Liquid laser ablation sampling system and method, storage medium and computer equipment

Abstract

The invention discloses a liquid laser denudation sampling system and method, a storage medium and computer equipment. The system comprises a liquid injection device, a denudation pool and a waste liquid discharge device, the liquid injection device is used for extracting a liquid sample and injecting the liquid sample into the liquid storage tank through the liquid injection port and the first channel; after the liquid sample is analyzed, the washing liquid is extracted and injected into the liquid storage tank through the liquid injection port and the first channel; the liquid discharge device is used for discharging the liquid sample through the second channel and the liquid discharge port after the liquid sample is analyzed; and when the first channel and the liquid storage tank are cleaned, the cleaning liquid after cleaning is discharged through the second channel and the liquid outlet. According to the liquid sample injection device, air in the liquid storage tank and the first channel can be fully discharged in the liquid sample injection process, meanwhile, the functions of liquid sample injection, denudation tank cleaning, waste liquid discharging and the like are integrated, and the liquid sample analysis process is more automatic, simpler and more convenient.

Description

Technical Field

[0001] This application relates to the technical field of laser ablation sampling, and in particular to a liquid laser ablation sampling system and method, a storage medium, and a computer device. Background Art

[0002] As a micro-area in-situ analysis technology, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been widely used in the field of earth science. Since the first report in 1985 on using laser as a sampling method in combination with ICP-MS for quantitative analysis of trace element composition in geological samples, laser has been widely accepted as an introduction technology for ICP-MS analysis of solid samples. In recent years, more and more studies have introduced laser into the field of liquid sample analysis, including: geological samples (such as pore water, seawater), biological samples (such as human blood, cerebrospinal fluid), environmental samples (such as atmospheric particulate matter, red wine), etc. Laser ablation of liquid samples can generate aerosol particles. Compared with traditional liquid sampling, this technology has the advantages of simple sample preparation, short time consumption, small sampling volume, no waste liquid generation, high aerosol transmission efficiency, ability to analyze complex matrix samples, and a higher concentration detection range.

[0003] In the prior art, when using laser to ablate and sample liquid samples, during the process of injecting the liquid sample into the ablation cell, air often remains in the injection pipeline, which directly affects the subsequent laser ablation effect; in addition, the automation degree of the existing sampling system is relatively low, greatly reducing the analysis efficiency of liquid samples. Summary of the Invention

[0004] In view of this, this application provides a liquid laser ablation sampling system and method, a storage medium, and a computer device, which are beneficial to fully discharging the air in the liquid storage tank and the first channel during the injection process of liquid samples, thereby solving the technical problem that the residual air in the pipeline floats in the form of bubbles and affects the laser ablation effect. In addition, this system integrates functions such as liquid sample injection, ablation cell cleaning, and waste liquid discharge, and can meet test requirements such as online real-time replacement of different liquid samples, automatic cleaning of the ablation cell, and timely discharge of waste liquid. It omits the offline manual liquid sample injection and ablation cell cleaning links, making the liquid sample analysis process more automated and simplified, and having stronger operability on the premise of improving the analysis efficiency of liquid samples.

[0005] According to one aspect of this application, a liquid laser ablation sampling system is provided, including a liquid injection device, an ablation cell, and a waste liquid discharge device;

[0006] Among them, the erosion cell includes a liquid injection port, a liquid discharge port, and a liquid storage pool. The liquid injection port is communicated with the bottom end of the liquid storage pool through a first channel. The liquid discharge port is communicated with the first channel through a second channel. And in the vertical direction, the liquid injection port is lower than the liquid discharge port. The liquid injection port is connected to the liquid injection device, and the liquid discharge port is connected to the waste liquid discharge device;

[0007] The liquid injection device is used to extract a liquid sample and inject the liquid sample into the liquid storage pool through the liquid injection port and the first channel; and, after the liquid sample is analyzed, extract the washing liquid and inject the washing liquid into the liquid storage pool through the liquid injection port and the first channel to clean the first channel and the liquid storage pool;

[0008] The waste liquid discharge device is used to discharge the liquid sample through the second channel and the liquid discharge port after the liquid sample is analyzed; and, when the first channel and the liquid storage pool are cleaned, discharge the washed washing liquid through the second channel and the liquid discharge port.

