CN113899806A - Novel artificial tracer suitable for putting and tracing analysis method thereof - Google Patents
Novel artificial tracer suitable for putting and tracing analysis method thereof Download PDFInfo
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Abstract
The invention provides a novel tracer and a tracing method thereof, comprising the following steps: A. sampling and pre-monitoring the upstream and downstream or suspected points of the water body, and confirming that the novel tracer cannot be detected in the water body; B. pouring the prepared tracer into a water body at the upstream; C. recovering and sampling the tracer: sampling underground water by a sampler; D. sample extraction and analysis: extracting a sample by adopting a nanofiber solid-phase extraction column; E. analyzing the tracer component by adopting an in-situ ionization mass spectrometer to finally obtain a concentration value of the tracer component; F. the leakage is estimated from the continuously monitored concentration values and peak values. A novel artificial tracer is an artificial sweetener, and the artificial sweetener is one or two of acesulfame potassium or sucralose. The invention adopts the novel nano material concentration and enrichment combined with the in-situ ionization method, improves the detection speed of the artificial sweetener and improves the detection sensitivity, thereby providing a reliable means for tracing the underground water.
Description
Technical Field
The invention belongs to the field of tracing or tracing analysis research, and relates to a method for judging the mutual conversion relationship between underground water and surface water or between underground water and underground water, in particular to a novel artificial tracer suitable for putting and a tracing method.
Background
Common tracing and tracing technique
(1) Solid particle tracer tracing technology
Scientific household solid particles have a long history as tracers for water body tracing research, common bran coats, sawdust, yellow mud and the like are mainly used, and coding paper sheets can be used when conditions permit. It was documented by the jewish historian Flavius Josephus that approximately 10 b.c. began using chaff as a tracer to link the spring source of jordan river to the nearby pond. However, the solid particle tracer is generally applicable only to a large channel due to its large particle size, and is not very accurate in determining the flow state of groundwater.
(2) Edible yeast
The edible yeast is nontoxic and harmless and has small particle size, so the edible yeast also becomes an effective tracer for tracing the water body. At the end of the 19 th century and at the beginning of the 20 th century, scientists first performed quantitative traceability tests on large karst areas in europe using bacteria in combination with chlorine and fluorine. Because there are many uncertain factors, such as the diffusion, reproduction and death of strains, which are caused by the uncertainty of natural conditions, using yeast as a tracing technology is still in the exploration stage at present and progresses slowly.
(3) Chemical tracing technology
Some chemical reagents become the current mainstream tracing means due to good stability and simple testing methods, besides conventional inorganic tracers such as sodium chloride and sodium bromide, some organic tracers also become new pets along with the progress of the tracing analysis technology, such as ammonium molybdate, fluorescein sodium, rhodamine, fluorescent whitening agents and the like, but the tracers have more sources and low specificity, and sometimes are interfered by background. For example, sodium chloride and sodium bromide belong to common substances in water bodies and have a lot of sources, and a conductivity method is also adopted in a detection method, so that the error of tracing work is large. Ammonium molybdate, fluorescein sodium, rhodamine, fluorescent whitening agent and the like have certain biotoxicity, and when the concentration is higher, the water body can present certain color, and the panic can be caused to the psychology of people when the ammonium molybdate, the fluorescein sodium, the rhodamine, the fluorescent whitening agent and the like are added.
Therefore, the continuous search and development of new chemical tracing methods become common tasks for analytical chemists, hydrogeologists and environmentalists.
The current mature testing methods of the artificial sweetener comprise a high-efficiency liquid phase evaporation light scattering method, a Fourier transform Raman spectroscopy method, a liquid chromatography-mass spectrometry combined method and the like. These methods are sufficient for satisfying the analysis requirements in food and beverage, but are still not satisfactory as artificial tracer research because the tracer is diluted by many times after being put into water and is in trace or ultra-trace state after being subjected to complex convection diffusion, thus bringing difficulty to analysis and detection.
