can carry out express-analysis, improve data processing speed and analysis efficiency, also greatly reduced the probability that agricultural chemicals is judged by accident, failed to judge simultaneously; The accurate mass number that carries out sample detection and extract agricultural chemicals with liquid chromatography-high resolution mass spectrum carries out qualitative and quantitative, can eliminate unknown compound disturb, have qualitative accurately, quantitatively reliable, have data integrate and handle and use characteristics such as convenient.The mass accuracy of 27 kinds of agricultural chemicals detects and is limited to 0.01～0.05mg/kg less than 1ppm among the present invention, and adding the recovery is 80%～100%, and relative standard deviation is less than 15%.
Description of drawings
Fig. 1 is the mass accuracy of 27 kinds of pesticide multi-residues of detection;
Fig. 2-5 is the extraction ion figure of the corresponding accurate mass number of 27 kinds of pesticide standard solution (0.5mg/L);
Fig. 6 is embodiment 1(tomato matrix) the extraction ion figure that detects the corresponding accurate mass number of agricultural chemicals;
Fig. 7 is embodiment 2(green vegetables matrix) the extraction ion figure that detects the corresponding accurate mass number of agricultural chemicals;
Fig. 8 is embodiment 3(Chinese cabbage matrix) the extraction ion figure that detects the corresponding accurate mass number of agricultural chemicals.
Embodiment
Further specify the present invention below in conjunction with embodiment.
1, instrument and reagent
Instrument: Thermo Scientifc LTQ-Orbitrap XL combined type high-resolution mass spectrometer (U.S. power ﹠ light company) and SURVEYOR-HPLC liquid chromatograph (U.S. power ﹠ light company), high speed dispersor (German IKA company).
Reagent: acetonitrile (chromatographically pure, German Merck company); Acetone, toluene, formic acid (chromatographically pure, U.S. Tedia company); PSA and C18 filler (particle diameter 40 μ m, Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A.); Anhydrous magnesium sulfate (analyze pure, Sigma-Aldrich company); Sodium chloride (analyze pure, Shishewei Chemical Co., Ltd., Shanghai), ammonium acetate (analyze pure, U.S. Fluka company); Water is Milli-Q high purity water; The 5mmol/L ammonium acetate that contains 0.1 % formic acid: get the dissolving of 0.385g ammonium acetate water, add 1mL formic acid again and be diluted with water to 1000mL.80 kinds of standard sample of pesticide (purity is not less than 95 %, Dr Ehrenstorfer company) are made into single mark of 1mg/mL respectively with acetone-toluene (3:7), and seal up for safekeeping under-40 ℃, are formulated as the mixed mark of desired concn before using with the acetonitrile stepwise dilution.
2, sample preparation
(1) sample extraction: take by weighing even sample (tomato matrix) 25g and place the 200mL plastic centrifuge tube, add the 25mL acetonitrile, place homogenate 2min under high speed dispersor 10000 r/min, then, in centrifuge tube, add 15g complex salt (anhydrous magnesium sulfate and sodium chloride mass ratio 10:1), homogenate 1min under 8000 r/min, last, centrifuge tube is positioned in the hydro-extractor centrifugal 5min under 4000 r/min.
(2) sample purification: get 4mL upper strata acetonitrile in the 20mL centrifuge tube, add 1.2g anhydrous magnesium sulfate, 0.1gPSA respectively, and 0.1gC18, behind vibration 1min on the vortex oscillator, centrifuge tube is positioned in the hydro-extractor centrifugal 2min under 10000 r/min.Get supernatant and cross the organic filter membrane of 0.22 μ m, to be measured.
