CN104713974A - Method for determining 55 kinds of pesticide residues in vegetable - Google Patents
Method for determining 55 kinds of pesticide residues in vegetable Download PDFInfo
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- CN104713974A CN104713974A CN201410804941.0A CN201410804941A CN104713974A CN 104713974 A CN104713974 A CN 104713974A CN 201410804941 A CN201410804941 A CN 201410804941A CN 104713974 A CN104713974 A CN 104713974A
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Abstract
The invention relates to a method for determining 55 kinds of pesticide residues in vegetable, which belongs to the technical field of physical and chemical detection for pesticide residues. The method comprises the following steps: preparing a sample, pre-treating the sample; weighting the sample, adding water for immersing, extracting by an organic solvent, removing pigment impurity with a PSA filling material, performing nitrogen blowing to a dry state, dissolving residues by a mobile phase, filtering a solution by a filter membrane for GPC-GC-MS analysis; preparing a standard solution; and performing an on-line GPC-GC-MS mass spectrograph determination. The method has the advantages of simple and fast operation, high automation degree, high extraction efficiency, and good recovery rate and repeatability.
Description
Technical field
The present invention relates to a kind of assay method of Determination of Pesticide Residues in Vegetable, be specifically related to the online gel chromatography series connection Gas Chromatography/Mass Spectrometric Method of 55 kinds of pesticide residue determinations in a kind of vegetables, belong to the physico-chemical examination technique field of residues of pesticides.
Background technology
Vegetables and daily life closely related, along with the raising of people's living standard, people have started the quality problems paying close attention to vegetables, and the nutritional labeling of people not only vegetables, also pays close attention to its quality problems.
Since the eighties in 20th century; the vegetable at protected field such as greenhouse, booth cultivated area increases sharply; continuous cropping, continuous cropping cause vegetable insect disease to increase the weight of; various places, in control vegetable insect disease, use chemical pesticide in a large number and continuously, make the sick worm of vegetables create the general resistance to the action of a drug to chemical pesticide; vegetable grower can only strengthen the use amount of agricultural chemicals; thus, Pesticide use and degree of dependence present vicious cycle state, and Determination of Pesticide Residues in Vegetable excessive problem is given prominence to.The agricultural chemicals of current use, some within a short period of time can become innoxious substance by biodegradation, and some organic chlorine agriculture chemicals are difficult to degraded, are the agricultural chemicals that residual is strong.
The main harm of chemical pesticide is that the residue not degradable on vegetable crop of chemical pesticide enters food, causes food pollution, directly poisons people and animals.Edible residues of pesticides are the vegetables of organophosphorus pesticide severe overweight, the nervous system that directly can jeopardize human body and the vitals such as liver, kidney particularly, somebody there will be the symptoms such as dizziness, headache, stomachache, anorexia, the dimness of vision, Nausea and vomiting, hidrosis after pesticide poisoning, severe intoxication person also there will be chest extruding sense, muscle tremors etc., serious occurred pulsation, accelerated breathing and potential quality stupor symptom, even causes acute poisoning and lethal.Long-term edible contaminated vegetables, remains of pesticide can cause some chronic diseases after people's body accumulation crosses certain limit, as cancer, artery sclerosis, cardiovascular disease, fetal anomaly, stillborn foetus, early die young, the disease such as early ageing.Residues of pesticides not only cause great harm to health, simultaneously also severe contamination environment for human survival, cause the pollutions such as air, soil, river, and constantly accumulate in the environment, cause animals and plants poisoning, destroy the ecologic equilibrium.
At present, the Detecting Pesticide many employings vapor-phase chromatography, GC-MS(gas chromatography-mass spectrography) etc. reported both at home and abroad.Because vapor-phase chromatography is generally merely able to analyze detection one compounds simultaneously, be difficult to the development trend meeting many kinds remain analysis.
Online gel chromatography series connection gaschromatographic mass spectrometry technology to be connected online with GC/MS by GPC purifying pretreating device and forms, adopt the separating power of miniature GPC chromatographic column and GC/MS Large volume injection newly developed, express-analysis while achieving many components of residues of pesticides.By online some report of gel chromatography series connection gas chromatography-mass spectrum technology for detection agricultural chemicals, Yang Huiqin utilizes online gel chromatography series connection gas chromatography-mass spectrum technology to analyze the germifuge in food, detects and is limited to 0.01 μ g/kg; Zheng Jiankun etc., by online gel chromatography series connection gas chromatography-mass spectrum technology, are studied 36 kinds of agricultural chemicals in soil.But this kind of document is often only limitted to a several or pesticide residue to carry out analysis and detects, by the Determination of Pesticide Residues in online gel chromatography series connection gas chromatography-mass spectrum technical Analysis vegetables, have not been reported, therefore, invent a kind of multi-pesticide residue detection method rapidly and efficiently and be necessary.