The current analysis of trace artificial sweeteners is mainly completed by a liquid chromatography-mass spectrometer. Scheurer et al developed a reverse phase liquid chromatography separation, columnTandem mass spectrometry with post addition of modifier (TRIS), Gan et al improved this process by adding the modifier TRIS directly to the mobile phase as an ion pair reagent to improve separation and also introducing TRIS during solid phase extraction to improve extraction efficiency. Similar methods have been developed by Berset and Edgar et al, but with different or higher performance mass spectrometers to accomplish multiple reaction monitoring. Wu et al used monitoring of adduct ions [ M + HCOO]-The method improves the sensitivity of the sucralose by 20 times, thereby realizing the direct analysis of the large-volume sample injection of the groundwater sample. Methods for simultaneously analyzing other target substances such as medicines, skin care products, endocrine disruptors and the like are developed continuously, but all methods adopt reversed phase separation tandem mass spectrometry detection methods, and all the methods have the problems of low sensitivity, difficult separation and the like because the methods use gradient elution and improve agents to realize separation, but the improve agents simultaneously have negative effects on the subsequent mass spectrometry detection, so that a pair of irreconcilable contradictions is formed.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and aims to provide a novel tracer agent suitable for putting in and used for communicating tracer research and an analysis method thereof, wherein the application range can cover the research on the relation between underground water and surface water, the research on dam leakage tracer monitoring, the research on quantitative tracer of karst underground rivers and the like.
The technical scheme adopted by the invention is as follows:
the novel artificial tracer is suitable for being put in, the tracer is an artificial sweetener, and the artificial sweetener is one or two of acesulfame potassium or sucralose.
A tracing method of a novel artificial tracer suitable for administration as claimed in claim 1, comprising the steps of:
A. on-site sampling and pre-monitoring: sampling and pre-monitoring the upstream and downstream or suspected points of the water body, and confirming that the novel tracer cannot be detected in the water body;
B. putting a tracer: pouring the prepared tracer into a water body at a position of more than 5-15 m upstream; estimating the flow velocity of the water body;
C. recovering, sampling and extracting a tracer: sampling underground water, and extracting the sample by adopting a nanofiber solid-phase extraction column containing nanofiber clusters;
D. mass spectrometry analysis: adopting an in-situ ionization mass spectrometer to analyze and detect the artificial tracer;
E. and continuously and dynamically monitoring the monitoring points.
Further, the tracer recovery sampling in the step C comprises the following specific steps: setting sampling points in nearby underground water, pumping out the upper layer stagnant water in the underground water well, observing the pH value and conductivity of the underground water in real time until all parameters are stable, then sampling the underground water by adopting a Beller tube sampler, wherein the sampling frequency is 1 time per hour, continuously sampling for 2 days, then sampling once every 6 hours, continuously sampling for 5 days, and testing the detection condition of the samples.
Further, the specific steps of the extraction in the step C are as follows: firstly, activating an extraction column by using 100 mu L-2mL of methanol, then passing 5-10mL of water sample through a nanofiber column, and directly completing activation in the field by using a 10mL injector; and then, taking 10mL of the collected sample water sample by using an injector, enabling the sample water sample to pass through a nanofiber column, and enriching the artificial tracer on a nanofiber cluster in the nanofiber column.
Further, the step D of mass spectrometry comprises the specific steps of: and (3) placing the nanofiber group enriched with the artificial tracer on a sample rack at an outlet of a discharge ion source, opening a mass spectrometer and the discharge ion source, ionizing the tracer molecules under the sputtering of ion current, and performing mass spectrometry under the driving of an electric field to finally obtain a concentration value of the tracer component.
Further, the specific surface area of the nanofiber solid-phase extraction column is larger than 1200m2Per g and the volume of the fiber mass is less than 0.3cm3To ensure the implementation of ionization efficiency.
Furthermore, a plurality of sample placing openings are sequentially arranged on the sample rack, and each sample can be detected one by one in a pulse mode; the sample frame and the discharge ion source are positioned on the same horizontal line and are vertically arranged, and the mass spectrometer and the plasma tail flame of the discharge ion source keep a certain angle in the horizontal direction; during detection, the plasma tail flame is directly splashed onto a sample, sample components on the sample rack are analyzed and ionized by the plasma tail flame and then directly enter the mass spectrometer inlet, and then the sample components enter the mass spectrometer under the driving of an electric field for detection.
