CN106885837B - 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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- CN106885837B CN106885837B CN201510934211.7A CN201510934211A CN106885837B CN 106885837 B CN106885837 B CN 106885837B CN 201510934211 A CN201510934211 A CN 201510934211A CN 106885837 B CN106885837 B CN 106885837B
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- thermal desorption
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
Abstract
The invention discloses a kind of methods of novel detection pesticide sample.This method is to be equipped with the rectilinear ion trap mass spectrum of Thermal desorption low temperature plasma ionization source and discontinuous atmospheric pressure interface as detecting instrument, pass through direct mass spectrum or cascade mass spectrometry, realize detection highly sensitive for 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, will be sampled the injection port of cloth insertion Thermal desorption low temperature plasma, are then started scanning of the mass spectrum, obtain sample mass spectrum in 1s.Thermal desorption low temperature plasma ionization source can be used one or more of helium, argon gas, nitrogen or air and discharge as discharge gas, and carrier gas can choose one of air, dry air, helium, argon gas or nitrogen or several.The detection pattern of matrix ion trap mass spectrograph selects negative ion mode.This method is used for the detection of pesticide sample, detection speed to be fast, high sensitivity, and stability is strong.
Description
Technical field
It is a kind of based on the mass spectrographic matter of rectilinear ion trap the present invention relates to the detection method of the pesticides such as organic phosphorus, organochlorine
Spectrum analysis method.This method analysis speed is fast, and the reproducibility of testing result is high, and stability is strong, and the spirit for pesticide sample
Sensitivity is high, and the detection limit of sample is in pg magnitude.
Background technique
Pesticide is important the means of production, it also brings problems while guaranteeing China cereal crops yield,
Such as: pesticide excessively uses polluted river soil, pesticide residue to endanger health of people.Especially in recent years " poison rice ", have
The exposure of the events such as malicious vegetables even more allows people to promote to a new high degree concern of Pesticides Testing.
Traditional Pesticides Testing technology is mainly chromatography (including gas-chromatography and liquid chromatogram) technology, shooting flow body colour
Spectral technology and chromatograph-mass spectrometer coupling (GC-MS, LC-MS) technology etc..These methods generally require complicated sample pre-treatments,
Such as: Solid Phase Extraction, solid phase microextraction, matrix solid phase dispersion and supercritical extract, it is not only complicated for operation, and sample analysis institute
The time needed is longer.And the Pesticides Testing method that this patent proposes, without complicated pre-treatment, fluid sample or solid sample can
Directly to carry out sample detection, single sample detection can be completed in 1s, and the reproducibility of testing result is high, and stability is strong,
And for the high sensitivity of pesticide sample, the detection limit of sample is in pg magnitude.
Summary of the invention
The invention discloses a kind of methods of novel detection pesticide sample.This method be equipped with Thermal desorption low temperature etc. from
The matrix ion trap mass spectrograph of daughter ionization source and discontinuous atmospheric pressure interface is detecting instrument, passes through direct mass spectrum or tandem
Mass spectral analysis, realizes detection highly sensitive for the fast and stable of pesticide sample, and single sample detection time is less than 1s.
The technical solution adopted by the invention is as follows:
In order to realize the highly sensitive detection of pesticide sample, the present invention is by lower temperature plasma technology and rectilinear ion trap matter
Spectral technology combination, i.e., using under atmospheric pressure low temperature plasma as the mass spectrographic ionization source of rectilinear ion trap, and with helium, argon
Gas, Krypton, nitrogen, oxygen or dry air are as discharge gas.
In order to improve the stability of Pesticides Testing, we introduce Thermal desorption sample injector, by first leading sample gasification again
Enter low temperature plasma to be ionized, to ensure that the stability of sample introduction.And gaseous molecular is relative to liquid and solid-state molecular,
Active area when being low temperature plasma interaction is bigger, thus also contributes to detection sensitivity to a certain extent
It improves.
In order to shorten analysis time, we have selected discontinuous atmospheric pressure interface as connection ionization source and mass spectrum vacuum system
The tie of system.When sample introduction, solenoid valve is opened, and sample introduction finishes, and solenoid valve is closed immediately, and the time that solenoid valve is opened is typically chosen
5ms-20ms.Discontinuous atmospheric pressure interface ensure that sample volume using one side, on the other hand also ensure in vacuum cavity
Air pressure be unlikely to have too great fluctuation process, reduce the sucking rate of pump, substantially reduce the time of analysis detection.
