CN103822994A - Method for measuring residual quantity of paraquat and diquat in food - Google Patents
Method for measuring residual quantity of paraquat and diquat in food Download PDFInfo
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- CN103822994A CN103822994A CN201410096085.8A CN201410096085A CN103822994A CN 103822994 A CN103822994 A CN 103822994A CN 201410096085 A CN201410096085 A CN 201410096085A CN 103822994 A CN103822994 A CN 103822994A
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Abstract
The invention relates to a method for measuring the residual quantity of paraquat and diquat in food. During pretreatment on a sample, paraquat and diquat in a food sample are extracted by a methanol solution, the extract liquid is purified by C18 and PSA dispersive solid-phase extraction agents, and finally, qualitative and quantitative measurement on the residual paraquat and diquat in the food is achieved through the precise mass number of compound ions with the combination of high performance liquid chromatography-quadrupole rod flight time tandem mass spectrum. The average recycling rate of paraquat is 80.6%-96.8%, the relative standard deviation of paraquat is 3.9%-7.1%, the limit of quantitation of paraquat is 10 microgram/kg, the recycling rate of diquat is 80.8%-97.3%, the relative standard deviation of diquat is 3.5%-7.8%, and the limit of quantitation of diquat is 10 microgram/kg. The method can effectively alleviate matrix interference to residual detection on paraquat and diquat in food, has the advantages of simplicity and convenience in operation, rapidness, accuracy, high sensitivity and good repeatability, and is supplement and improvement on a conventional QuEChERS method.
Description
Technical field
The invention belongs to the determination techniques field of persticide residue, relate in particular to the assay method of paraquat and diquat dibromide residual quantity in a kind of food.
Background technology
In the proportion of crop planting processes such as fruit, vegetables, Cereals, farmland weed produces material impact to crop yield and quality.The use of herbicide in agricultural production, has not only saved a large amount of heavy weeding manual labors and weeding by machine's operation, the more important thing is and has reduced the agricultural output that causes because of crop smothering and the loss of quality, obtains considerable economic benefit.But along with the concern of people to food-safety problem, herbicide residue also receives much attention to the harm of human health.
Paraquat (paraquat) chemical name 1,1 ,-dimethyl-4,4 ,-bipyridine cation, belongs to organic heterocyclic class quaternary ammonium salt herbicide.As broad spectrum weeding, agent is widely used, paraquat sales volumes in 2011 rank the 2nd in global herbicide is sold.Paraquat has stronger toxic action to people and animals, and the redox activity influence to biosome after absorption is very large, and lung, the heart, liver, kidney etc. are all harmful to, and paraquat poisoning there is no effective methods for the treatment of at present.China, Codex Alimentary Commission (CAC), the U.S., European Union and Japan and other countries have all been formulated residue limits standard to paraquat, the maximum residue limit 0.01～3.5mg/kg in the numerous food such as fruit, vegetables, fish, meat.
Diquat dibromide (diquat) chemical name 1,1 ,-ethylene-4,4 ,-bipyridine cation belongs to organic heterocyclic class nonselective herbicide.Urge witheredly for crops such as potatos, cotton, soybean, corn, Chinese sorghum, flax, sunflower, in the time that crop is ripe, remaining green portion and weeds are dried-up rapidly, can gather in ahead of time; Prevent and kill off for farmland weed: weeding that summer corn is no-tillage, orchard weed growth animated period carry out weeds foliar treatment.Diquat dibromide, to belonging to moderate toxicity herbicide, has spread effect to skin and eyes.China, the U.S., European Union and Japan and other countries have all been formulated residue limits standard to diquat dibromide, the maximum residue limit 0.05～2mg/kg in the numerous food such as fruit, vegetables, fish, meat.