Further, the discharge ion source is a dielectric barrier discharge ion source operating under atmospheric pressure, the mass number of the mass spectrometer comprises 35-500u, and the mass resolving power of the mass analyzer is 5000 or higher.
Further, the operation steps and parameters of the mass spectrometric detection are as follows:
a-1, opening a mass spectrometer to enable vacuum to reach an appointed state, and setting a mass scanning range to be 35-500 u;
b-1, opening a dielectric barrier electron source discharge power switch, adjusting the voltage and the frequency to 3500V, and adjusting the frequency to 26 kHz; opening a helium switch of reaction gas, adjusting the gas flow rate to 200mL/min, and igniting to stabilize the plasma tail flame;
c-1, fixing the nanofiber group enriched with the tracer on a sample rack, and moving the sample to the tail end of a plasma tail flame;
d-1, starting a mass spectrometer analysis and acquisition system, and recording and outputting a detection result;
the collection mode selects the negative ion mode, and the voltage parameters are as the following table;
the beneficial effects obtained by the invention are as follows: the invention adopts the novel nano material concentration and enrichment combined with the in-situ ionization method, improves the detection speed of the artificial sweetener and improves the detection sensitivity, thereby providing a reliable means for tracing the underground water. The invention selects artificial sweetener as tracer for the first time, develops a novel analysis and test method as technical support of the tracer process, extracts and enriches by novel small-volume nanofiber materials, rapidly analyzes and ionizes the extracted components by using an in-situ ionization method, and rapidly detects by adopting a high-resolution time-of-flight mass spectrum (the improvement of resolution ratio is also greatly improved for qualitative identification capability), thereby realizing the rapid tracer analysis of tracers such as acesulfame potassium and sucralose. The implementation of field rapid sampling extraction is matched, so that the whole process is rapid and efficient, and the identification rate is high; and the sample does not need to be eluted during detection, so that the detection is more convenient and faster.
The artificial sweetener is used as a tracer, and has the following advantages: 1. the water-soluble fluorescent powder is very easy to dissolve in water, is not easy to be adsorbed by media such as soil and the like, has extremely weak adsorbability compared with sodium fluorescein, rhodamine and the like, and has natural tracing advantages; 2. has high physical, chemical and biological stability, is not easy to metabolize, precipitate, degrade and volatilize; 3. no natural source exists, and the influence of the background concentration of the underground water is not required to be considered; 4. the product does not contain any toxin per se and has no radioactive hazard; 5. because the substances can be eaten, the substances are ensured to be non-toxic and harmless, and no safety concern exists when the substances are thrown into water.
Drawings
FIG. 1 is a mass spectrum of the detection result of the tracer in example 1 of the present invention;
FIG. 2 is a mass spectrum of the result of tracer detection in example 2 of the present invention;
FIG. 4 is a diagram of a tracer analytical mass spectrometry apparatus according to the invention;
FIG. 3 is a schematic diagram of the tracing method of the present invention;
in the figure: 11. a discharge tube; 12. a high-voltage electrode plate; 13. a grounding electrode plate; 14. a dielectric barrier discharge power supply; 15. an insulating sleeve; 16. an annular insulating sheet; 17. an air inlet pipe; 18. a flow controller; 21. a sample holder; 22. moving the slide rail; 23. a support; 31. a mass spectrometer; 32. a mass spectrometer inlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example one: judging the communication condition between a river and underground water
A. On-site sampling and pre-monitoring:
sampling the groundwater at the upstream, downstream and nearby of the river to confirm that the acesulfame potassium can not be detected in the water body; the monitoring step is referred to the steps (C) to (D).
B. Preparing and putting a tracer:
dissolving 1000 g of the novel tracer acesulfame potassium in 1L of pure water, uniformly shaking, and pouring the solution into a water body at the position 25m upstream; and estimating the flow velocity of the water body.
C. Recovering and sampling the tracer:
setting sampling points in nearby underground water, pumping out the upper layer stagnant water in an underground water well, observing in real time by adopting parameters such as pH value, conductivity and the like until all the parameters are stable, sampling the underground water by adopting a Beller tube sampler, wherein the sampling frequency is 1 time per hour, the sampling is continuously carried out for 2 days, and then the sampling is carried out once in 6 hours and the sampling is continuously carried out for 5 days; and testing the detection condition of the sample.