Detecting instrument of the matrix ion trap mass spectrograph as pesticide is selected, is on the one hand because rectilinear ion trap is in addition to having
The common advantage of mass spectrum (such as: high sensitivity, amount of samples is few, and analysis speed is fast, separate and identify while carrying out etc.) except, also
Has the advantages that oneself uniqueness, high sensitivity, amount of samples is few, and analysis speed is fast, separates and identifies while carrying out.Single sample
MS-MS analysis is completed in 1s.
Advantages of the present invention is as follows:
Low-temperature plasma generator under Thermal desorption sample injector and atmospheric pressure is formed into ionization source, is crimped by discontinuous atmosphere
Mouth is docked with rectilinear ion trap mass spectrum, the detection for pesticide sample.This method detection speed is fast, and stability is strong, high sensitivity.
Compared with traditional Pesticides Testing method, the method that this patent proposes is not necessarily to cumbersome sample pre-treatments, detection speed
Degree is fast (single sample analysis is completed in 1s), sensitivity it is higher (for pesticide sample detection limit in pg magnitude).With other
Mass spectrograph is compared, matrix ion trap mass spectrograph compact, light-weight, and field assay may be implemented, and can be convenient into
The accuracy of row cascade mass spectrometry, qualitative, quantitative is higher.
Detailed description of the invention
The mass spectrographic structural schematic diagram of Fig. 1 Thermal desorption low temperature plasma rectilinear ion trap；
The voltage timing of Fig. 2 rectilinear ion trap mass spectrographic concrete analysis process and each stage；
The mass spectrogram of tetra- kinds of pesticide samples of Fig. 3 (phosmet, mirex, heptachlor and oxadiazon).
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and embodiments:
It is related to a kind of new method for measuring pesticide sample to invent, with the Thermal desorption low temperature plasma square of negative ion mode
Shape ion trap mass spectrometry technology is basic detection technique, by carrying out direct mass spectral analysis or cascade mass spectrometry to sample,
Achieve the purpose that qualitative or quantitative.
The overall structure diagram of instrument is as shown in Figure 1.This instrument includes consisting of part: Thermal desorption sample injector I, big
Air pressure low temperature plasma ionization source II, discontinuous atmospheric pressure interface III, rectilinear ion trap Mass Spectrometer Method system IV.Wherein square
Shape ion trap mass spectrometry detection system includes: cavity 1, molecular pump 2, diaphragm pump (fore pump) 3, rectilinear ion trap mass analyzer again
4, electron multiplier 5, amplifier and signal processing system 6.
Thermal desorption sample injector is mainly used for that liquid or solid sample is made to become gaseous molecular, the gaseous molecular after parsing by
Carrier gas carrier band enters atmos low-temperature plasma ionization source.Atmos low-temperature plasma ionization source generate plasma with
Gaseous sample molecular collision realizes the ionization to sample molecule by energy or electric charge transfer to sample molecule.Sample ions are again
Enter mass spectrometer system by discontinuous atmospheric pressure interface to be detected.The realization of cascade mass spectrometry is in direct mass spectrum point
On the basis of analysis plus the preceding paragraph swift waveform smashes parent ion to filter out parent ion, then by AC resonance technique, in turn
Obtain the MS-MS information of sample.
Embodiment 1
Fig. 2 gives the mass spectrographic concrete analysis process of Thermal desorption low temperature plasma rectilinear ion trap and voltage timing.From
It can be seen that sample is completed from sample introduction to analysis in figure, 4 stages are divided into, is the sample introduction stage respectively, ion cooling stage, sweeps
Retouch analysis phase and zero stage.Entire used time analysis time is less than 500ms, illustrates Thermal desorption low temperature plasma rectangular ion
Trap mass spectrum is a kind of quick detection means.
Embodiment 2
Fig. 3 gives detectable concentration under Thermal desorption low temperature plasma rectilinear ion trap mass spectrum anionic textiles mode
The phosmet of 10ppm, mirex, heptachlor and oxadiazon mass spectrogram.Phosmet belongs to organophosphorus pesticide, and mirex belongs to
Insecticide, heptachlor belong to cyclodienes insecticide, and oxadiazon belongs to herbicide.It can be seen from the figure that four kinds of pesticide samples are equal
There is stronger mass spectrum response signal.And the relative standard deviation of phosmet, mirex, heptachlor and oxadiazon sample detection
It (RSD) is 15%, 13%, 10% and 8% respectively.Therefore illustrate, Thermal desorption low temperature plasma rectilinear ion trap mass spectrum is one
Quick, the highly sensitive and strong stability Pesticides Testing method of kind.
