CN106501345A - The detection method of Microcystins in Water - Google Patents
The detection method of Microcystins in Water Download PDFInfo
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Abstract
The present invention relates to a kind of detection method of Microcystins in Water, the detection method is Direct Analysis ion gun-mass spectrography, comprises the following steps：(1) water sample pre-treatment prepares testing sample；(2) testing sample is ionized with direct ionization source；(3) testing sample that Mass Spectrometer Method has been ionized.The method only needs to simple filtration or filters the pre-treatment for adding flash baking to water sample, can direct detection, improve detection efficiency, disclosure satisfy that detection requirement real-time, quick, in situ, solve sample pre-treatments in existing detection technique complicated, it is difficult to detect the problem of Microcystins in Water real-time.The detection method that the present invention is provided can carry out qualitative and relative quantitative assay simultaneously, can analyze various microcystins simultaneously, be providing convenience property of practical operation.
Description
Technical field
The present invention relates to analysis technical field, more particularly to a kind of detection method of Microcystins in Water.
Background technology
In recent years, with economic fast development, water body eutrophication degree aggravates, and is harmful to blue algae water grey hair
Life is increased.Breakout of cyanobacteria blooms not only causes deteriorating water quality, and Microcystis aeruginosa, anabena, the algae that quivers etc.
Also to water body release microcapsule Algae toxins, the safety of aquatic ecosystem is endangered.
The monocyclic polypeptide that Microcystin (Microcystin, MC) basic structure is made up of 7 amino acid,
The monocyclic hepatotoxin of also referred to as 7 peptides, relative molecular weight is 1000 or so.Due to polypeptide variable position upper amino acid kind
The change of class, result in the diversity of MC.Hitherto it is found that more than 90 kinds of MCs isomers, toxicity is relatively strong,
The larger MC of yield is that (L, R, Y represent leucine, essence respectively for MC-LR, MC-RR and MC-YR
Propylhomoserin and tyrosine).MC has hepatotoxicity and tumor enhancement, and it not only produces poison to aquatile
Evil effect, it is also possible to which human health is endangered by the biological concentration of drinking water and food chain.
MC has large number of isomers and analog, when blue-green alga bloom breaks out, has usually contained multiple in water body
Miscellaneous MC mixtures, also have other kinds of cyanophycean toxin sometimes, and the MC monitored in water body is relatively stranded
Difficult.Only find the presence of MC in water body in time, specific aim process could be carried out to which, reduce human body and be good for
Health risk.
At present, impacts of the MC to water environment and the mankind and hydrobiological toxic have increasingly been caused entirely
The extensive concern in the world, this results in the tight demand to its detection method.Multiple being based on is developed in recent years
Biochemistry or the MC detection methods based on complicated analytical instrument.The existing biochemistry for determining Algae toxins
Although analysis method can determine the total amount of Microcystin within a few houres, Microcystin can not be recognized
Species, and easily there is false positive phenomenon in biochemical process；The existing instrument analytical method for determining Microcystin,
The pretreatment for carrying out complexity is needed mostly, poisonous organic reagent in a large number is consumed, object disengaging time is longer,
This causes the relatively costly of sample test, causes serious threat to environment and the healthy of experimental implementation person,
It is unfavorable for the quick detection of a large amount of samples, it is impossible to accomplish detection requirement real-time, quick, in situ.
Some methods with regard to using LC/MS detect Microcystins in Water are had both at home and abroad,
These reports are different from the sample pretreatment mode of the present invention, input mode, ionization method, Cleaning Principle
(Elisabeth J.Faassen,Miquel Lürling.Occurrence of the Microcystins MC-LW and
MC-LF in Dutch Surface Waters and Their Contribution to Total Microcystin Toxicity.