D. Sample extraction and analysis:
a nanofiber solid phase extraction column (manufactured by Suzhou Xianwei Nano Co., Ltd., model: XWy-01) was activated with 100. mu.L of methanol and 200. mu.L of pure water in this order, and 10mL of the collected water sample was taken out by an appropriate syringe and passed through the nanofiber column.
The specific surface area of the nano-fiber solid phase extraction column or similar materials is larger than 1200m2/g, 10mL of samples are extracted in the field, a target substance is adsorbed on a filler smaller than 0.5g, the concentration is equivalent to more than 1000 times after the target substance is directly and completely desorbed, and the volume of a fiber mass is generally smaller than 0.3cm3 so as to ensure the implementation of ionization efficiency.
E. Ionization source debugging and mass spectrometry: and (3) taking out the nanofiber clusters in the nanofiber column, placing the nanofiber clusters at an ion source outlet, opening a mass spectrometer 31 and an ion source, ionizing tracer molecules under the sputtering of ion current, and allowing the tracer molecules to enter the mass spectrometer 31 under the driving of an electric field for analysis to finally obtain a concentration value of the tracer.
As shown in fig. 3, the ion source is a dielectric barrier discharge ion source, and ionizes the reaction gas under normal pressure to generate a plasma tail flame; the sample frame 21 and the dielectric barrier discharge ion source are positioned on the same horizontal line and are vertically placed, the mass spectrometer and the plasma tail flame keep a certain angle in the horizontal direction, during detection, the plasma tail flame directly splashes onto the sample, sample components on the sample frame 21 are analyzed and ionized by the plasma tail flame and then directly enter the mass spectrometer inlet 32, and then the sample components enter the mass spectrometer 31 under the driving of an electric field for detection.
The dielectric barrier discharge ion source is developed by the inventor in the previous work, and as shown in fig. 2, the main structure of the dielectric barrier discharge ion source comprises a dielectric barrier discharge power supply 14, a high-voltage electrode plate 12, a grounding electrode plate 13 and a discharge tube 11, an insulating sleeve 15 is wrapped outside the discharge tube 11, an annular high-voltage electrode plate 12 and a grounding electrode plate 13 are wrapped outside the discharge tube 11 in the insulating sleeve 15, and the high-voltage electrode plate 12 and the grounding electrode plate 13 are separated by an annular insulating sheet 16. Two small holes for electrode wires to pass through are arranged on the insulating sleeve 15, and the electrode wires pass through the small holes to respectively electrically connect the high-voltage electrode plate 12 and the grounding electrode plate 13 with the dielectric barrier discharge power supply 14. An air inlet pipe 17 is arranged at one end of the discharge tube 11, and a flow controller 18 is arranged on the air inlet pipe 17 and used for adjusting air inflow to ensure that an air path is stable. The discharge tube 11 is made of quartz or ceramic, the length is 10cm, the outer diameter is 3mm, the inner diameter is 0.3mm, the insulating sleeve 15 is made of polytetrafluoroethylene, and the annular insulating sheet 16 is made of ceramic. The sample holder 21 is held at a vertical distance of 3mm from the end of the discharge vessel 11.
A plurality of sample placing openings are sequentially arranged on the sample rack 21, and the sample rack 21 moves on the movable slide rail 22 by means of the bracket 23 to realize continuous sample introduction.
The operating steps and various parameters of the instrument are as follows: a-1, opening a mass spectrometer 31 to enable vacuum to reach an appointed state, and setting a mass scanning range to be 35-500 u;
b-1, opening a dielectric barrier discharge power supply 14 switch, adjusting the voltage and the frequency to 3500V, and adjusting the frequency to 26 kHz; opening a helium switch of reaction gas, adjusting the gas flow rate to 200mL/min, and igniting to stabilize the plasma tail flame;
c-1, fixing the nanofiber cluster enriched with the tracer acesulfame on a sample rack 21, and moving the sample 21 to the tail end of a plasma tail flame;
d-1, starting a mass spectrometer 31 analysis acquisition system, and recording and outputting a detection result.