Claims (7)
1. a kind of method of the highly sensitive detection pesticide sample of fast and stable, it is characterised in that: to assemble Thermal desorption low-temperature plasma
The rectilinear ion trap mass spectrum of body (LTP) ionization source and discontinuous atmospheric pressure interface (DAPI) is detecting instrument, Thermal desorption low temperature etc.
Gas ions ionization source includes Thermal desorption sample injector and plasma generator, and T-type glass tube is one of plasma generator
Point；Pesticide sample is parsed and is ionized by Thermal desorption low temperature plasma ionization source, after ionization to sample cloth as carrier
Sample ions by discontinuous atmospheric pressure sample introduction interface enter rectilinear ion trap mass analyzer carry out direct mass spectral analysis or
Cascade mass spectrometry, to realize the qualitative or quantitative detection of pesticide sample；
Thermal desorption low temperature plasma ionization source includes Thermal desorption sample injector and plasma generator；Plasma generator is again
Including radio-frequency power supply, annular electrode, column to electrode, discharge gas, T-type glass tube and tee tube；T-type glass tube left end and three
Port is connected on the right side of siphunculus, and T-type glass tube right end is connected with the import of discontinuous atmospheric pressure interface, the upper end branch of T-type glass tube
Pipe is connected with the outlet of Thermal desorption sample injector；Annular electrode is sheathed in the outside wall surface of T-type glass tube left end, column to electrode from
Port stretches to the circular region of T-type glass tube left end inner annular electrode on the left of tee tube, the upper port of tee tube with
Discharge gas gas source is connected；Annular electrode and column are connected respectively to electrode with radio-frequency power supply positive and negative anodes；Discharge gas is from threeway
One end of pipe enters between annular electrode and columnar electrode, generates plasma；Discharge gas is helium, argon gas, Krypton, nitrogen
One of gas, oxygen or dry air or two kinds or more；Sample gas is introduced by the branch pipe of T-type glass tube, in glass
Interaction is generated with plasma inside pipe and is ionized.
2. according to the method described in claim 1, it is characterized by: sampling cloth be for accepting liquid or solid sample,
Material is polytetrafluoroethylene (PTFE), and the specification for sampling cloth is 105mm*28mm.
3. according to the method described in claim 1, it is characterized by: the effect of the Thermal desorption sample injector is to make liquid or solid
The gasification of body sample, the pyrolysis eutectoid temperature of sample injector can be from room temperatures to arbitrarily adjusting 240 DEG C；Sample injector connection one is road-load
Gas enters low-temperature plasma generator for carrying the sample molecule after Thermal desorption；Sample injector carrier gas is air, dry sky
One of gas, oxygen, nitrogen, helium, argon gas or Krypton or two kinds or more.
4. according to the method described in claim 1, it is characterized by: discontinuous atmospheric pressure interface is as connection ionization source and matter
The critical component of spectra system is made of an impulse electromagnetic valve and one section of electricity conductive hose；When impulse electromagnetic valve receives an arteries and veins
When rushing signal, valve is opened, and ionization source is connected with mass spectrum vacuum system；The time that valve is opened can be any from 5ms to 20ms
It adjusts.
5., can be with according to the method described in claim 1, it is characterized by: mass spectrometric mass analyzer is rectilinear ion trap
Direct mass spectral analysis and cascade mass spectrometry are carried out to sample, by analyze on resulting mass spectrogram sample parent ion and fragment from
The peak position of son pesticide sample can be carried out it is qualitative, can be with by comparing the peak height or peak area of sample peak and standard items
Quantitative analysis is carried out to sample.
6. according to the method described in claim 1, it is characterized by: the pesticide sample include it is organic phosphorus, organochlorine, have
Machine fluorine, organic nitrogen insecticide, organic phosphorus, organic sulfurcontaining fungicide, amides, organic phosphates, in sulfonylurea herbicide
It is one or two or more kinds of.
7. according to the method described in claim 1, it is characterized by: annular electrode present position is in T-type glass tube upper end branch pipe
Left side；Annular electrode and column are coaxial to electrode；Column must go deep into the glass that annular electrode is surrounded to the right side side of electrode
Glass pipe inner region.
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| Application Number | Priority Date | Filing Date | Title |
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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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| 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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| CN106885837A CN106885837A (en) | 2017-06-23 |
| CN106885837B true CN106885837B (en) | 2019-04-09 |
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Families Citing this family (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 |
| CN113406184B (en) * | 2020-03-16 | 2022-05-31 | 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 |
| CN112098395B (en) * | 2020-08-06 | 2021-10-01 | 北京航空航天大学 | Dielectric barrier discharge plasma emission spectrometer based on online detection |
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 |
| 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 |
-
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 |
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