The Chinese invention extraction and purification methods of Organophosphorus Pesticide Residue " in a kind of vegetables and fruits ", application number 201310175339.0 discloses the method for Organophosphorus Pesticide Residue in a kind of vegetables and fruits; The Chinese invention detection method of residues of organophosphate pesticides " in the capsicum red pigment ", application number 201210220762.3 discloses the detection method of residues of organophosphate pesticides in a kind of capsicum red pigment.These detection methods can only detect the remains of pesticide of a few species, can not carry out relatively comprehensively Detecting Pesticide.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of simple to operate, fast, automaticity is high, and extraction efficiency is high, the method for 55 kinds of pesticide residue determinations in the recovery and reproducible vegetables.
For realizing the object of foregoing invention, the technical scheme that the present invention takes is as follows:
55 kinds of persticide residue methods for measuring in a kind of vegetables, comprise the steps:
(1) sample preparation: sample is rubbed homogenate, freezen protective;
(2) sample pre-treatments: take freezing sample in 50.0mL acrylic plastering centrifuge tube, add 5.0mL deionized water, soak 10 minutes, add acetonitrile, 15000rpm homogeneous 2min, add sodium chloride and anhydrous sodium sulfate after homogeneous, the centrifugal 10min of 9000rpm, Aspirate supernatant 5mL is in centrifuge tube; PSA filler is added in centrifuge tube, after vortex 2.0min, the centrifugal 10min of 9000rpm, Aspirate supernatant 10mL is in test tube; Water-bath under temperature 45 C, High Purity Nitrogen air-blowing is near dry; With 1mL acetone+cyclohexane constant volume, through 0.22 μm of organic membrane filtration of micropore, for online gel chromatography-gaschromatographic mass spectrometric analysis;
(3) preparation of standard solution: hybrid standard working fluid acetone: cyclohexane dilutes;
(4) online gel chromatography series connection Gas Chromatography-Mass Spectrometry: the hybrid standard working fluid of preparation variable concentrations, injects and is furnished with online gel chromatography series connection gas chromatograph-mass spectrometer (GCMS);
(5) calculating of determination of residual amount result: to combine with SIM method with retention time and carry out the qualitative analysis of 55 kinds of agricultural chemicals, carry out the quantitative test of 55 kinds of agricultural chemicals with peak area, use external standard method result of calculation; Described sample is spinach; The described freezen protective condition of step (1) is-18 DEG C;
The volume adding acetonitrile described in step (2) is that every gram of sample adds 5mL, the described quality adding sodium chloride and anhydrous sodium sulfate is that every gram of sample adds 1 gram of sodium chloride and 1 gram of anhydrous sodium sulfate respectively, the amount of described PSA filler is, every milliliter of extract adds the PSA filler of 10mg;
Described sodium chloride and anhydrous sodium sulfate before use, all in muffle furnace 400 DEG C oven dry; The volume ratio of the described constant volume liquid acetone+cyclohexane of step (2) is 3+7; Step (3) described solvent acetone: the volume ratio of cyclohexane is 3:7; The graded series concentration of the described hybrid standard working fluid of step (4) is 0.01,0.02,0.05,0.1,0.2 and 0.5 μ g/mL;
The GPC condition of step (5) described employing: chromatographic column: Shodex CLNpak EV-200 (2.1mm × 150mm); Acetone/the cyclohexane of mobile phase: volume ratio 3+7; Flow velocity: 0.1mL/min; Column temperature: 40 DEG C; Sample size: 10 μ L; GCMS condition: chromatographic column: inertia quartz ampoule: 5m × 0.53mm; Pre-column: Rtx-5MS, 5m × 0.25mm × 0.25 μm; Analytical column: Rtx-5MS, 25m × 0.25mm × 0.25 μm; PTV injector temperature: 120 DEG C; Column temperature program: 82 DEG C (5min)-8 DEG C/min-300 DEG C (7.75min); Carrier gas: helium; Splitless injecting samples: 7min; Solvent delay: 9.7min; Interface temperature: 300 DEG C; Ion source temperature: 230 DEG C; Acquisition mode: ion monitoring mode.
The invention has the beneficial effects as follows:
Detect vegetable pesticide residue amount by this method, pesticide species broad covered area, processes simple to operate, and fast, automaticity is high, and extraction efficiency is high, is a kind of method of recovery and reproducible mensuration vegetable pesticide residue amount.
