CN106885837A - A kind of method of the highly sensitive detection pesticide sample of fast and stable - Google Patents
A kind of method of the highly sensitive detection pesticide sample of fast and stable Download PDFInfo
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- CN106885837A CN106885837A CN201510934211.7A CN201510934211A CN106885837A CN 106885837 A CN106885837 A CN 106885837A CN 201510934211 A CN201510934211 A CN 201510934211A CN 106885837 A CN106885837 A CN 106885837A
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Abstract
The invention discloses a kind of method of novel detection pesticide sample.This method is detecting instrument to be equipped with the rectilinear ion trap mass spectrum of Thermal desorption low temperature plasma ionization source and discontinuous atmospheric pressure interface, by direct mass spectrum or cascade mass spectrometry, realize that, for the highly sensitive detection of the fast and stable of pesticide sample, single sample detection time is less than 1s.Operating process：Solid or fluid sample are placed on sampling cloth, cloth of sampling is inserted the injection port of Thermal desorption low temperature plasma, then start scanning of the mass spectrum, sample mass spectrum is obtained in 1s.Thermal desorption low temperature plasma ionization source can be discharged using one or more in helium, argon gas, nitrogen or air as discharge gas, and carrier gas can select one or several in air, dry air, helium, argon gas or nitrogen.The detection pattern selection negative ion mode of matrix ion trap mass spectrograph.This method is used for the detection of pesticide sample, detection speed to be fast, and sensitivity is high, and stability is strong.
Description
Technical field
It is that one kind is based on rectilinear ion trap matter the present invention relates to the detection method of the agricultural chemicals such as organophosphor, organochlorine
The mass spectrometry of spectrum.This method analyze speed is fast, and the reappearance of testing result is high, and stability is strong, and
And it is high for the sensitivity of pesticide sample, the detection limit of sample is in pg magnitudes.
Background technology
Agricultural chemicals is the important means of production, and it also brings many while China's cereal crops yield is ensured
Problem, such as：Agricultural chemicals excessively endangers health of people etc. using polluted river soil, residues of pesticides.Especially
The exposure of the event such as " poison rice ", poisonous vegetables, even more allowed people for the concern of Pesticides Testing in recent years
Lifted to a new high degree.
Traditional Pesticides Testing technology is mainly chromatogram (including gas-chromatography and liquid chromatogram) technology, surpasses and face
Boundary's Fluid Chromatography technology and chromatograph-mass spectrometer coupling (GC-MS, LC-MS) technology etc..These methods are often needed
Complicated sample pre-treatments are wanted, such as：SPE, SPME, matrix solid phase dispersion and overcritical extraction
Take, not only the time needed for complex operation, and sample analysis is more long.And the agricultural chemicals inspection that this patent is proposed
Survey method, without complicated pre-treatment, fluid sample or solid sample can directly carry out sample detection, single
Individual sample detection can be completed in 1s, and the reappearance of testing result is high, and stability is strong, and for
The sensitivity of pesticide sample is high, and the detection limit of sample is in pg magnitudes.
The content of the invention
The invention discloses a kind of method of novel detection pesticide sample.This method is low to be equipped with Thermal desorption
The matrix ion trap mass spectrograph of isothermal plasma ionization source and discontinuous atmospheric pressure interface is detecting instrument, is passed through
Direct mass spectrum or cascade mass spectrometry, realize for the highly sensitive detection of the fast and stable of pesticide sample, single
Sample detection time is less than 1s.
The technical solution adopted by the present invention is as follows：
In order to realize the high-sensitivity detection of pesticide sample, the present invention by lower temperature plasma technology and rectangle from
The combination of sub- trap mass-spectrometric technique, i.e., using under atmospheric pressure low temperature plasma as the mass spectrographic ionization of rectilinear ion trap
Source, and with helium, argon gas, Krypton, nitrogen, oxygen or dry air as discharge gas.
In order to improve the stability of Pesticides Testing, we introduce Thermal desorption injector, by first by sample gas
Change imports low temperature plasma and is ionized again, so as to ensure that the stability of sample introduction.And gaseous molecular is relative
It is that active area when low temperature plasma interacts is bigger in liquid and solid-state molecular, thus one
Determine to be also contributed in degree the raising of detection sensitivity.