The Sample Pretreatment Technique that QuEChERS method is got up as new development is to represent sample-pretreating method quick, simple, inexpensive, efficient, stable and safety (Quick, Easy, Cheap, Effective, Rugged, Safe).There is the recovery high, analyze agricultural chemicals scope wide, the advantage such as processing speed is fast, and solvent use amount is few, easy and simple to handle.At present internationally extensively recognize spendable QuEChERS method and have EN15662 that European Union formulates and the AOAC2007.01 standard method of the analytical chemistry Shi Xiehui of official of the U.S..2 methods all comprise extraction, purify 2 steps: 1 use acetonitrile or the acetonitrile containing 1% acetic acid extract sample, realize acetonitrile and separate with the liquid-liquid of sample place water by adding buffer salt potpourri to carry out salting-out extraction; 2 use disperse solid extracting agent and anhydrous magnesium sulfate to extracting solution purification, disperse the character of solid extracting agent according to sample substrate and testing compound, can select PSA, GCB, C18EC etc.But all must add anhydrous magnesium sulfate to remove moisture residual in middle acetonitrile.
But paraquat and diquat dibromide belong to strong polarity quaternary ammonium compound, are very easily dissolved in water, be difficult to extract from water with acetonitrile, therefore cannot adopt existing QuEChERS method to carry out sample pre-treatments.Conventionally paraquat and diquat dibromide pre-treatment adopt Solid-Phase Extraction column purification, and method is more complicated, and the recovery is low, and operating personnel are had relatively high expectations; Or without purifying direct-detection, matrix interference is large, serious to instrumental pollution.Therefore seek and set up the QuEChERS pre-treating method that adapts to paraquat and diquat dibromide residue detection to be very important.
Summary of the invention
The object of this invention is to provide the assay method of paraquat and diquat dibromide residual quantity in a kind of food, to make up the deficiencies in the prior art.
Another object of the present invention is to provide a kind of sample-pretreating method, extensively recognizes to make up the existing world deficiency that spendable QuEChERS method cannot be used for paraquat and diquat dibromide residue detection.
Sample pre-treatments of the present invention is supplementing and improving existing QuEChERS method, due to paraquat and the very easily water-soluble characteristic of diquat dibromide, acetonitrile or cannot be practical containing the extracting method of acetonitrile salting-out extraction from water of 1% acetic acid for existing QuEChERS method, it is to extract solvent directly to extract from sample that the present invention selects methanol aqueous solution, has guaranteed the extraction efficiency of paraquat.In purifying step, because extracting solvent is mainly water, so existing method adds anhydrous magnesium sulfate also infeasible divided by the method for removing residual moisture in extract, therefore the present invention only uses and disperses solid extracting agent to purify extract, and do not add anhydrous magnesium sulfate, and disperse solid extracting agent can only select C18 and PSA.
Therefore, detection of the present invention, its pre-treatment is first to extract paraquat and the diquat dibromide in food samples with methanol aqueous solution, select again C18 and PSA to disperse solid extracting agent to purify extract, finally in conjunction with high performance liquid chromatography-Quadrupole-time of flight mass spectrometry (LC-Q TOF), accurate mass number by compound ions is realized accurate qualitative and quantitative analysis, to make up in prior art the technological deficiency that cannot use the pre-treatment of QuEChERS method to paraquat and diquat dibromide residue detection, reach and improve the sensitivity that LC-Q TOF detects, realize the residual accurate analysis of paraquat in food.
Assay method of the present invention comprises the steps:
(1) extract
Take the food samples homogenizing in tool plug plastic centrifuge tube, add the vibration of methanol aqueous solution vortex, centrifugal;
(2) purify
Pipette the supernatant of (1) acquisition in plastic centrifuge tube, add Dispersive solid phase extraction agent, vortex vibration, centrifugal, to draw supernatant and cross 0.22 μ m filter membrane, gained sample liquid is to be determined;
(3) preparation matrix standard operation solution
Blank sample is processed by above-mentioned steps (1), (2), within the scope of 10～1000 μ g/L, prepared paraquat and diquat dibromide series concentration standard operation liquid with this blank sample matrix solution;
(4) liquid chromatography--Quadrupole-time of flight mass spectrometry (LC-Q TOF) is measured
A) quantitative measurement: the each concentration matrix standard operation liquid in step (3) is carried out to LC-Q TOF mensuration, with the chromatographic peak area of each concentration matrix standard operation liquid, its respective concentration is carried out to regretional analysis, obtain standard working curve; The sample liquid under the same conditions step (2) being obtained is injected LC-Q TOF and is measured, record the chromatographic peak area of target compound in sample liquid, substitution typical curve, obtain target compound content in sample liquid, then the Mass Calculation of liquid representative sample obtains target compound residual quantity in sample per sample.