The mass spectrometer 31 used in this example was an atmospheric time-of-flight mass spectrometer, model API-TOFMS5000, with the acquisition mode selected for the negative ion mode and the other voltage parameters as given in the table below.
| Parameter(s) | Voltage value/V |
| Capillary | -130 |
| FocusLens | -115 |
| OutPlate | -77 |
| SK1 | -44 |
| DCQUp | -32.5 |
| DCQDown | -32.5 |
| DCQLeft | -32.5 |
| DCQRight | -32.5 |
| OutOrifice | 20 |
| |
23 |
| LensDown | 22.5 |
| Pulse 1 | -980 |
| |
800 |
| COM1 | -16 |
| COM2 | \ |
| SkimmerH | -31 |
| SkimmerL | \ |
| Pulse frequency (Hz) | 10000 |
| Pulse width (mus) | 6 |
| Trig + pulse width (mus) | 6 |
| Skimmer2 mode | DC mode |
| Grid | -20 |
| B-plate | -1504 |
| Focus | 420 |
| ACCE | 4200 |
| MCP | 5980 |
| Peak to peak RFQ | 580 |
| MIR peak to peak value | 120 |
| RFQ biasing | -32.5 |
F. And continuously and dynamically monitoring the underground water.
And continuously and dynamically monitoring the underground water sample, and directly and qualitatively judging whether the water body is communicated according to whether the tracer is detected.
As shown in figure 1, under the above parameters, the fragments with the mass number of 161.98 are molecular ion fragments after acesulfame potassium ionization, 77.97 are fragments after further fragmentation, if the above two fragments appear simultaneously, the tracer acesulfame potassium is detected, and in the case, through continuous monitoring, the intensity of the two fragments gradually increases, and the local underground water and the surface river water are communicated.
Example two: investigation and tracing discrimination of certain dam leakage condition
A. On-site sampling and pre-monitoring:
sampling the seepage water in and around the dam reservoir area (as shown in fig. 4) to confirm that sucralose cannot be detected in the water body; the monitoring step is referred to the steps (C) to (D).
B. Preparing and putting a tracer:
dissolving 1000 g of novel tracer sucralose in 1L of pure water, shaking up, and pouring the solution into a water body at a position 25m upstream; and estimating the flow velocity of the water body.
C. Recovering and sampling the tracer:
and (3) setting sampling points near the spring water, and sampling at the sampling frequency of 1 sampling per hour for 2 days continuously, and then sampling once again for 6 hours for 5 days continuously. And testing the detection condition of the sample.
D. Sample extraction and analysis:
a nanofiber solid phase extraction column (manufactured by Suzhou Xianwei Nano Co., Ltd., model: XWy-01) was activated with 100. mu.L of methanol and 200. mu.L of pure water in this order, and 10mL of the collected water sample was taken out by an appropriate syringe and passed through the nanofiber column.
E. Ionization source debugging and mass spectrometry: and (3) taking out the nanofiber clusters in the nanofiber column, placing the nanofiber clusters at an ion source outlet, opening a mass spectrometer 31 and an ion source, ionizing tracer molecules under the sputtering of ion current, and allowing the tracer molecules to enter the mass spectrometer 31 under the driving of an electric field for analysis to finally obtain a concentration value of the tracer.
The ion source is a dielectric barrier discharge ion source, and the reaction gas is ionized under normal pressure to generate plasma tail flames; the sample frame and the dielectric barrier discharge ion source are positioned on the same horizontal line and are vertically placed, the mass spectrometer keeps a certain angle with the plasma tail flame in the horizontal direction, during detection, the plasma tail flame directly splashes onto the sample, and sample components on the sample frame 21 are analyzed and ionized by the plasma tail flame and then directly enter the mass spectrometer inlet 32 and then enter the mass spectrometer 31 under the driving of an electric field for detection.