Marine drugs.11(2013)2643-2654.).And sample is needed also exist for through complicated pretreatment.In addition,
Also have the document report that detection acetone, medicine, explosive is analyzed using Direct Analysis ion-source mass spectrometer both at home and abroad
Road, these report with the present invention sample pretreatment mode, input mode, ion gun setting, testing goal,
Detection object difference (Guangming Xu, Bo Chen, Guozhu Liu, Shouzhuo Yao.Rapid
analysis of acetone in human plasma by derivatizating on desorption electrospray
ionization.Analyst.2010,135(9):2415-2419.).
Real-time Microcystin mass spectrum detection is not found in prior art, is therefore developed a kind of real
When, quick Microcystin mass spectrum detection of crucial importance.
Content of the invention
This is based on, it is an object of the invention to provide a kind of detection method of Microcystins in Water, can
Realize real-time, the quick detection of Microcystins in Water.
For achieving the above object, concrete technical scheme is as follows：
A kind of detection method of Microcystins in Water, the detection method are Direct Analysis ion gun-mass spectrum
Method, comprises the following steps：(1) water sample pre-treatment prepares testing sample；(2) testing sample is used and is directly divided
Component of isolating is ionized；(3) testing sample that Mass Spectrometer Method has been ionized.
Wherein in some embodiments, the Direct Analysis ion gun is selected from electron spray desorption ionization source, medium
One kind in barrier discharge ion gun, electron spray extraction ionization source.
Wherein in one embodiment, the Direct Analysis ion gun is electron spray desorption ionization source；Step (1)
The method of the water sample pre-treatment is：Water sample to be measured is taken, with the glass fibre that aperture is Φ 40～Φ 120mm
Filter membrane carries out vacuum filtration, filtrate is dropped in and be heated on sample stage 50～80 DEG C of dryings 30～200 seconds, system
Obtain testing sample；The parameter setting of step (2) is as follows：The angle of EFI solution line and sample stage is 30～
80 °, the distance of EFI solution line and sample is 1～3mm, the angle of mass spectrograph atmospheric pressure interface and sample stage
Spend for 10～60 °, mass spectrograph atmospheric pressure interface is 1～5mm with the distance of sample.
Wherein in one embodiment, the aperture of step (1) glass fiber filter is 50～Φ of Φ 70,
The temperature of the drying is 50 DEG C～60 DEG C, and the time of the drying is 85～95 seconds；The ginseng of step (2)
Number arranges as follows：The angle of EFI solution line and sample stage is 45～55 °, EFI solution line and sample
Distance be 1mm, the angle of mass spectrograph atmospheric pressure interface and sample stage is 30～40 °, mass spectrograph atmospheric pressure
Interface is 2.5～3.5mm with the distance of sample.
Wherein in one embodiment, the Direct Analysis ion gun is that electron spray extracts ionization source；Step (1)
The method of the water sample pre-treatment is：Water sample to be measured is taken, with the glass fibre that aperture is Φ 40～Φ 120mm
Filter membrane carries out vacuum filtration, and filtrate is testing sample；The parameter setting of step (2) is as follows：EFI solution
Angle between pipeline and sample introduction pipeline be 20～150 °, EFI solution line outlet with sample introduction tube outlet it
Between distance be 1～20mm, the angle between sample introduction pipeline and mass spectrograph atmospheric pressure interface be 100～170 °,
Distance at EFI solution line (or sample introduction pipeline) outlet and mass spectrum atmospheric pressure interface is 5～20mm, treats test sample
The flow of product solution is 1-40 μ L/min.
Wherein in one embodiment, the aperture of step (1) glass fiber filter is 50～Φ of Φ 70；
The parameter setting of step (2) is as follows：Angle between EFI solution line and sample introduction pipeline is 45～55 °,
The distance between the outlet of EFI solution line and sample introduction tube outlet are 3～7mm, and sample introduction pipeline and mass spectrograph are big
Angle between air pressure interface is 150～160 °, and EFI solution line (or sample introduction pipeline) outlet and mass spectrograph are big
The distance of air pressure interface is 8～12mm, and the flow of testing sample solution is 15～25 μ L/min.