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with matrix standard operation solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number matrix standard solution suitable for concentration, judges in this sample and have target compound; If above-mentioned two conditions can not meet simultaneously, judgement is not containing target compound.
In above-mentioned steps (2), the volumetric concentration of particular methanol aqueous solution is 20%.。
Above-mentioned steps (2) mesostroma disperses solid extracting agent by C
18with PSA composition, C in every milliliter of extract
18be respectively 50mg with PSA addition.
In above-mentioned steps (4), the mobile phase of liquid chromatography is A: methyl alcohol and Mobile phase B: containing 0.1% formic acid-5mmol/L ammonium formate aqueous solution, adopt A:B volume ratio 20:80 isocratic elution, flow velocity: 0.2mL/min.
In above-mentioned steps (4), the chromatographic column of liquid chromatography is hydrophilic chromatographic post (HILIC).
In above-mentioned steps (4), Mass Spectrometer Method is used electrospray ionization source (ESI) positive ion mode, capillary voltage is+4000V, atomization gas pressure is 275.8kPa, dry gas is nitrogen, dry gas temperature is 350 ℃, dry gas flow velocity is 10.0L/min, reference ion m/z121.050873 and m/z922.009798, sweep limit 50-1100m/z.
In above-mentioned steps (4), Mass Spectrometer Method is used one-level full scan pattern, the accurate molecular weight 186.1159 of paraquat quasi-molecular ion, the accurate molecular weight 184.3322 of diquat dibromide quasi-molecular ion.
Vortex duration of oscillation in above-mentioned steps (1) and (2) is 1min.
Centrifugal 5000r/min in above-mentioned steps (1) and (2), centrifugation time 3～5min.
The container including centrifuge tube that in above-mentioned steps (1)～(4), sample touches all should be plastic material and makes.
Beneficial effect of the present invention is:
The present invention can effectively reduce the matrix interference in paraquat and diquat dibromide residue detection in food, this pre-treating method is applied to paraquat and the qualitative confirmation of diquat dibromide and quantitatively detection in food in conjunction with HPLC-Q TOF, paraquat average recovery rate 80.6%～96.8%, relative standard deviation (RSD) is 3.9%～7.1%; The recovery 80.8%～97.3% of diquat dibromide, relative standard deviation (RSD) is 3.5%～7.8%.It is easy and simple to handle, quick, accurate, highly sensitive and reproducible that the present invention has advantages of, is supplementing and improving existing QuEChERS method.Can meet China and European Union, the U.S., the technical requirement of Japan to corresponding product safety detection completely, will provide strong technical support for ensureing that Chinese people people's food security and export abroad trade develop in a healthy way.
Accompanying drawing explanation
Fig. 1 is that 10ng/mL matrix standard paraquat extracts chromatography of ions figure.
Fig. 2 paraquat standard mass spectrogram.
Fig. 3 is that 10ng/mL matrix standard diquat dibromide extracts chromatography of ions figure.
Fig. 4 diquat dibromide standard mass spectrogram.
Embodiment
Now with following embodiment, the present invention is described, but is not to limit the scope of the invention.