The dielectric barrier discharge ion source is developed by the inventor in the previous work, and mainly structurally comprises a dielectric barrier discharge power supply 14, a high-voltage electrode plate 12, a grounding electrode plate 13 and a discharge tube 11, wherein an insulating sleeve 15 is wrapped outside the discharge tube 11, an annular high-voltage electrode plate 12 and an annular grounding electrode plate 13 are wrapped outside the discharge tube 11 in the insulating sleeve 15, and the high-voltage electrode plate 12 and the grounding electrode plate 13 are separated by an annular insulating sheet 16. Two small holes for electrode wires to pass through are arranged on the insulating sleeve 15, and the electrode wires pass through the small holes to respectively electrically connect the high-voltage electrode plate 12 and the grounding electrode plate 13 with the dielectric barrier discharge power supply 14. An air inlet pipe 17 is arranged at one end of the discharge tube 11, and a flow controller 18 is arranged on the air inlet pipe 17 and used for adjusting air inflow to ensure that an air path is stable. The discharge tube 11 is made of quartz or ceramic, the length is 10cm, the outer diameter is 3mm, the inner diameter is 0.3mm, the insulating sleeve 15 is made of polytetrafluoroethylene, and the annular insulating sheet 16 is made of ceramic. The sample holder 21 is held at a vertical distance of 3mm from the end of the discharge vessel 11.
A plurality of sample placing openings are sequentially arranged on the sample rack 21, and the sample rack 21 moves on the movable slide rail 22 by means of the bracket 23 to realize continuous sample introduction.
The operating steps and various parameters of the instrument are as follows: a-1, opening a mass spectrometer 31 to enable vacuum to reach an appointed state, and setting a mass scanning range to be 35-500 u;
b-1, opening a dielectric barrier discharge power supply 14 switch, adjusting the voltage and the frequency to 3500V, and adjusting the frequency to 26 kHz; opening a helium switch of reaction gas, adjusting the gas flow rate to 200mL/min, and igniting to stabilize the plasma tail flame;
c-1, fixing the nanofiber cluster enriched with the tracer acesulfame on a sample rack 21, and moving the sample 21 to the tail end of a plasma tail flame;
d-1, starting a mass spectrometer 31 analysis acquisition system, and recording and outputting a detection result.
The mass spectrometer 31 used in this example was an atmospheric time-of-flight mass spectrometer, model API-TOFMS5000, with the acquisition mode selected for the negative ion mode and the other voltage parameters as given in the table below.
| Parameter(s) | Voltage value/V |
| Capillary | -130 |
| FocusLens | -115 |
| OutPlate | -85 |
| SK1 | -57 |
| DCQUp | -32.5 |
| DCQDown | -32.5 |
| DCQLeft | -32.5 |
| DCQRight | -32.5 |
| OutOrifice | 20 |
| |
23 |
| LensDown | 22.5 |
| Pulse 1 | -980 |
| |
800 |
| COM1 | -16 |
| COM2 | \ |
| SkimmerH | -31 |
| SkimmerL | \ |
| Pulse frequency (Hz) | 10000 |
| Pulse width (mus) | 6 |
| Trig + pulse width (mus) | 6 |
| Skimmer2 mode | DC mode |
| Grid | -20 |
| B-plate | -1504 |
| Focus | 420 |
| ACCE | 4200 |
| MCP | 5980 |
| Peak to peak RFQ | 580 |
| MIR peak to peak value | 120 |
| RFQ biasing | -32.5 |
F. And continuously and dynamically monitoring the underground water.
And continuously and dynamically monitoring the slope water sample, and directly and qualitatively judging whether the slope seepage is the seepage of water in a dam of a nearby reservoir according to whether the tracer is detected.
As shown in fig. 2, under the above analysis parameters, the mass spectrum of sucralose should be 395.0, 397.0, 399.0, and the simultaneous occurrence of three fragment peaks indicates that sucralose has been detected in the water body, and it can be determined that the side slope water is dam leakage according to the fact that sucralose has been detected.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A novel artificial tracer agent suitable for putting is characterized in that: the artificial tracer is an artificial sweetener, and the artificial sweetener is one or two of acesulfame potassium or sucralose.