In order to shorten analysis time, we have selected discontinuous atmospheric pressure interface as connection ionization source and mass spectrum
The tie of vacuum system.During sample introduction, magnetic valve is opened, and sample introduction is finished, and magnetic valve is closed immediately, magnetic valve
The time of unlatching is typically chosen 5ms-20ms.On the one hand using for discontinuous atmospheric pressure interface ensure that sample size,
On the other hand also ensure that the air pressure in vacuum cavity is unlikely to have too great fluctuation process, reduce the rate of air sucked in required of pump,
Substantially reduce the time of analysis detection.
Matrix ion trap mass spectrograph is selected as the detecting instrument of agricultural chemicals, on the one hand because rectilinear ion trap is removed
Have the advantages that mass spectrum is common (such as：Sensitivity is high, and amount of samples is few, and analyze speed is fast, separates and reflects
Carry out simultaneously calmly etc.) outside, also there is oneself uniqueness, sensitivity is high, and amount of samples is few, analysis
Speed is fast, separates and identification is carried out simultaneously.Single sample MS-MS is analyzed and completed in 1s.
Advantages of the present invention is as follows：
By low-temperature plasma generator composition ionization source under Thermal desorption injector and atmospheric pressure, by discontinuous big
Air pressure interface is docked with rectilinear ion trap mass spectrum, for the detection of pesticide sample.The method detection speed is fast,
Stability is strong, and sensitivity is high.
Compared with traditional Pesticides Testing method, the method that this patent is proposed without cumbersome sample pre-treatments,
Detection speed is fast (single sample is analyzed and completed in 1s), and sensitivity is higher (for the detection of pesticide sample
Limit is in pg magnitudes).It is matrix ion trap mass spectrograph compact, lightweight compared with other mass spectrographs, can
To realize field assay, and cascade mass spectrometry can be easily carried out, the degree of accuracy of qualitative, quantitative is higher.
Brief description of the drawings
Fig. 1 Thermal desorption mass spectrographic structural representations of low temperature plasma rectilinear ion trap；
The mass spectrographic concrete analysis process of Fig. 2 rectilinear ion traps and the voltage sequential in each stage；
The mass spectrogram of tetra- kinds of pesticide samples of Fig. 3 (phosmet, mirex, heptachlor and oxadiazon).
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention is further detailed explanation：
For invention be related to it is a kind of determine pesticide sample new method, with Thermal desorption low temperature of negative ion mode etc. from
Daughter rectilinear ion trap mass-spectrometric technique is basic detection technique, by sample carried out direct mass spectral analysis or
Person's cascade mass spectrometry, reaches qualitative or quantitative purpose.
The overall structure diagram of instrument is as shown in Figure 1.This instrument includes consisting of part：Thermal desorption enters
Sample device I, atmos low-temperature plasma ionization source II, discontinuous atmospheric pressure interface III, rectilinear ion trap matter
Spectrum detecting system IV.Wherein rectilinear ion trap Mass Spectrometer Method system includes again：Cavity 1, molecular pump 2, diaphragm
Pump (fore pump) 3, rectilinear ion trap mass analyzer 4, electron multiplier 5, amplifier and signal transacting
System 6.
Thermal desorption injector is mainly used in making liquid or solid sample become gaseous molecular, the gaseous state after parsing
Molecule enters atmos low-temperature plasma ionization source by carrier gas carrier band.Atmos low-temperature plasma ionization source
The plasma of generation and gaseous sample molecular collision, by energy or electric charge transfer to sample molecule, realize
Ionization to sample molecule.Sample ions enter mass spectrometer system and are detected by discontinuous atmospheric pressure interface again
Survey.The realization of cascade mass spectrometry is on the basis of direct mass spectral analysis plus the preceding paragraph swift waveforms are used
To filter out parent ion, then parent ion is smashed by AC resonance techniques, and then obtain the MS-MS letters of sample
Breath.
