CN104062306A - Mass-spectrum rapid analysis method for pesticide residue in fruits and vegetables - Google Patents

Mass-spectrum rapid analysis method for pesticide residue in fruits and vegetables Download PDF

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CN104062306A
CN104062306A CN201410291479.9A CN201410291479A CN104062306A CN 104062306 A CN104062306 A CN 104062306A CN 201410291479 A CN201410291479 A CN 201410291479A CN 104062306 A CN104062306 A CN 104062306A
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sample
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mass spectrum
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pesticide
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CN104062306B (en
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王喆
刘源才
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Jing Brand Co Ltd
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Jing Brand Co Ltd
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Abstract

The invention discloses a mass-spectrum rapid analysis method for the pesticide residue in fruits and vegetables. A triple quadrupole mass spectrum is adopted as an analyzer, a discharging low-temperature plasma is used as a mass spectrum ionization source, and a sample is placed on a continuous sample introduction belt in front of the low-temperature plasma ionization source; a heating lamp is used for performing rapid non-contact thermal analysis of the sample; the sample is detected in an anion detection mode and compared with the early established spectrogram in a pesticide standard quality mass spectrum library to rapidly judge whether the residue of corresponding pesticide exists in the sample; the method disclosed by the invention improves the qualitative analysis ability and signal strength of the device; and compared with the traditional pesticide residue detection method, the method has the advantages of simple pretreatment, small dosage of organic solvent, short detection period of single sample and the like.