[0009] According to another aspect of the present application, a liquid laser ablation sampling method is provided, which is applied to the liquid laser ablation sampling system described in any one of the above, and includes:

[0010] The liquid injection device extracts a liquid sample and injects the liquid sample into the liquid storage pool of the erosion cell through the liquid injection port and the first channel of the erosion cell. The first channel is the connection channel between the liquid injection port and the bottom end of the liquid storage pool;

[0011] After the liquid sample is analyzed, the waste liquid discharge device discharges the liquid sample through the second channel and the liquid discharge port of the erosion cell. The second channel is the connection channel between the liquid discharge port and the first channel;

[0012] The liquid injection device extracts the washing liquid and injects the washing liquid into the liquid storage pool through the liquid injection port and the first channel to clean the first channel and the liquid storage pool;

[0013] When the first channel and the liquid storage pool are cleaned, the waste liquid discharge device discharges the washed washing liquid through the second channel and the liquid discharge port.

[0014] According to another aspect of the present application, a storage medium is provided, on which a computer program is stored. When the program is executed by a processor, the above liquid laser ablation sampling method is implemented.

[0015] According to another aspect of the present application, there is provided a computer device, including a storage medium, a processor, and a computer program stored on the storage medium and executable on the processor. When the processor executes the program, the above-mentioned liquid laser ablation sampling method is implemented.

[0016] By means of the above technical solution, a liquid laser ablation sampling system and method, a storage medium, and a computer device provided by the present application integrate the liquid injection port and the liquid discharge port inside the ablation cell in the vertical direction into the same pipeline (finally integrated on the first channel), and communicate with the bottom of the liquid storage tank. And the position of the liquid injection port is lower than the position of the liquid discharge port in the vertical direction, which is beneficial to fully discharge the air in the liquid storage tank and the first channel during the injection process of the liquid sample, thereby solving the technical problem that the residual air in the pipeline floats in the form of bubbles and affects the laser ablation effect. In addition, the system integrates functions such as liquid sample injection, ablation cell cleaning, and waste liquid discharge, and can meet test requirements such as online real-time replacement of different liquid samples, automatic cleaning of the ablation cell, and timely discharge of waste liquid. It omits the offline manual liquid sample injection and ablation cell cleaning links, making the liquid sample analysis process more automated and simplified, and having stronger operability on the premise of improving the liquid sample analysis efficiency.

[0017] The above description is only an overview of the technical solution of the present application. In order to be able to understand the technical means of the present application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features and advantages of the present application more obvious and understandable, the specific embodiments of the present application are specifically described below. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The drawings described herein are used to provide a further understanding of the present application, and constitute a part of the present application. The schematic embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation of the present application. In the drawings:

[0019] Figure 1 Shows a schematic structural diagram of a liquid laser ablation sampling system provided by an embodiment of the present application;

[0020] Figure 2 Shows a schematic diagram of the influence of the horizontal distance between the extraction tube nozzle and the laser ablation point on the signal intensity of four representative elements, namely Li, Rb, La, and Pb;

[0021] Figure 3 Shows a schematic diagram of the influence of the horizontal distance between the extraction tube nozzle and the laser ablation point on the signal stability of four representative elements, namely Li, Rb, La, and Pb;

[0022] Figure 4Shows a schematic cross-sectional shape of an erosion cell provided by an embodiment of the present application on a target cross-section;

[0023] Figure 5 Shows a schematic structural diagram of another liquid laser ablation sampling system provided by an embodiment of the present application;

[0024] Figure 6 Shows a schematic structural diagram of an erosion cell provided by an embodiment of the present application;