3, the preparation of standard operation solution
Accurately take by weighing standard items respectively: acephatemet, orthene, omethoate, Aldicarb sulfoxide, Azodrin, carbendazim, Aldicarb sulfone, probenazole, 3-hydroxyl carbofuran, Imidacloprid, Rogor, tricyclazole, Aphox, carbofuran, carbaryl, paclobutrazol, phonetic mould amine, triazolone, Hostathion, propiconazole, alachlor, Acetochlor, Difenoconazole, Quizalotop-ethyl, butachlor, pyridaben, Avermectin, with acetone-toluene (3:7) dissolving, be made into the single pesticide standard stock solution of 1.0mg/mL respectively.According to the response of each agricultural chemicals, become blended standard operation liquid during use with dilution in acetonitrile.
4, sample determination method
Standard operation liquid and sample liquid to be measured is the difference sample introduction on liquid chromatography-high-resolution mass spectrometer.
Liquid phase chromatogram condition: chromatographic column: moving phase: A is 5mM ammonium acetate+0.1% aqueous formic acid, and B is an acetonitrile;
Gradient elution: 0-10min, 10%-90% B; 10-18min, 90%B; 18-18.1min, 90%-10% B; 18.1-25min, 10% B; Sample size: 5 μ L; Flow velocity: 0.3mL/min; Column temperature: 30 ℃.
Mass spectrum condition: mass analyzer: FT Orbitrap; Scan pattern: positive ion-full scan pattern; Mass range: 100-1000; Resolution: 60000; Ion gun: electric spray ion source (ESI); Spray voltage: 4.5kV; Sheath atmospheric pressure: 45arb; Assist gas pressure power: 5arb.
5, interpretation of result
The structure of database: set up the compound molecule formula database information table of each agricultural chemicals with ToxID software, comprise agricultural chemicals English name, molecular formula, adduct type (seeing Table 1).
Qualitative and quantitative: with the quasi-molecular ion peak of compound (with H
+Or NH4
+The adduct form) accurate mass number is qualitative ion and quota ion.Mass concentration X with standard operation liquid is a horizontal ordinate, and the peak area Y of quota ion is an ordinate, and the drawing standard curve carries out quantitatively sample with standard working curve; And it is qualitative with retention time and qualitative ion (accurate mass number).Sample liquid to be measured after extracting is measured, and is the peak area of quota ion with the peak area that records agricultural chemicals, the substitution typical curve, and the carbendazim and the phonetic mould amine of trying to achieve in the sample are respectively 0.081mg/kg and 0.0032mg/kg.
Accuracy for determination methods, the carbendazim and the phonetic mould amine of 0.005mg/kg that add 0.10mg/kg in this sample are subscripted level, repeat above sample pre-treatments and Instrument measuring process, the carbendazim and the phonetic mould amine content that record in sample this moment are respectively 0.176mg/kg and 0.0075mg/kg, the recovery of subscripting that is carbendazim and phonetic mould amine is respectively 95.0% and 86.0%, illustrates that the method is accurately.
The information table of table 1 agricultural chemicals database
| Sequence number | Chinese | Molecular formula | Accurate molecular weight | The adduct type | Retention time | The accurate mass number |
| ? | Acephatemet | C2H8NO2PS | 141.00079 | H + | 1.73 | 142.00850 |
| 2 | Orthene | C4H10NO3PS | 183.01135 | H + | 1.74 | 184.01920 |