Description

A kind of mass spectrum rapid analysis of fruit and vegetable Pesticide Residues
Technical field
The invention belongs to mass spectrometric analysis method, particularly a kind of mass spectrum rapid analysis of fruit and vegetable Pesticide Residues.
Prior art
Agricultural chemicals, in order to improve crop yield and quality, has vital effect in modern agricultural production.But the use lack of standardization of agricultural chemicals, can cause agricultural byproducts, water body, Pesticide Residue in Soil residual content to exceed standard equally.Residual agricultural chemicals can be enriched in human body by food chain, and the food and the drink that eat for a long time and drink residues of pesticides content overproof can cause damage to people's health, even cause death.
Detecting Pesticide mode comprises liquid chromatography, liquid chromatography-tandem mass spectrometry, gas chromatography, gas chromatography-mass spectrum etc. at present.Chromatogram and mass spectrum or tandem mass spectrum coupling have the features such as accurate, sensitive.But complicated pre-treatment and detect the factors such as required time is long, is not suitable for the fast detecting of residues of pesticides.
The atmospheric pressure ionization mass spectrometry technology that development in recent years is got up can directly be analyzed most compounds under the condition without sample pre-treatments, has the features such as quick, efficient, sensitive.Low temperature plasma ionization source is exactly wherein a kind of, it is to apply rf electric field by the outer wall at insulating medium, discharge gas in insulating medium is ionized formation plasma, and plasma gas is directly injected on sample, can realize sample ionization.Because it is simple in structure, features such as processing ease and be subject to extensive concern, low temperature plasma ionization source mass spectrum has been successfully applied to the aspects such as explosive, illicit drugs inspection, can detect sample in trace and complex matrices.But the ionization mode under atmospheric pressure environment, is subject to surrounding environment as larger in the impact of humidity, temperature, and signal intensity relative standard deviation (RSD) is between 10%-30%, and the accuracy of quantitative test is unsatisfactory.Low temperature plasma ionization source has very high sensitivity to little molecule volatile compound, for the compound analysis that volatility is poor, often by means of pyrolysis, analyses raising sensitivity.But traditional type of heating is that analytic sample is positioned on heating plate and is heated.This type of heating is more applicable for fluid sample, but be unwell to, has definite shape as the detection of the samples such as fruit and vegetable.Therefore, inventing the quilitative method of the crops Pesticide Residues such as a kind of energy fast detecting fruit and vegetable, is an important step guaranteeing food security.
Summary of the invention
Object of the present invention is just to provide a kind of mass spectrum rapid analysis of fruit and vegetable Pesticide Residues; The inventive method is positioned over sample on the continuous sample introduction band before low temperature plasma ionization source, utilize the quick contactless pyrolysis of heating lamp to analyse sample, under negative ion detection mode, detect, and compare with the spectrogram in the standard sample of pesticide mass spectrum spectrum storehouse of prior foundation, can judge fast in this sample, whether have the residual of corresponding certain agricultural chemicals; Have maneuverability good, sample, without pre-treatment, can carry out qualitative detection to the fruit and vegetable of cash sale in supermarket, and the time is short, accuracy high.
Technical scheme of the present invention is to have adopted triple level Four bar mass spectrums as analyzer, usings the low temperature plasma that discharges as mass spectrum ionization source, and concrete steps are:
1. set up standard sample of pesticide mass spectrum spectrum storehouse
Choose three kinds of conventional Chlorothalonils, Rogor, malathion standard solution, with methyl alcohol, be diluted to 5 μ g/mL respectively, with micro syringe, get 1 μ L sample drop on sample introduction band, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 ° to blowing sample, mass spectrum sample introduction kapillary, higher than sample introduction band 1 mm, in same vertical plane, is 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, make light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyze, obtain respectively the mass spectrogram of Bravo, Rogor, malathion standard solution, with this, set up standard sample of pesticide mass spectrum spectrum storehouse;
2. sample detection
A. the detection of solid sample
Adopt after teflon sampling cloth wiping solid sample epidermis, by sampling placement on sample feeding platform, electric discharge quartz glass tube gas vent 2 mm above sampling cloth, with 45 ° to blowing sample, mass spectrum sample introduction kapillary is higher than sampling cloth 1 mm, in same vertical plane, be 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sampling cloth top, makes light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyzes, and can obtain the mass spectrogram of this sample;
B. the detection of fluid sample
By after sample squeezing, the juice of getting 1 μ L sample drips on sample introduction band, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 ° to blowing sample, mass spectrum sample introduction kapillary, higher than sample introduction band 1 mm, in same vertical plane, is 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, makes light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyzes, and can obtain the mass spectrogram of this sample;
3. testing result
Resulting sample mass spectrogram and the mass spectrogram in the standard sample of pesticide mass spectrum spectrum storehouse of setting up are compared one by one, as there is the spectrum peak identical with mass spectrogram in standard sample of pesticide mass spectrum spectrum storehouse in sample, can judge and in this sample, have the residual of corresponding certain agricultural chemicals.
In the present invention, the principle of work of instrument and feature are, low temperature plasma ionization source is a kind of of dielectric barrier discharge, the present invention uses the quartz glass tube of external diameter 8 mm, internal diameter 6 mm as discharge medium, discharge gas is He gas, discharge gas flows in quartz glass tube, and by suspended body flowmeter, controlling flow is 0.15 L/min.High-voltage radio-frequency power supply to ground electrode dielectric barrier discharge, excites He gas by quartz ampoule, forms low temperature plasma bombardment sample, and then produces sample ions.Sample is by continuous sample introduction band sample introduction.Electric discharge quartz glass tube gas vent 2 mm above sample, with 45 °, to blowing sample, mass spectrum sample introduction kapillary, higher than sample introduction band 1 mm, in same vertical plane, is 135 ° of angles with electric discharge quartz glass tube.Low temperature plasma ionization source can ionized sample form negative ion, can more fully detect sample.