Embodiment 1
When Fig. 2 gives the mass spectrographic concrete analysis process of Thermal desorption low temperature plasma rectilinear ion trap and voltage
Sequence.As can be seen from the figure：Sample is completed from sample introduction to analysis, is divided into 4 stages, is respectively sample introduction rank
Section, ion cooling stage, scanning analysis stage and zero stage.Whole used time analysis time is less than 500ms,
Illustrate that Thermal desorption low temperature plasma rectilinear ion trap mass spectrum is a kind of quick detection means.
Embodiment 2
Fig. 3 detects dense under giving Thermal desorption low temperature plasma rectilinear ion trap mass spectrum anionic textiles pattern
Degree is the mass spectrogram of phosmet, mirex, heptachlor and the oxadiazon of 10ppm.Phosmet belongs to be had
Machine phosphorus insecticide, mirex belongs to insecticide, and heptachlor belongs to cyclodienes insecticide, and oxadiazon belongs to herbicide.
It can be seen that four kinds of pesticide samples have stronger mass spectrum response signal.And phosmet, go out
The relative standard deviation (RSD) of ant spirit, heptachlor and oxadiazon sample detection is respectively 15%, 13%, 10% and
8%.Therefore illustrate, Thermal desorption low temperature plasma rectilinear ion trap mass spectrum is a kind of quick, highly sensitive and steady
Qualitative strong Pesticides Testing method.
Claims (8)
1. a kind of fast and stable it is highly sensitive detection pesticide sample method, it is characterised in that：To assemble pyrolysis
The rectilinear ion trap matter of analysis low temperature plasma (LTP) ionization source and discontinuous atmospheric pressure interface (DAPI)
It is detecting instrument to compose, and Thermal desorption low temperature plasma ionization source includes that Thermal desorption injector and plasma occur
Device, T-shaped glass tube is a part for plasma generator；Pesticide sample is passed through with cloth as carrier of sampling
Thermal desorption low temperature plasma ionization source is parsed and ionized, and the sample ions after ionization are by discontinuous big
Air pressure sample introduction interface carries out direct mass spectral analysis or tandem mass spectrometry point into rectilinear ion trap mass analyzer
Analysis, so as to realize the qualitative or quantitative detection of pesticide sample.
2. method according to claim 1, it is characterised in that：Sampling cloth be for accept liquid or
Solid sample, its material is polytetrafluoroethylene (PTFE), and the specification of cloth of sampling is 105mm*28mm.
3. method according to claim 1, it is characterised in that：Thermal desorption low temperature plasma ionization source
Including Thermal desorption injector and plasma generator；Plasma generator includes radio-frequency power supply, annular again
Electrode, column are to electrode, discharge gas, T-shaped glass tube and three-way pipe；T-shaped glass tube left end and three-way pipe
Right side port is connected, and T-shaped glass tube right-hand member is connected with the import of discontinuous atmospheric pressure interface, T-shaped glass tube
Upper end branch pipe be connected with the outlet of Thermal desorption injector；Annular electrode is sheathed on the outer of T-shaped glass tube left end
On wall, column stretches to T-shaped glass tube left end inner annular electrode institute to electrode from three-way pipe left side port
Circular region, the upper port of three-way pipe is connected with discharge gas source of the gas；Annular electrode and column are to electrode
It is connected with radio-frequency power supply both positive and negative polarity respectively；Discharge gas enters annular electrode and column electricity from one end of three-way pipe
Between pole, plasma is produced；Discharge gas is helium, argon gas, Krypton, nitrogen, oxygen or drying
One or two or more kinds in air；Sample gas is introduced by the branch pipe of T-shaped glass tube, in glass tube
Portion produces with plasma and interacts and be ionized.
4. method according to claim 1, it is characterised in that：The effect of the Thermal desorption injector is
Liquid or solid sample is set to gasify, the pyrolysis eutectoid temperature of injector can be from room temperature to any 240 DEG C
Regulation；Injector connects carrier gas all the way, and low temperature plasma is entered for carrying the sample molecule after Thermal desorption
Generator；Injector carrier gas is air, dry air, oxygen, nitrogen, helium, argon gas or Krypton etc.
In one or two or more kinds.
5. the method according to profit requires 1, it is characterised in that：Discontinuous atmospheric pressure interface is used as connection electricity
From source and the critical component of mass spectrometer system, it is made up of an impulse electromagnetic valve and one section of electricity conductive hose；Work as pulse
When magnetic valve receives a pulse signal, valve is opened, and ionization source is connected with mass spectrum vacuum system；Valve
The time of opening can arbitrarily be adjusted from 5ms to 20ms.