| 3 | Omethoate | C5H12NO4PS | 213.02192 | H + | 1.76 | 214.02983 |
| 4 | The Aldicarb sulfoxide | C7H14N2O3S | 206.07196 | H + | 1.77 | 207.07990 |
| 5 | Azodrin | C7H14NO5P | 223.06041 | H + | 2.70 | 224.06822 |
| 6 | Carbendazim | C9H9N3O2 | 191.06893 | H + | 2.73 | 192.07671 |
| 7 | The Aldicarb sulfone | C7H14N2O4S | 222.06688 | NH 4 + | 2.95 | 240.10117 |
| 8 | Probenazole | C10H7N3S | 201.03552 | H + | 3.05 | 202.04329 |
| 9 | 3-hydroxyl carbofuran | C12H15NO4 | 237.09956 | NH 4 + | 4.35 | 255.13402 |
| 10 | Imidacloprid | C9H10ClN5O2 | 255.05175 | H + | 4.66 | 256.05951 |
| 11 | Rogor | C5H12NO3PS2 | 228.99907 | H + | 4.91 | 230.00693 |
| 12 | Tricyclazole | C9H7N3S | 189.03552 | H + | 4.92 | 190.04330 |
| 13 | Aphox | C11H18N4O2 | 238.14243 | H + | 5.92 | 239.15038 |
| 14 | Carbofuran | C12H15NO3 | 221.10464 | H + | 7.29 | 222.11253 |
| 15 | Carbaryl | C12H11NO2 | 201.07843 | H + | 7.64 | 202.08626 |
| 16 | Paclobutrazol | C15H20ClN3O | 293.12894 | H + | 8.87 | 294.13678 |
| 17 | Phonetic mould amine | C12H13N3 | 199.11040 | H + | 9.12 | 200.11826 |
| 18 | Triazolone | C14H16ClN3O2 | 293.09256 | H + | 9.80 | 294.10040 |
| 19 | Hostathion | C12H16N3O3PS | 313.06445 | H + | 10.47 | 314.07242 |
| 20 | Propiconazole | C15H17Cl2N3O2 | 341.06923 | H + | 10.76 | 342.07715 |
| 21 | Alachlor | C14H20ClNO2 | 269.11771 | H + | 10.78 | 270.12558 |
| 22 | Acetochlor | C14H20ClNO2 | 269.11771 | H + | 10.84 | 270.12558 |
| 23 | Difenoconazole | C19H17Cl2N3O3 | 405.06415 | H + | 11.19 | 406.07193 |
| 24 | Quizalotop-ethyl | C19H17ClN2O4 | 372.08714 | H + | 12.58 | 373.09482 |
| 25 | Butachlor | C17H26ClNO2 | 311.16466 | H + | 13.69 | 312.17267 |
| 26 | Pyridaben | C19H25ClN2OS | 364.13706 | H + | 15.99 | 365.14499 |
| 27 | Avermectin | C48H72O14 | 872.49166 | NH 4 + | 16.33 | 890.52643 |
1, sample preparation
(1) sample extraction: take by weighing even sample (green vegetables matrix) 30g and place the 200mL plastic centrifuge tube, add the 35mL acetonitrile, place homogenate 3min under high speed dispersor 8000 r/min, then, in centrifuge tube, add 20g complex salt (anhydrous magnesium sulfate and sodium chloride mass ratio 10:1), homogenate 2min under 10000 r/min, last, centrifuge tube is positioned in the hydro-extractor centrifugal 6min under 5000 r/min.
(2) sample purification: get 2mL upper strata acetonitrile in the 20mL centrifuge tube, add 0.6g anhydrous magnesium sulfate, 0.05gPSA respectively, and 0.05gC18, behind vibration 2min on the vortex oscillator, centrifuge tube is positioned in the hydro-extractor centrifugal 3min under 8000 r/min.Get supernatant and cross the organic filter membrane of 0.22 μ m, to be measured.
2, the preparation of standard operation solution
Accurately take by weighing standard items respectively: acephatemet, orthene, omethoate, Aldicarb sulfoxide, Azodrin, carbendazim, Aldicarb sulfone, probenazole, 3-hydroxyl carbofuran, Imidacloprid, Rogor, tricyclazole, Aphox, carbofuran, carbaryl, paclobutrazol, phonetic mould amine, triazolone, Hostathion, propiconazole, alachlor, Acetochlor, Difenoconazole, Quizalotop-ethyl, butachlor, pyridaben, Avermectin, with acetone-toluene (3:7) dissolving, be made into the single pesticide standard stock solution of 1.0mg/mL respectively.According to the response of each agricultural chemicals, become blended standard operation liquid during use with dilution in acetonitrile.