2. A tracing method of a novel artificial tracer adapted to be administered according to claim 1, wherein: the method comprises the following steps:
A. on-site sampling and pre-monitoring: sampling and pre-monitoring the upstream and downstream or suspected points of the water body, and confirming that the novel tracer cannot be detected in the water body;
B. putting a tracer: pouring the prepared tracer into a water body at a position of more than 5-15 m upstream; estimating the flow velocity of the water body;
C. recovering, sampling and extracting a tracer: sampling underground water, and extracting the sample by adopting a nanofiber solid-phase extraction column containing nanofiber clusters;
D. mass spectrometry analysis: directly analyzing and detecting the artificial tracer on the nanofiber cluster by adopting an in-situ ionization mass spectrometer;
E. and continuously and dynamically monitoring the monitoring points.
3. The tracing method of the novel artificial tracer suitable for being dosed according to claim 2, wherein: the concrete steps of tracer recovery and sampling in the step C are as follows: setting sampling points in nearby underground water, pumping out the upper layer stagnant water in the underground water well, observing the pH value and conductivity of the underground water in real time until all parameters are stable, then sampling the underground water by adopting a Beller tube sampler, wherein the sampling frequency is 1 time per hour, continuously sampling for 2 days, then sampling once every 6 hours, continuously sampling for 5 days, and testing the detection condition of the samples.
4. The tracing method of the novel artificial tracer suitable for being dosed according to claim 2, wherein: the concrete steps of the extraction in the step C are as follows: firstly, activating an extraction column by using 100 mu L-2mL of methanol, then passing 5-10mL of water sample through a nanofiber column, and directly completing activation in the field by using a 10mL injector; and then, taking 10mL of the collected sample water sample by using an injector, enabling the sample water sample to pass through a nanofiber column, and enriching the artificial tracer on a nanofiber cluster in the nanofiber column.
5. The tracing method of the novel artificial tracer suitable for being dosed according to claim 2, wherein: the step D of mass spectrometry comprises the following specific steps: and (3) placing the nanofiber group enriched with the artificial tracer on a sample rack at an outlet of a discharge ion source, opening a mass spectrometer and the discharge ion source, ionizing the tracer molecules under the sputtering of ion current, and performing mass spectrometry under the driving of an electric field to finally obtain a concentration value of the tracer component.
6. The tracing method of the novel artificial tracer suitable for being dosed according to claim 2, wherein: the specific surface area of the nanofiber solid-phase extraction column is more than 1200m2Per g and the volume of the fiber mass is less than 0.3cm3To ensure the implementation of ionization efficiency.
7. The tracing method of the novel artificial tracer suitable for being dosed according to claim 5, wherein: a plurality of sample placing openings are sequentially arranged on the sample rack, and each sample can be detected one by one in a pulse mode; the sample frame and the discharge ion source are positioned on the same horizontal line and are vertically arranged, and the mass spectrometer and the plasma tail flame of the discharge ion source keep a certain angle in the horizontal direction; during detection, the plasma tail flame is directly splashed onto a sample, sample components on the sample rack are analyzed and ionized by the plasma tail flame and then directly enter the mass spectrometer inlet, and then the sample components enter the mass spectrometer under the driving of an electric field for detection.
8. The tracing method of the novel artificial tracer suitable for being dosed according to claim 5, wherein: the discharge ion source is a dielectric barrier discharge ion source working under atmospheric pressure, the mass number of the mass spectrum detector comprises 35-500u, and the mass resolution of the mass analyzer is 5000 or higher.
9. The tracing method of the novel artificial tracer suitable for being dosed according to claim 5, wherein: the operating steps and parameters of the mass spectrometric detection are as follows:
a-1, opening a mass spectrometer to enable vacuum to reach an appointed state, and setting a mass scanning range to be 35-500 u;
b-1, opening a dielectric barrier electron source discharge power switch, adjusting the voltage and the frequency to 3500V, and adjusting the frequency to 26 kHz; opening a helium switch of reaction gas, adjusting the gas flow rate to 200mL/min, and igniting to stabilize the plasma tail flame;
c-1, fixing the nanofiber group enriched with the tracer on a sample rack, and moving the sample to the tail end of a plasma tail flame;
d-1, starting a mass spectrometer analysis and acquisition system, and recording and outputting a detection result;
the collection mode selects the negative ion mode, and the voltage parameters are as the following table;
。
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