6. the method according to profit requires 1, it is characterised in that：Mass spectrometric mass analyzer be rectangle from
Sub- trap, can carry out direct mass spectral analysis and cascade mass spectrometry, the mass spectrogram as obtained by analysis to sample
The peak position of upper sample parent ion and fragment ion pesticide sample can be carried out it is qualitative, by comparative sample peak
Peak height or peak area with standard items can also carry out quantitative analysis to sample.
7. the method according to profit requires 1, it is characterised in that：Described pesticide sample include organophosphor,
Organochlorine, Organic fluoride, organic nitrogen insecticide, organophosphor, organic sulfurcontaining fungicide are amide-type, organic
One or two or more kinds in Phosphorus, sulfonylurea herbicide.
8. the method according to profit requires 3, it is characterised in that：Annular electrode present position is in T-shaped glass
The left side of pipe upper end branch pipe；Annular electrode and column are coaxial to electrode；Column must be deep to the right side side of electrode
Enter the glass tube inner region that annular electrode is surrounded.
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| CN201510934211.7A CN106885837B (en) | 2015-12-15 | 2015-12-15 | A kind of method of the highly sensitive detection pesticide sample of fast and stable |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109839422A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of method of Quick narcotics appraising and constituent analysis |
| CN112098395A (en) * | 2020-08-06 | 2020-12-18 | 北京航空航天大学 | Dielectric barrier discharge plasma emission spectrometer based on online detection |
| CN113406184A (en) * | 2020-03-16 | 2021-09-17 | 中国科学院大连化学物理研究所 | In-situ thermal desorption photoionization device for improving mass spectrum drug detection sensitivity |
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| WO2005079410A2 (en) * | 2004-02-16 | 2005-09-01 | Nelsestuen Gary L | Biological profiles and methods of use |
| CN203606200U (en) * | 2013-12-05 | 2014-05-21 | 中国科学院大连化学物理研究所 | Rapid thermal desorption sampling device |
| CN103871826A (en) * | 2012-12-12 | 2014-06-18 | 中国科学院大连化学物理研究所 | Dielectric barrier discharge (DBD) mass-spectrum ionization source device added with selective detection reagent |
| CN104062306A (en) * | 2014-06-26 | 2014-09-24 | 劲牌有限公司 | Mass-spectrum rapid analysis method for pesticide residue in fruits and vegetables |
| CN104576287A (en) * | 2013-10-16 | 2015-04-29 | 北京理工大学 | Ion source system and mass spectrometer for atmospheric pressure interface |
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2015
- 2015-12-15 CN CN201510934211.7A patent/CN106885837B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005079410A2 (en) * | 2004-02-16 | 2005-09-01 | Nelsestuen Gary L | Biological profiles and methods of use |
| CN103871826A (en) * | 2012-12-12 | 2014-06-18 | 中国科学院大连化学物理研究所 | Dielectric barrier discharge (DBD) mass-spectrum ionization source device added with selective detection reagent |
| CN104576287A (en) * | 2013-10-16 | 2015-04-29 | 北京理工大学 | Ion source system and mass spectrometer for atmospheric pressure interface |
| CN203606200U (en) * | 2013-12-05 | 2014-05-21 | 中国科学院大连化学物理研究所 | Rapid thermal desorption sampling device |
| CN104062306A (en) * | 2014-06-26 | 2014-09-24 | 劲牌有限公司 | Mass-spectrum rapid analysis method for pesticide residue in fruits and vegetables |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109839422A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of method of Quick narcotics appraising and constituent analysis |
| CN113406184A (en) * | 2020-03-16 | 2021-09-17 | 中国科学院大连化学物理研究所 | In-situ thermal desorption photoionization device for improving mass spectrum drug detection sensitivity |
| CN112098395A (en) * | 2020-08-06 | 2020-12-18 | 北京航空航天大学 | Dielectric barrier discharge plasma emission spectrometer based on online detection |
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| CN106885837B (en) | 2019-04-09 |
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