3, sample determination method
Standard operation liquid and sample liquid to be measured is the difference sample introduction on liquid chromatography-high-resolution mass spectrometer.
Liquid phase chromatogram condition: chromatographic column: moving phase: A is 5mM ammonium acetate+0.1% aqueous formic acid, and B is an acetonitrile;
Gradient elution: 0-10min, 10%-90% B; 10-18min, 90%B; 18-18.1min, 90%-10% B; 18.1-25min, 10% B; Sample size: 5 μ L; Flow velocity: 0.3mL/min; Column temperature: 30 ℃.
Mass spectrum condition: mass analyzer: FT Orbitrap; Scan pattern: positive ion-full scan pattern; Mass range: 100-1000; Resolution: 60000; Ion gun: electric spray ion source (ESI); Spray voltage: 4.5kV; Sheath atmospheric pressure: 45arb; Assist gas pressure power: 5arb.
4, interpretation of result
The structure of database: set up the compound molecule formula database information table of each agricultural chemicals with ToxID software, comprise agricultural chemicals English name, molecular formula, adduct type (seeing Table 1).
The qualitative, quantitative ion: with the quasi-molecular ion peak of compound (with H
+Or NH4
+The adduct form) accurate mass number is qualitative and quota ion.Mass concentration X with standard operation liquid is a horizontal ordinate, and the peak area Y of quota ion is an ordinate, and the drawing standard curve carries out quantitatively sample with standard working curve; And it is qualitative with retention time and accurate mass number.Sample liquid to be measured after extracting is measured, and is the peak area of quota ion with the peak area that records agricultural chemicals, and the substitution typical curve is tried to achieve the carbendazim in the sample and the residual quantity of Imidacloprid and is respectively 0.932mg/kg and 0.059mg/kg.
Accuracy for determination methods, the carbendazim and the 0.05mg/kg Imidacloprid that add 1.00mg/kg in this sample are subscripted level, repeat above sample pre-treatments and Instrument measuring process, the carbendazim and the Imidacloprid content that record in sample this moment are respectively 1.765mg/kg and 0.099mg/kg, the recovery of subscripting that is carbendazim and Imidacloprid is respectively 83.3% and 80.0%, illustrates that the method is accurately.
Embodiment 3
1, sample preparation
(1) sample extraction: take by weighing even sample (Chinese cabbage matrix) 50g and place the 200mL plastic centrifuge tube, add the 50mL acetonitrile, place homogenate 3min under high speed dispersor 12000 r/min, then, in centrifuge tube, add 25g complex salt (anhydrous magnesium sulfate and sodium chloride mass ratio 10:1), homogenate 3min under 12000 r/min, last, centrifuge tube is positioned in the hydro-extractor centrifugal 4min under 3000 r/min.
(2) sample purification: get 6mL upper strata acetonitrile in the 20mL centrifuge tube, add 1.8g anhydrous magnesium sulfate, 0.2gPSA respectively, and 0.2gC18, behind vibration 1.5min on the vortex oscillator, centrifuge tube is positioned in the hydro-extractor centrifugal 4min under 12000 r/min.Get supernatant and cross the organic filter membrane of 0.22 μ m, to be measured.
2, the preparation of standard operation solution
Accurately take by weighing standard items respectively: acephatemet, orthene, omethoate, Aldicarb sulfoxide, Azodrin, carbendazim, Aldicarb sulfone, probenazole, 3-hydroxyl carbofuran, Imidacloprid, Rogor, tricyclazole, Aphox, carbofuran, carbaryl, paclobutrazol, phonetic mould amine, triazolone, Hostathion, propiconazole, alachlor, Acetochlor, Difenoconazole, Quizalotop-ethyl, butachlor, pyridaben, Avermectin, with acetone-toluene (3:7) dissolving, be made into the single pesticide standard stock solution of 1.0mg/mL respectively.According to the response of each agricultural chemicals, become blended standard operation liquid during use with dilution in acetonitrile.