Accompanying drawing explanation
The standard mass spectrogram (concentration is 0.1 μ g/mL) of Fig. 1: 55 kinds of agricultural chemicals:
In figure, 1-10 is followed successively by: acephatemet, DDVP, orthene, metrifonate, omethoate, phonamiphos, sulfotep, phosmet, Azodrin, Rogor; In figure, 11-20 is followed successively by: terbufos, Fonofos, diazinon, phosphorus ammonium, Entex, parathion, isocarbophos, Isofenphos methyl, phosfolan, quinalphos; In figure, 21-29 is followed successively by: methidathion, Profenofos, Hostathion, parathion-methyl, fenifrothion, malathion, chlopyrifos, Phosalone, Resistox; In figure, 30-39 is followed successively by: α-666, pentachloronitrobenzene, β-666, γ-666, triazolone, dicofol, phenthoate dimephenthoate cidial, procymidone, 5a,6,9,9a-hexahydro-6,9-methano-2,4, p, p'-DDE; In figure, 40-49 is followed successively by: p, p'-DDD, o, p'-DDT, Bravo, δ-666, vinclozolin, iprodione, p, p'-DDT, Fenpropathrin, lambda-cyhalothrin, Permethrin; In figure, 50-55 is followed successively by: cyfloxylate, taufluvalinate, cypermethrin, flucythrinate, fenvalerate, decis;
Fig. 2: vegetables blank sample Selective ion mode flow graph;
Fig. 3: vegetable sample 55 kinds of agricultural chemicals total ions chromatogram (concentration is 0.1 μ g/mL).
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention.
Embodiment 1
55 kinds of persticide residue methods for measuring in a kind of vegetables, comprise the steps:
(1) sample preparation: measure 5 spinach samples, pulls an oar sample, freezen protective under-18 DEG C of conditions;
(2) sample pre-treatments: take the freezing sample of 5g in 50.0mL acrylic plastering centrifuge tube, add 5.0mL deionized water, soak 10 minutes, add 20.0mL acetonitrile, 15000rpm homogeneous 2min, add 5.0g sodium chloride and 5.0g anhydrous sodium sulfate after homogeneous, the centrifugal 10min of 9000rpm, Aspirate supernatant 5mL is in centrifuge tube; PSA filler 50mg is added in centrifuge tube, after vortex 2.0min, the centrifugal 10min of 9000rpm, Aspirate supernatant 10mL is in test tube; Water-bath under temperature 45 C, High Purity Nitrogen air-blowing is near dry; With 1mL acetone+cyclohexane (volume ratio 3+7) constant volume, through 0.22 μm of organic membrane filtration of micropore, for online gel chromatography-gaschromatographic mass spectrometric analysis;
(3) preparation of standard solution: hybrid standard working fluid acetone: cyclohexane (volume ratio is 3:7) dilutes;
(4) online gel chromatography series connection Gas Chromatography-Mass Spectrometry: the hybrid standard working fluid of preparation variable concentrations, injection is furnished with online gel chromatography series connection gas chromatograph-mass spectrometer (GCMS), and the graded series concentration of hybrid standard working fluid is 0.01,0.02,0.05,0.1,0.2 and 0.5 μ g/mL;
(5) calculating of determination of residual amount result: to combine with SIM method with retention time and carry out the qualitative analysis of 55 kinds of agricultural chemicals, the quantitative test of 55 kinds of agricultural chemicals is carried out with peak area, use external standard method result of calculation, result detects agricultural chemicals in three spinach samples, the results are shown in Table 1.
The content of remains of pesticide in table 1 spinach samples
The mensuration of repeatability and the recovery.
Negative spinach samples (55 kinds of agricultural chemicals are all without detecting) is adopted to measure, the detectability analyzing thing is determined with 3 times of signal to noise ratio (S/N ratio)s, the quantitative limit analyzing thing is determined with 10 times of signal to noise ratio (S/N ratio)s, in conjunction with the recovery and sample size, quantitatively detecting of method is limited to 10-30ug/kg, adopt the method for adding standard solution in sample, under same sample preparation, recovery of standard addition experiment is carried out to 55 kinds of agricultural chemicals, the results are shown in Table 2.
In table 2 spinach, 55 kinds of agricultural chemicals carry out recovery of standard addition (n=5)
Online gel chromatography-the gaschromatographic mass spectrometry of table 3 measures characteristic ion, related coefficient, the detection limit of 55 kinds of target compounds in vegetables
Online gel chromatography-the gaschromatographic mass spectrometry of table 3 measures the recovery and the standard deviation (n=5) of 55 kinds of target compounds in spinach samples
Above-described embodiment is only be described the preferred embodiment of the present invention; not that scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (9)
1. 55 kinds of persticide residue methods for measuring in vegetables, is characterized in that: comprise the steps:
(1) sample preparation: sample is rubbed homogenate, freezen protective;
(2) sample pre-treatments: take freezing sample in 50.0 mL acrylic plastering centrifuge tubes, add 5.0 mL deionized waters, soak 10 minutes, add acetonitrile, 15000 rpm homogeneous 2 min, add sodium chloride and anhydrous sodium sulfate after homogeneous, centrifugal 10 min of 9000 rpm, Aspirate supernatant 5 mL is in centrifuge tube; PSA filler is added in centrifuge tube, after vortex 2.0 min, centrifugal 10 min of 9000 rpm, Aspirate supernatant 10 mL is in test tube; Water-bath under temperature 45 C, High Purity Nitrogen air-blowing is near dry; With 1 mL acetone+cyclohexane constant volume, through 0.22 μm of organic membrane filtration of micropore, for online gel chromatography-gaschromatographic mass spectrometric analysis;
(3) preparation of standard solution: hybrid standard working fluid acetone, cyclohexane dilute;
(4) online gel chromatography series connection Gas Chromatography-Mass Spectrometry: the hybrid standard working fluid of preparation variable concentrations, injects and is furnished with online gel chromatography series connection gas chromatograph-mass spectrometer (GCMS);
(5) calculating of determination of residual amount result: to combine with SIM method with retention time and carry out the qualitative analysis of 55 kinds of agricultural chemicals, carry out the quantitative test of 55 kinds of agricultural chemicals with peak area, use external standard method result of calculation.
2. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1, is characterized in that: described sample is spinach.
3. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1, is characterized in that: the described freezen protective condition of step (1) is-18 DEG C of preservations.
4. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1, it is characterized in that: the addition of the acetonitrile described in step (2) is that every gram of sample adds 5 mL, described sodium chloride and the addition of anhydrous sodium sulfate are that every gram of sample adds 1 gram of sodium chloride and 1 gram of anhydrous sodium sulfate respectively, and the addition of described PSA filler is that every milliliter of extract adds 10 mg.
5. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1 or 4, is characterized in that: described sodium chloride and anhydrous sodium sulfate before use, all 400 DEG C of oven dry in muffle furnace.
6. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1, is characterized in that: step (2) described acetone: the volume ratio of cyclohexane is 3: 7.
7. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1, is characterized in that: the graded series concentration of the described hybrid standard working fluid of step (4) is 0.01,0.02,0.05,0.1,0.2 and 0.5 μ g/mL.
8. 55 kinds of persticide residue methods for measuring in a kind of vegetables according to claim 1, is characterized in that: the GPC condition of step (5) described employing: chromatographic column: Shodex CLNpak EV-200,2.1 mm × 150 mm; Mobile phase: the acetone/cyclohexane of volume ratio 3/7; Flow velocity: 0.1 mL/min; Column temperature: 40 DEG C; Sample size: 10 μ L; GCMS condition: chromatographic column: inertia quartz ampoule: 5 m × 0.53 mm; Pre-column: Rtx-5 MS, 5 mm × 0.25 μm, m × 0.25; Analytical column: Rtx-5 MS, 25 mm × 0.25 μm, m × 0.25; PTV injector temperature: 120 DEG C; Column temperature program: 82 DEG C, 5 min-8 DEG C/min-300 DEG C, 7.75 min; Carrier gas: helium; Splitless injecting samples: 7 min; Solvent delay: 9.7 min; Interface temperature: 300 DEG C; Ion source temperature: 230 DEG C; Acquisition mode: ion monitoring mode.
9. an application for 55 kinds of persticide residue methods for measuring in vegetables, is characterized in that: according to any one of claim 1 ~ 8, method is detecting the application in vegetable pesticide residue amount.
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Cited By (5)
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| CN105974015A (en) * | 2016-05-07 | 2016-09-28 | 中国热带农业科学院农产品加工研究所 | Method for determining dimethomorph and gibberellin residual quantity of vegetables and fruits |
| CN106018715A (en) * | 2016-05-03 | 2016-10-12 | 成都亿信标准认证集团有限公司 | Automatic grain pesticide residue detection system |
| CN110007024A (en) * | 2019-04-17 | 2019-07-12 | 安徽三联学院 | A kind of accurate quick On Detection of Organophosphorus Pesticide of vegetables |
| CN110146625A (en) * | 2019-06-18 | 2019-08-20 | 浙江树人学院（浙江树人大学） | The organophosphorous pesticides of Isofenphos methyl-tandem mass spectrum detection method in fruits and vegetables |
| CN110824060A (en) * | 2019-11-26 | 2020-02-21 | 江苏韵沣检测有限公司 | Method for determining pesticide residue in vegetables by gas chromatography |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106018715A (en) * | 2016-05-03 | 2016-10-12 | 成都亿信标准认证集团有限公司 | Automatic grain pesticide residue detection system |
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| CN110146625A (en) * | 2019-06-18 | 2019-08-20 | 浙江树人学院（浙江树人大学） | The organophosphorous pesticides of Isofenphos methyl-tandem mass spectrum detection method in fruits and vegetables |
| CN110824060A (en) * | 2019-11-26 | 2020-02-21 | 江苏韵沣检测有限公司 | Method for determining pesticide residue in vegetables by gas chromatography |
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