Wherein in one embodiment, step (2) is described ionize the EFI solution used selected from methyl alcohol, water,
One or more in acetonitrile, formic acid, acetic acid, the flow of EFI solution is 1～50 μ L/min, and EFI is molten
The voltage that liquid is applied in is 3～5kV.
Wherein in one embodiment, step (2) the EFI solution that uses that ionizes is that volume ratio is 80：
19：The mixed liquor of 1 methyl alcohol, water and acetic acid or volume ratio are 1:1 acetonitrile and the mixed liquor of water, EFI are molten
The flow of liquid is 8～12 μ L/min, and the voltage that EFI solution is applied in is 3kV or 5kV.
Wherein in one embodiment, step (2) atomization gas that uses that ionize are nitrogen, helium or xenon
Gas, the linear velocity of atomization gas is 200～350m/s.
Wherein in one embodiment, step (2) atomization gas that uses that ionize are nitrogen, atomization gas
Linear velocity is 180～220m/s.
The invention has the advantages that：
The invention provides a kind of method of Direct Analysis ion gun-Mass Spectrometer Method Microcystins in Water, leads to
After Direct Analysis ionization source is crossed by Microcystin ionization in water sample, entering mass spectrograph carries out qualitative and quantitative point
Analysis.Prior art detects Microcystin by liquid chromatography-tandem mass, needs to enter sample
Row extraction repeatedly and enrichment, take time and effort, and detection efficiency is low, and the method to the extraction of water sample and was enriched with
Journey has been included in detection process, so as to simplify pretreatment, it is only necessary to water sample is carried out simply filter or
Person filter plus flash baking pre-treatment, you can direct detection, improve detection efficiency, disclosure satisfy that in real time,
Quickly, detection in situ is required, solves sample pre-treatments in existing detection technique complicated, it is difficult to fast in real time
The problem of speed detection Microcystins in Water.The detection method that the present invention is provided can carry out qualitative and phase simultaneously
To quantitative analysis, various microcystins can be analyzed simultaneously, be providing convenience property of practical operation.
Description of the drawings
Fig. 1 is the schematic flow sheet that Direct Analysis ion gun-mass spectrography detects Microcystins in Water；
Fig. 2 is electron spray desorption ionization source schematic diagram；
Electron spray desorption ionization source schematic diagrames of the Fig. 3 for embodiment 1；
Fig. 4 is that electron spray extracts ionization source schematic diagram；
Electron spray extraction ionization source schematic diagrames of the Fig. 5 for embodiment 2；
Fig. 6 is the mass spectrogram of the water sample of MC-RR containing Microcystin and MC-LR in embodiment 1；
Fig. 7 is the mass spectrogram of the water sample of MC-RR containing Microcystin and MC-LR in embodiment 2.
Specific embodiment
Below with reference to specific embodiment, the present invention will be further described.
Microcystin in 1 electron spray desorption ionization source of embodiment-mass spectrography detection water body
First, laboratory apparatus
Electron spray desorption ionization source is prepared according to a conventional method, and as shown in Figures 2 and 3, critical piece includes：
Three-dimensional mobile platform, EFI liquid pipeline, atomizer, sample stage etc., the structure of ionization source and principle are with reference to beautiful
The achievement in research of Purdue University of state：R.Graham Cooks,Zheng Ouyang,Zoltan Takats,Justin M.
Wiseman.Ambient Mass Spectrometry.Science 311(2006):1566-1570.
2nd, experimental technique
1st, water sample is prepared：500 250 μ g of μ g and MC-LR of MC-RR are weighed, with 500 μ L first after mixing
Alcohol dissolves, then is settled to 500ml with pure water, as Standard Stock solutions, MC-RR in this Standard Stock solutions,
The solubility of MC-LR is respectively 1 μ g/mL, 0.5 μ g/mL.With environmental water sample (according to GB/T 20466-2006
Detection, does not detect Microcystin) Microcystin Standard Stock solutions are diluted to MC-RR, MC-LR
Solubility be respectively 10 μ g/L, 5 μ g/L, as solution to be measured, be stored in be measured in refrigerator.