The instrument using in the embodiment of the present invention and reagent:
T18Basic homogenizer (IKA, Germany); CR21G III type high speed freezing centrifuge (Hitachi, Japan); MS3 type vortex mixer (IKA, Germany); 1200 high performance liquid chromatography-6520 level Four bar flight time mass spectrums (Agilent, USA); PSA disperses solid extracting agent (Agilent, USA); C18 disperses solid extracting agent (Agilent, USA).
Reagent: methyl alcohol (HPLC level, Merke, Germany); Ammonium formate (HPLC level, CNW, Germany); Formic acid (HPLC level, CNW, Germany).
Standard substance: paraquat purity is 97.5%, diquat dibromide purity is 99.0%, all purchased from German Dr Ehrenstorfer company.
Embodiment 1: the detection of paraquat and diquat dibromide residual quantity in apple
(1) sample pre-treatments
Take the apple sample 10.0g homogenizing in 50mL tool plug plastic centrifuge tube, add 10mL methanol aqueous solution, vortex 1min, the centrifugal 5min of 5000r/min.After centrifugal, get 2mL supernatant extract to 100mg C is housed
18in the centrifuge tube of 100mg PSA, vortex 1min, the centrifugal 3min of 5000r/min.Get supernatant and cross after 0.22 μ m filter membrane, gained sample liquid is measured for liquid chromatography-Quadrupole-time of flight mass spectrometry (LC-Q TOF).
(2) preparation of standard operation solution
Take respectively 25 ± 0.1mg paraquat, diquat dibromide standard items in 25mL plastics volumetric flask, with acetonitrile dissolving, constant volume obtains its standard reserving solution concentration 1000.0 μ g/mL; Pipette respectively paraquat and the each 1.0mL of diquat dibromide standard reserving solution is placed in 100mL plastics volumetric flask, obtain 10.0 μ g/mL hybrid standard intermediate liquids with acetonitrile constant volume;
With after testing not containing the apple of paraquat and diquat dibromide as blank sample, prepare vehicle solution by above-mentioned pre-treatment step, by standard intermediate liquid with vehicle solution dilution be mixed with 10,20,50,100,200,500,1000ng/mL series matrix standard operation solution.
(3) liquid chromatography-Quadrupole-time of flight mass spectrometry (LC-Q TOF) is measured
Quantitative measurement: the each concentration matrix standard operation liquid in step (3) is carried out to LC-Q TOF mensuration, with the chromatographic peak area of each concentration matrix standard operation liquid, its respective concentration is carried out to regretional analysis, obtain standard working curve; The sample liquid under the same conditions step (2) being obtained is injected LC-Q TOF and is measured, record the chromatographic peak area of target compound in sample liquid, substitution typical curve, obtain target compound content in sample liquid, then the Mass Calculation of liquid representative sample obtains target compound residual quantity in sample per sample.
Wherein chromatographic condition is: BEH HILIC chromatographic column (2.1mm × 100mm, 1.7 μ m; U.S. Waters); Mobile phase: methyl alcohol and containing 0.1% formic acid-5mmol/L ammonium formate water, with volume ratio 20:80 isocratic elution; Flow velocity: 0.2mL/min; Column temperature: 30 ℃; Sample size: 2 μ L.
Wherein mass spectrum parameter is: the scanning of electrospray ionization source (ESI) positive ion mode; 350 ℃ of dry gas temperature, dry gas flow velocity 10L/min, atomization gas pressure 275.8kPa, capillary voltage 4kV, capillary outlet voltage 190V, scan mode: one-level full scan, reference ion m/z121.050873 and m/z922.009798, sweep limit 50-1100m/z.
Qualitative Identification: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with matrix standard operation solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number matrix standard solution suitable for concentration, judges in this sample and have target compound; If above-mentioned two conditions can not meet simultaneously, judgement is not containing target compound.
Standard working curve and detection limit:
Chromatographic peak area with matrix standard operation solution carries out regretional analysis to its respective concentration, obtains standard working curve.Using target compound concentration in sample corresponding to 3 times of signal to noise ratio (S/N ratio)s (S/N) as detection limit (LOD), in the sample of 10 times of signal to noise ratio (S/N ratio)s (S/N) correspondence, target compound concentration, as quantitative limit (LOQ), obtains detection limit and the quantitative limit of each target compound.The results are shown in Table 1.