Due at room temperature, pesticide sample saturated vapor pressure is lower, and gained sample signal intensity is lower, and spectrogram sharpness is poor, and the present invention uses heating lamp (as Halogen lamp LED) to be placed in 40 mm places, sample top, and halogen light shines directly on sample.Triple level Four bar mass spectrums of metal capillary direct injected under atmospheric pressure, ion takes the mode of vacsorb to enter in triple level Four bar mass spectrometers, under negative ion mode, carry out quality analysis, sample signal intensity is strengthened greatly, and resulting spectrogram sharpness also greatly improves.Solved that traditional type of heating is confined to fluid sample and the problem that is not suitable for solid sample.
The present invention both can also can analyze fluid sample solid sample, had maneuverability good, and sample is without pre-treatment, and detection time is short, the feature that accuracy is high, and the fast qualitative that can realize the fresh fruit Pesticide Residues in Vegetables to selling in supermarket detects.
accompanying drawing explanation
Bravo standard solution mass spectrogram at room temperature under Fig. 1 negative ion mode;
The Bravo standard solution mass spectrogram of heat by lalonge lamp 3 s at room temperature under Fig. 2 negative ion mode;
Rogor standard solution mass spectrogram at room temperature under Fig. 3 negative ion mode;
The Rogor standard solution mass spectrogram of heat by lalonge lamp 3 s at room temperature under Fig. 4 negative ion mode;
Malathion mass spectrogram at room temperature under Fig. 5 negative ion mode;
The standard solution mass spectrogram of heat by lalonge lamp 3 s at room temperature in malathion under Fig. 6 negative ion mode;
Snow pear epidermis blank sample mass spectrogram at room temperature under Fig. 7 negative ion mode;
Under Fig. 8 room temperature, snow pear epidermis applies the mass spectrogram under the negative ion mode after chlorothalonil pesticide;
Tomato juice's blank sample mass spectrogram at room temperature under Fig. 9 negative ion mode;
Figure 10 at room temperature Tomato juice applies the mass spectrogram under negative ion mode after Bravo, Rogor, three kinds of malathions agricultural chemicals.
embodiment
Embodiment 1
The present embodiment has adopted the triple level Four bar of this QBB1606 of water mass spectrum as analyzer, usings the low temperature plasma that discharges as mass spectrum ionization source, and concrete steps are:
1. set up standard sample of pesticide mass spectrum spectrum storehouse
Choose three kinds of conventional Chlorothalonils, Rogor, malathion standard solution, with methyl alcohol, be diluted to 5 μ g/mL respectively, with micro syringe, get 1 μ L sample drop on sample introduction band, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 ° to blowing sample, mass spectrum sample introduction kapillary, higher than sample introduction band 1 mm, in vertical same plane, is 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, make light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyze, obtain respectively the mass spectrogram of Bravo, Rogor, malathion standard solution, with this, set up standard sample of pesticide mass spectrum spectrum storehouse;
Bravo used because being easily degraded into M in methanol solution 1(4-hydroxyl-2,5,6-trichlorine m-dicyanobenzene) and M 2(the chloro-m-dicyanobenzene of 1,3-bis-), therefore the quasi-molecular ions [M that mass spectra peak is degradation product 1-H] -( m/z245) and [M 2-H+NO 2] -( m/z241); At room temperature, because pesticide sample saturated vapor pressure is lower, gained sample signal intensity is lower, referring to Fig. 1, when taking approximately 120 ℃ of heat by lalonge lamp 3 s() after, the signal intensity of Bravo has improved 52 times, referring to Fig. 2.In the situation of room temperature and heat by lalonge lamp 3 s, record the mass spectrogram of Rogor respectively as shown in Figure 3 and Figure 4, the characteristic peak [M-CH of Rogor can be detected 3] -( m/z214); Take after heat by lalonge lamp 3 s, the signal intensity of Rogor has improved 55 times.In the situation of room temperature and heat by lalonge lamp 3 s, record the mass spectrogram of malathion respectively as shown in Figure 5 and Figure 6, in malathion, phosphordithiic acid ester group easily departs from parent becomes fragmention [M-C 8o 4h 13] -( m/z157) be detected; Take after heat by lalonge lamp 3 s, the signal intensity of malathion has improved 37 times.
2. sample detection
The present embodiment is chosen the snow pear that does not apply agricultural chemicals, adopt after teflon sampling cloth wiping snow pear epidermis, by sampling placement on sample feeding platform, electric discharge quartz glass tube gas vent 2 mm above sampling cloth, with 45 ° to blowing sample, mass spectrum sample introduction kapillary, higher than sampling cloth 1 mm, in same vertical plane, is 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sampling cloth top, make light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyze, can obtain the mass spectrogram of snow pear epidermis blank sample, as shown in Figure 7, at m/z242 place, there is composing more by force peak.
To be diluted to 5 μ g/mL chlorothalonil pesticide standard solution with methyl alcohol again, and with micro syringe, get 1 μ L and drip 1 cm in above-mentioned snow pear 2on epidermis, until solvent evaporates completely after, adopt teflon sampling cloth wiping snow pear epidermis, by sampling placement on sample feeding platform, by the detection method identical with snow pear epidermis blank sample, detect, can obtain snow pear epidermis and apply the mass spectrogram after chlorothalonil pesticide; As shown in Figure 8, can clearly detect the characteristic peak (m/z241,243,247) of chlorothalonil pesticide.
Embodiment 2
The unit type that the present embodiment adopts and the method for setting up standard sample of pesticide mass spectrum spectrum storehouse are with embodiment 1, the vegetables that detect are new fresh tomato, to not apply after the tomato squeezing of agricultural chemicals, get 1 μ L tomato supernatant juice sample drop on sample introduction band, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 °, to blowing sample, mass spectrum sample introduction kapillary is higher than sample introduction band 1 mm, in same vertical plane, be 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, makes light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyzes, and obtains the mass spectrogram of this tomato blank sample; As shown in Figure 9, at m/z240,241 places, there is composing more by force peak.
Get again the tomato supernatant juice sample of above-mentioned squeezing, Bravo, Rogor, three kinds of malathions pesticide standard solution are splashed into respectively in tomato juice, the content that makes every kind of agricultural chemicals in juice is 5 μ g/mL, with micro syringe, get 1 μ L juice sample drop on sample introduction band again, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 °, to blowing sample, mass spectrum sample introduction kapillary is higher than sample introduction band 1 mm, in same vertical plane, be 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, make light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyze, the characteristic peak (m/z157,214,241,243) that can clearly detect three kinds of agricultural chemicals, shows that in 5 ng samples, three kinds of agricultural chemicals are all detected.As shown in Figure 10.
Above-mentioned testing result explanation the inventive method can be used for the qualitative detection of fruit and vegetable Pesticide Residues.