2nd, water sample pre-treatment：Take a certain amount of water sample, with glass fiber filter (Φ 60) 150mbar bar
Vacuum filtration under part, filtrate drop in heat drying 90s on sample stage (50 DEG C), and testing sample is obtained.
3rd, ionize and detect：
(1) instrument testing：Adjustment EFI solution line is 50 ° with the angle of sample stage, EFI solution line
Distance with sample is 1mm, and mass spectrograph atmospheric pressure interface is 35 ° with the angle of sample stage, mass spectrograph air
The distance of crimping mouth and sample is 3mm, and the flow of EFI solution is 10 μ L/min, and atomization gas linear velocity is
200m/s.
(2) sample introduction and detection：EFI solution (methyl alcohol used:Water:The volume ratio of acetic acid is 80：19：1)
First by the voltage of in addition 3kv, and spray from the inner sleeve of atomizer, the high speed nitrogen that atomizer outer tube sprays
Solvent is atomized rapidly and accelerates which by gas, makes powered drop strike testing sample surface.Testing sample
There is sputtering after being clashed into by high speed drop and enter gas phase, simultaneously because the purging of nitrogen and desiccation, contain
There is desolvation in the charged drop of testing sample, enter capillary atmospheric crimping mouth, then mass spectrometric
Detector is detected.
3rd, experimental result
Water sample of the present embodiment with MC-RR containing Microcystin (10 μ g/L) and MC-LR (5 μ g/L)
As sample, m/z=519.79 (MC-RR, [M+2H] is obtained2+) and m/z=498.282 (MC-LR,
[M+2H]2+) mass spectral characteristic peak, 2 times for MC-LR of the characteristic peak area of MC-RR, such as Fig. 6 institutes
Show.Result of the test shows：After 1 pair of sample carries out simply pretreatment, can be with the Microcystis aeruginosa in direct detection water body
Toxin；2 according to mass-to-charge ratio, it is possible to determine that the species of Microcystin；3 according to the characteristic peak of Microcystin
Area, can carry out quantitative analysis to which；In 4 testing results, the mass-to-charge ratio numerical value of Microcystin can be accurate
2 significant digits are arrived, such that it is able to separate Microcystin characteristic peak and impurity peaks according to mass-to-charge ratio.
Microcystin in 2 electron spray of embodiment extraction ionization source-mass spectrography detection water body
First, laboratory apparatus
Electron spray extraction ionization source is prepared according to a conventional method, and as shown in Figure 4 and Figure 5, critical piece includes：
Three-dimensional mobile platform, EFI liquid pipeline, atomizer, sample introduction pipeline etc., ionogenic structure and principle reference
The design of Chen etc.：Chen,H.W.；Venter,A.；Cooks,R.G.,Extractive electrospray
ionization for direct analysis of undiluted urine,milk and other complex mixtures
without sample preparation.Chem.Commun.19(2006):2042-2044.
2nd, experimental technique
1st, water sample is prepared：750 250 μ g of μ g and MC-LR of MC-RR are weighed, with 500 μ L first after mixing
Alcohol dissolves, then is settled to 500ml with pure water, as Standard Stock solutions, MC-RR in this Standard Stock solutions,
The solubility of MC-LR is respectively 1.5 μ g/mL, 0.5 μ g/mL.With environmental water sample (according to GB/T 20466-2006
Detection, does not detect Microcystin) Microcystin Standard Stock solutions are diluted to MC-RR, MC-LR
Solubility be respectively 15 μ g/L, 5 μ g/L, as solution to be measured, be stored in be measured in refrigerator.Other concentration
The Microcystin water sample of ratio is also configured according to the method described above.