3, sample determination method
Standard operation liquid and sample liquid to be measured is the difference sample introduction on liquid chromatography-high-resolution mass spectrometer.
Liquid phase chromatogram condition: chromatographic column: moving phase: A is 5mM ammonium acetate+0.1% aqueous formic acid, and B is an acetonitrile;
Gradient elution: 0-10min, 10%-90% B; 10-18min, 90%B; 18-18.1min, 90%-10% B; 18.1-25min, 10% B; Sample size: 5 μ L; Flow velocity: 0.3mL/min; Column temperature: 30 ℃.
Mass spectrum condition: mass analyzer: FT Orbitrap; Scan pattern: positive ion-full scan pattern; Mass range: 100-1000; Resolution: 60000; Ion gun: electric spray ion source (ESI); Spray voltage: 4.5kV; Sheath atmospheric pressure: 45arb; Assist gas pressure power: 5arb.
4, interpretation of result
The structure of database: screen the compound molecule formula database information table that software is set up each agricultural chemicals with ToxID, comprise agricultural chemicals English name, molecular formula, adduct type (seeing Table 1).
Qualitative and quantitative: with the quasi-molecular ion peak of compound (with H
+Or NH4
+The adduct form) accurate mass number is qualitative ion and quota ion.Mass concentration X with standard operation liquid is a horizontal ordinate, and the peak area Y of quota ion is an ordinate, and the drawing standard curve carries out quantitatively sample with standard working curve; And it is qualitative with retention time and qualitative ion (accurate mass number).Sample liquid to be measured after extracting is measured, and is the peak area of quota ion with the peak area that records agricultural chemicals, and the substitution typical curve is tried to achieve the carbendazim in the sample and the residual quantity of Imidacloprid and is respectively 0.022mg/kg and 0.043mg/kg.
Accuracy for determination methods, the carbendazim and the phonetic mould amine of 0.05mg/kg that add 0.05mg/kg in this sample are subscripted level, repeat above sample pre-treatments and Instrument measuring process, the carbendazim and the phonetic mould amine content that record in sample this moment are respectively 0.065mg/kg and 0.085mg/kg, the recovery of subscripting that is carbendazim and phonetic mould amine is respectively 86.0% and 85.0%, illustrates that the method is accurately.
By experimental results demonstrate, as sample, it also can reach technique effect same as the previously described embodiments at last by method of the present invention to select to use the different vegetable (as cucumber, eggplant, celery etc.) of different agricultural chemicals in the table 1.
Claims (7)
1. the liquid chromatography high resolution mass spectrum detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that may further comprise the steps:
1) acetonitrile of residues of pesticides extracts in the sample
Take by weighing 25～50g vegetable sample, add 25～50ml acetonitrile, carrying out high speed dispersion handles, obtain the mixing homogenate solution formed by vegetables matrix, water and acetonitrile, in above-mentioned homogenate solution, add 15～25g complex salt reagent of saltouing, carry out high speed dispersion again and handle, carry out centrifugally operated, standing demix then;
2) the dispersion Solid-Phase Extraction of sample extraction solution purifies
Get 2～6ml upper strata acetonitrile, add 0.6～1.8g anhydrous magnesium sulfate, 0.05～0.2g N-propyl group-ethylenediamine (PSA) and 0.05～0.2gC respectively
18, the centrifuging and taking of vibrating again supernatant, supernatant are crossed the organic filter membrane of 0.22 μ m, promptly obtain sample solution;
3) use liquid chromatography-high-resolution mass spectrometer to detect
A) preparation of standard solution: accurately taking by weighing the standard items agricultural chemicals respectively, is acetone-toluene solution dissolving of 3:7 with volume ratio, is made into the standard inventory solution of 1.0mg/mL respectively, according to the response of each agricultural chemicals, becomes standard operation liquid with dilution in acetonitrile during use;
B) use liquid chromatography-high resolution mass spectroscope examination criteria working fluid and the sample solution after purifying: draw standard operation liquid and sample solution respectively by automatic sampler, inject liquid chromatography-high resolution mass spectroscope, pesticide composition separates through liquid-phase chromatographic column in the sample solution, and the high resolution mass spectrum full scan detects;
4) interpretation of result
The structure of database: with ToxID software establishment step 3) the compound molecule formula database information table of standard items agricultural chemicals in;
Quantitatively and qualitative: the accurate mass number with the quasi-molecular ion peak of compound is qualitative ion and quota ion; Mass concentration X with standard operation liquid is a horizontal ordinate, and the peak area Y of qualitative, quantitative ion is an ordinate, the drawing standard working curve, and it is quantitative with standard working curve sample to be carried out single ion external standard method; Accurate mass number with chromatographic peak retention time that occurs in the sample solution and qualitative ion carries out qualitative.