Retention time, regression equation, related coefficient, quantitative limit and the detection limit of table 1 paraquat
| Title | Retention time (min) | Regression equation | Related coefficient | Quantitative limit (μ g/kg) | Detection limit (μ g/kg) |
| Paraquat | 3.65 | Y=11019.1307X-44748.6835 | 0.9990 | 10 | 5 |
| Diquat dibromide | 3.85 | Y=5822.0997X-45428.5839 | 0.9992 | 10 | 5 |
Recovery of standard addition and repeatability:
With after testing not containing the apple of paraquat as blank sample, add paraquat and the diquat dibromide mixed standard solution of low middle high variable concentrations level, after adding 30min, carry out the determination of residual amount by above-mentioned treatment step, mensuration concentration and the theoretical concentration of adding of agricultural chemicals are compared, obtain agricultural chemicals and add the recovery, each interpolation horizontal parallel is measured 6 times, obtains its relative standard deviation, and measurement result is in table 2.As can be seen from Table 2, in 3 mark-on levels, the recovery of paraquat is 80.6%～96.8%, and relative standard deviation (RSD) is 3.9%～7.1%, the recovery 80.8%～97.3% of diquat dibromide, and relative standard deviation (RSD) is 3.5%～7.8%.The recovery that the inventive method is described is higher, reproducible.
Above embodiment is described the preferred embodiment of the present invention, not scope of the present invention is limited, design under the prerequisite of spirit not departing from the present invention, various modification and improvement that the common engineering in this area is made technical scheme of the present invention, all should fall into claim of the present invention.
Claims (10)
1. an assay method for paraquat and diquat dibromide residual quantity in food, is characterized in that comprising the steps:
(1) extract
Take the food samples homogenizing in tool plug plastic centrifuge tube, add the vibration of methanol aqueous solution vortex, centrifugal;
(2) purify
Pipette the supernatant of above-mentioned steps (1) acquisition in plastic centrifuge tube, add Dispersive solid phase extraction agent, vortex vibration, centrifugal, to draw supernatant and cross 0.22 μ m filter membrane, gained sample liquid is to be determined;
(3) preparation matrix standard operation solution
Blank sample is processed by above-mentioned steps (1), (2), within the scope of 10～1000 μ g/L, prepared paraquat and diquat dibromide series concentration standard operation liquid with this blank sample matrix solution;
(4) liquid chromatography--Quadrupole-time of flight mass spectrometry is measured
A) quantitative measurement: the each concentration matrix standard operation liquid in step (3) is carried out to LC-Q TOF mensuration, with the chromatographic peak area of each concentration matrix standard operation liquid, its respective concentration is carried out to regretional analysis, obtain standard working curve; The sample liquid under the same conditions step (2) being obtained is injected LC-Q TOF and is measured, record the chromatographic peak area of paraquat and diquat dibromide in sample liquid, substitution typical curve, obtain paraquat and diquat dibromide content in sample liquid, then the Mass Calculation of liquid representative sample obtains paraquat and diquat dibromide residual quantity in sample per sample;
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with matrix standard operation solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number matrix standard solution suitable for concentration, judges in this sample and have target compound; If above-mentioned two conditions can not meet simultaneously, judgement is not containing target compound.
2. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, is characterized in that the volumetric concentration of methanol aqueous solution in above-mentioned steps (2) is 20%.
3. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, is characterized in that above-mentioned steps (2) mesostroma disperses solid extracting agent to be made up of C18 and PSA, and in every milliliter of extract, C18 and PSA addition are respectively 50mg.
4. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, the mobile phase that it is characterized in that liquid chromatography in above-mentioned steps (4) is A: methyl alcohol and Mobile phase B: containing 0.1% formic acid-5mmol/L ammonium formate aqueous solution, adopt A:B volume ratio 20:80 isocratic elution, flow velocity: 0.2mL/min.
5. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, is characterized in that the chromatographic column of liquid chromatography in above-mentioned steps (4) is hydrophilic chromatographic post.
6. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, it is characterized in that in above-mentioned steps (4), Mass Spectrometer Method is used electrospray ionization source positive ion mode, capillary voltage is+4000V, atomization gas pressure is 275.8kPa, dry gas is nitrogen, and dry gas temperature is 350 ℃, and dry gas flow velocity is 10.0L/min, reference ion m/z121.050873 and m/z922.009798, sweep limit 50-1100m/z.
7. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, it is characterized in that in above-mentioned steps (4), Mass Spectrometer Method is used one-level full scan pattern, the accurate molecular weight 186.1159 of paraquat quasi-molecular ion, the accurate molecular weight 184.3322 of diquat dibromide quasi-molecular ion.
8. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, is characterized in that the vortex duration of oscillation in above-mentioned steps (1) and (2) is 1min.
9. pre-treating method according to claim 1, is characterized in that the centrifugal 5000r/min in above-mentioned steps (1) and (2), centrifugation time 3～5min.
10. the assay method of paraquat and diquat dibromide residual quantity in food as claimed in claim 1, is characterized in that sample touches in above-mentioned steps (1)～(4) the container including centrifuge tube all should be plastic material and makes.
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Cited By (5)
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| CN108593811A (en) * | 2018-07-10 | 2018-09-28 | 南方医科大学 | A method of measuring Detection of Paraquat in Biological Fluid and diquat dibromide content |
| CN110133132A (en) * | 2019-05-15 | 2019-08-16 | 广州金至检测技术有限公司 | The extracting method and detection method of diquat dibromide in a kind of food |
| CN110383060A (en) * | 2017-03-08 | 2019-10-25 | 沃特世科技公司 | Polarity pesticide is determined using chromatography |
| CN111001184A (en) * | 2019-12-25 | 2020-04-14 | 中国科学院长春应用化学研究所 | Method for efficiently inducing water-organic solvent mixed solution phase separation by inorganic salt |
| CN112730372A (en) * | 2020-11-26 | 2021-04-30 | 中国科学院合肥物质科学研究院 | Flexible surface enhanced Raman substrate, preparation method thereof and paraquat detection method |
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| CN102608230A (en) * | 2012-03-09 | 2012-07-25 | 深圳市宇驰检测技术有限公司 | Detection method of residual content of paraquat in environment |
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| JP2008096320A (en) * | 2006-10-13 | 2008-04-24 | Nippon Flour Mills Co Ltd | Method for analyzing agricultural chemical using liquid chromatography-tandem mass spectrometry (lc-ms/ms) |
| CN102608230A (en) * | 2012-03-09 | 2012-07-25 | 深圳市宇驰检测技术有限公司 | Detection method of residual content of paraquat in environment |
Non-Patent Citations (7)
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110383060A (en) * | 2017-03-08 | 2019-10-25 | 沃特世科技公司 | Polarity pesticide is determined using chromatography |
| CN108593811A (en) * | 2018-07-10 | 2018-09-28 | 南方医科大学 | A method of measuring Detection of Paraquat in Biological Fluid and diquat dibromide content |
| CN110133132A (en) * | 2019-05-15 | 2019-08-16 | 广州金至检测技术有限公司 | The extracting method and detection method of diquat dibromide in a kind of food |
| CN111001184A (en) * | 2019-12-25 | 2020-04-14 | 中国科学院长春应用化学研究所 | Method for efficiently inducing water-organic solvent mixed solution phase separation by inorganic salt |
| CN112730372A (en) * | 2020-11-26 | 2021-04-30 | 中国科学院合肥物质科学研究院 | Flexible surface enhanced Raman substrate, preparation method thereof and paraquat detection method |
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