2nd, water sample pre-treatment：Take a certain amount of water sample, with glass fiber filter (Φ 60) 150mbar bar
Vacuum filtration under part, is obtained testing sample solution.
3rd, ionize and detect：
(1) instrument testing：Angle between the outlet of adjustment EFI solution line and sample introduction pipeline is 50 °, electricity
The distance between the outlet of spray solution line and sample introduction tube outlet are 5mm, sample introduction pipeline and mass spectrograph atmospheric pressure
Angle between interface is 155 °, and EFI solution line (or sample introduction pipeline) is exported and mass spectrograph atmospheric pressure interface
The distance at place is 10mm.The flow of EFI solution is 10 μ L/min, and testing sample solution flow is 20 μ
L/min, the linear velocity of atomization gas is 200m/s.
(2) sample introduction and detection：EFI solution (acetonitrile used:The volume ratio of water is 1:1) first by addition 5kv's
Voltage, and spray from the inner sleeve of atomizer, the high speed nitrogen that atomizer outer tube sprays is rapidly by solvent mist
Change and make which to accelerate；Testing sample solution is in sample introduction pipeline equally by high speed nitrogen atomization；EFI solution and
The droplet of testing sample solution is simultaneously entered in the three dimensions before mass spectrograph atmospheric pressure interface, EFI solution pair
Sample carries out micro-extraction and ionization, subsequently into mass spectrograph atmospheric pressure interface, is examined by mass spectrometric detector
Survey.
3rd, experimental result
Water sample of the present embodiment with MC-RR containing Microcystin (15 μ g/L) and MC-LR (5 μ g/L)
As sample, m/z=519.79 (MC-RR, [M+2H] is obtained2+) and m/z=498.282 (MC-LR,
[M+2H]2+) mass spectral characteristic peak, 3 times for MC-LR of the characteristic peak area of MC-RR, such as Fig. 7 institutes
Show.Result of the test shows：After 1 pair of sample carries out simply pretreatment, can be with the Microcystis aeruginosa in direct detection water body
Toxin；2 according to mass-to-charge ratio, it is possible to determine that the species of Microcystin；3 according to the characteristic peak of Microcystin
Area, can carry out quantitative analysis to which；In 4 testing results, the mass-to-charge ratio numerical value of Microcystin can be accurate
2 significant digits are arrived, such that it is able to separate Microcystin characteristic peak and impurity peaks according to mass-to-charge ratio.
Each technical characteristic of embodiment described above arbitrarily can be combined, for making description succinct, not right
The all possible combination of each technical characteristic in above-described embodiment is all described, as long as however, these skills
There is no contradiction in the combination of art feature, be all considered to be the scope of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed,
But therefore can not be construed as limiting the scope of the patent.It should be pointed out that for this area
For those of ordinary skill, without departing from the inventive concept of the premise, some deformations can also be made and is changed
Enter, these belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended power
Profit requires to be defined.
Claims (10)
1. a kind of detection method of Microcystins in Water, it is characterised in that the detection method is direct
Analysis ion gun-mass spectrography, comprises the following steps：(1) water sample pre-treatment prepares testing sample；(2) will treat
Test sample product are ionized with Direct Analysis ion gun；(3) testing sample that Mass Spectrometer Method has been ionized.
2. the detection method of Microcystins in Water according to claim 1, it is characterised in that institute
It is electron spray desorption ionization source, dielectric barrier discharge ion gun, electron spray extraction electricity to state Direct Analysis ion gun
One kind in source.