2. liquid chromatography high resolution mass spectrum as claimed in claim 1 detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that in the described step 1) that the complex salt reagent of saltouing is anhydrous magnesium sulfate and sodium chloride mix reagent, anhydrous magnesium sulfate and sodium chloride mass ratio 10:1 in anhydrous magnesium sulfate and the sodium chloride mix reagent.
3. liquid chromatography high resolution mass spectrums as claimed in claim 1 detect the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that in the described step 1) adding in the vegetable sample behind the acetonitrile homogenate 1～3min under dispersion machine medium speed 8000～12000 r/min, add the complex salt homogenate 0.5～2min under rotating speed 8000～12000 r/min that saltouts behind the reagent, at last centrifugal 4～6min under 3 000～5 000 rpm in hydro-extractor.
4. liquid chromatography high resolution mass spectrum as claimed in claim 1 detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that described step 2) at the middle and upper levels acetonitrile add anhydrous magnesium sulfate, N-propyl group-ethylenediamine and C
18, the 0.5～2min that on the vortex oscillator, vibrates, centrifugal 2～4min under hydro-extractor 8 000～12 000 r/min then.
5. liquid chromatography high resolution mass spectrum as claimed in claim 1 detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that the standard items agricultural chemicals is acephatemet, orthene, omethoate, Aldicarb sulfoxide, Azodrin, carbendazim, Aldicarb sulfone, probenazole, 3-hydroxyl carbofuran, Imidacloprid, Rogor, tricyclazole, Aphox, carbofuran, carbaryl, paclobutrazol, phonetic mould amine, triazolone, Hostathion, propiconazole, alachlor, Acetochlor, Difenoconazole, Quizalotop-ethyl, butachlor, pyridaben and Avermectin in the described step 3).
6. liquid chromatography high resolution mass spectrum as claimed in claim 1 detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that liquid phase chromatogram condition in the described step 3): chromatographic column: XDB-C18,1.8 μ m, 4.6 * 50mm; Moving phase: A is 5mM ammonium acetate+0.1% aqueous formic acid, and B is an acetonitrile; Gradient elution: 0～10min, 20%～90% B; 10～18min, 90%B; 18～18.1min, 90%～20% B; 18.1～25min, 20% B; Sample size: 5 μ L; Flow velocity: 0.3mL/min; Column temperature: 30 ℃;
Mass spectrum condition: mass analyzer: the mass analyzer that the accurate mass number can be provided; Scan pattern: positive ion-full scan pattern; Mass range: 100～1000; Resolution: 60000; Ion gun: electric spray ion source; Spray voltage: 4.5kV; Sheath atmospheric pressure: 45arb; Assist gas pressure power: 5arb.
7. liquid chromatography high resolution mass spectrum as claimed in claim 1 detects the method for the many residual quantities of agricultural chemicals in the vegetable sample, it is characterized in that qualitative ion and quota ion in the described step 4) are the H of agricultural chemicals
+And NH4
+Adduct, and be the accurate mass number.
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