Claims (1)

1. a fruit and vegetable Pesticide Residues mass spectrum rapid analysis, is to have adopted triple level Four bar mass spectrums as analyzer, usings the low temperature plasma that discharges as mass spectrum ionization source, it is characterized in that:
1. set up standard sample of pesticide mass spectrum spectrum storehouse
Choose three kinds of conventional Chlorothalonils, Rogor, malathion standard solution, with methyl alcohol, be diluted to 5 μ g/mL respectively, with micro syringe, get 1 μ L sample drop on sample introduction band, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 ° to blowing sample, mass spectrum sample introduction kapillary, higher than sample introduction band 1 mm, in same vertical plane, is 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, make light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyze, obtain respectively the mass spectrogram of Bravo, Rogor, malathion standard solution, with this, set up standard sample of pesticide mass spectrum spectrum storehouse;
2. sample detection
A. the detection of solid sample
Adopt after teflon sampling cloth wiping solid sample epidermis, by sampling placement on sample feeding platform, electric discharge quartz glass tube gas vent 2 mm above sampling cloth, with 45 ° to blowing sample, mass spectrum sample introduction kapillary is higher than sampling cloth 1 mm, in same vertical plane, be 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sampling cloth top, makes light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyzes, and can obtain the mass spectrogram of this sample;
B. the detection of fluid sample
By after sample squeezing, the juice of getting 1 μ L sample drips on sample introduction band, electric discharge quartz glass tube gas vent 2 mm above sample, with 45 ° to blowing sample, mass spectrum sample introduction kapillary, higher than sample introduction band 1 mm, in same vertical plane, is 135 ° of angles with electric discharge quartz glass tube; Heating lamp is placed in to 40 mm places, sample top, makes light shine directly into 3-4 second on sample, sample ions enters in triple level Four bar mass spectrometers in the mode of vacsorb, under negative ion mode, analyzes, and can obtain the mass spectrogram of this sample;
3. testing result
Resulting sample mass spectrogram and the mass spectrogram in the standard sample of pesticide mass spectrum spectrum storehouse of setting up are compared one by one, as there is the spectrum peak identical with mass spectrogram in standard sample of pesticide mass spectrum spectrum storehouse in sample, can judge and in this sample, have the residual of corresponding certain agricultural chemicals.
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CN109799201A (en) * 2018-12-29 2019-05-24 芯视界(北京)科技有限公司 Laminated body is used in the residual rapid detection method of agricultural product agriculture and detection
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CN109856230B (en) * 2019-01-30 2021-09-21 山东博戎伝创信息科技有限公司 Organic compound residue analysis method and device and intelligent monitoring system thereof
CN109916989A (en) * 2019-04-01 2019-06-21 山东博戎伝创信息科技有限公司 A kind of organic object detecting method, apparatus and system based on artificial intelligence
CN109916989B (en) * 2019-04-01 2021-12-10 山东博戎伝创信息科技有限公司 Organic matter detection method, device and system based on artificial intelligence
WO2022121056A1 (en) * 2020-12-12 2022-06-16 广州禾信仪器股份有限公司 Continuous mass spectrum sample injection device and mass spectrum detection apparatus
CN113075281A (en) * 2021-03-22 2021-07-06 兰州海关技术中心 Pretreatment method of medlar sample and high-throughput qualitative detection method for pesticide residues in medlar sample

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