3. the detection method of Microcystins in Water according to claim 2, it is characterised in that institute
Direct Analysis ion gun is stated for electron spray desorption ionization source；The method of step (1) the water sample pre-treatment is：
Water sample to be measured is taken, and vacuum filtration is carried out with the glass fiber filter that aperture is Φ 40～Φ 120mm, by filtrate
Drop in, testing sample is obtained；The ginseng of step (2)
Number arranges as follows：The angle of EFI solution line and sample stage is 30～80 °, EFI solution line and sample
Distance be 1～3mm, the angle of mass spectrograph atmospheric pressure interface and sample stage is 10～60 °, and mass spectrograph is big
Air pressure interface is 1～5mm with the distance of sample.
4. the detection method of Microcystins in Water according to claim 3, it is characterised in that step
Suddenly the aperture of (1) described glass fiber filter is 50～Φ of Φ 70, and the temperature of the drying is 50 DEG C～60 DEG C,
The time of the drying is 85～95 seconds；The parameter setting of step (2) is as follows：EFI solution line and sample
The angle of sample platform is 45～55 °, and the distance of EFI solution line and sample is 1～1.5mm, mass spectrograph air
The angle of crimping mouth and sample stage is 30～40 °, the distance of mass spectrograph atmospheric pressure interface and sample is 2.5～
3.5mm.
5. the detection method of Microcystins in Water according to claim 2, it is characterised in that institute
State Direct Analysis ion gun ionization source is extracted for electron spray；The method of step (1) the water sample pre-treatment is：
Water sample to be measured being taken, vacuum filtration being carried out with the glass fiber filter that aperture is Φ 40～Φ 120mm, filtrate is
For testing sample；The parameter setting of step (2) is as follows：The angle of EFI solution line and sample introduction pipeline is 20～
150 °, the outlet of EFI solution line and the distance between sample introduction tube outlet are 1～20mm, sample introduction pipeline and
Angle between mass spectrograph atmospheric pressure interface is 100～170 °, EFI solution line or sample introduction tube outlet and
Distance at mass spectrograph atmospheric pressure interface is 5～20mm, and the flow of testing sample solution is 1～40 μ L/min.
6. the detection method of Microcystins in Water according to claim 5, it is characterised in that step
Suddenly the aperture of (1) described glass fiber filter is 50～Φ of Φ 70；The parameter setting of step (2) is as follows：
EFI solution line is 45～55 ° with the angle of sample introduction pipeline, and the outlet of EFI solution line is gone out with sample introduction pipeline
Mouthful the distance between be 3～7mm, the angle between sample introduction pipeline and mass spectrograph atmospheric pressure interface be 150～
160 °, EFI solution line or sample introduction tube outlet and the distance at mass spectrograph atmospheric pressure interface be 8～
12mm, the flow of testing sample solution is 15～25 μ L/min.
7. the detection method of the Microcystins in Water according to claim 3-6, it is characterised in that
The one kind or many of the EFI solution of step (2) ionization in methyl alcohol, water, acetonitrile, formic acid, acetic acid
Kind, the flow of EFI solution is 1～50 μ L/min, and the voltage that EFI solution is applied in is 3～5kV.
8. the detection method of Microcystins in Water according to claim 7, it is characterised in that step
Suddenly the EFI solution of (2) described ionization is that volume ratio is 80：19：The mixed liquor of 1 methyl alcohol, water and acetic acid
Or volume ratio is 1:1 acetonitrile and the mixed liquor of water, the flow of EFI solution is 8～12 μ L/min, EFI
The voltage that solution is applied in is 3kV or 5kV.
9. the detection method of the Microcystins in Water according to claim 3-6, it is characterised in that
The atomization gas of step (2) ionization are nitrogen, helium or xenon, the linear velocity of atomization gas is 200～
350m/s.
10. the detection method of Microcystins in Water according to claim 9, it is characterised in that step
Suddenly the atomization gas of (2) described ionization are nitrogen, and the linear velocity of atomization gas is 180～220m/s.
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| CN107202833A (en) * | 2017-06-21 | 2017-09-26 | 佛山科学技术学院 | The quick determination method of copper ion pollution level in a kind of water body |
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