[0025] Figure 7 Shows a schematic flowchart of a liquid laser ablation sampling method provided by an embodiment of the present application;

[0026] Figure 8 Shows a schematic diagram of the device structure of a computer device provided by an embodiment of the present application. Detailed implementation manners

[0027] The present application will be described in detail below with reference to the drawings and in conjunction with embodiments. It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0028] In this embodiment, a liquid laser ablation sampling system is provided. As Figure 1 shown, the system includes: a liquid injection device 1, an erosion cell 2, and a waste liquid discharge device 3;

[0029] Among them, the erosion cell 2 includes a liquid injection port 21, a liquid discharge port 22, and a liquid storage pool 23. A first channel 24 is provided for communicating between the bottom end of the liquid injection port 21 and the liquid storage pool 23. A second channel 25 is provided for communicating between the liquid discharge port 22 and the first channel 24. In the vertical direction, the liquid injection port 21 is lower than the liquid discharge port 22. The liquid injection port 21 is connected to the liquid injection device 1, and the liquid discharge port 22 is connected to the waste liquid discharge device 3;

[0030] The liquid injection device 1 is configured to extract a liquid sample and inject the liquid sample into the liquid storage pool 23 through the liquid injection port 21 and the first channel 24; and, after the liquid sample is analyzed, extract a cleaning solution and inject the cleaning solution into the liquid storage pool 23 through the liquid injection port 21 and the first channel 24 to clean the first channel 24 and the liquid storage pool 23;

[0031] The waste liquid discharge device 3 is configured to discharge the liquid sample through the second channel 25 and the liquid discharge port 22 after the liquid sample is analyzed; and, when cleaning the first channel 24 and the liquid storage pool 23, discharge the cleaned cleaning solution through the second channel 25 and the liquid discharge port 22.

[0032] A liquid laser ablation injection system provided by an embodiment of the present application can achieve automatic injection of liquid samples, washing liquids and other liquids. Specifically, the system may include a liquid injection device 1, an ablation cell 2, and a waste liquid discharge device 3. The ablation cell may include a liquid injection port 21, a liquid discharge port 22, and a liquid storage pool 23. Among them, the liquid injection port 21 of the ablation cell 2 and the bottom end of the liquid storage pool 23 are connected through a first channel 24, and the liquid discharge port 22 and the first channel 24 may be connected through a second channel 25. Specifically, the second channel 25 may be a branch channel on the first channel 24, and the other side of the branch channel is connected to the liquid discharge port 22. In addition, in the vertical direction, the position of the liquid injection port 21 of the ablation cell 2 may be lower than the position of the liquid discharge port 22. In the embodiment of the present application, by integrating the liquid injection port 21 and the liquid discharge port 22 of the ablation cell 2 in the vertical direction into the same pipeline (finally integrated on the first channel 24), and connecting them to the bottom of the liquid storage pool 23, and the position of the liquid injection port 21 is lower than the position of the liquid discharge port 22 in the vertical direction. In terms of microfluidic injection, adopting this structural design is beneficial to avoiding the problem that there is a little air remaining in the pipeline at the bottom of the liquid storage pool 23 due to factors such as the surface tension of the material and the gas pressure in the pipeline. If the air in the pipeline at the bottom of the liquid storage pool 23 is not completely discharged, this part of the gas will float in the form of bubbles during the analysis of the liquid sample, which will affect the good contact between the liquid level in the liquid storage pool 23 and the cover of the liquid storage pool 23, and further seriously affect the laser focusing and laser ablation processes. Therefore, ensuring that the air in the liquid storage pool 23 and its bottom pipeline is completely discharged during the injection process is very crucial for the accurate quantitative analysis of the trace element composition of the liquid sample. In addition, the liquid injection port 21 of the ablation cell 2 and the liquid injection device 1 may be connected through a hose, and the liquid discharge port 22 of the ablation cell 2 and the waste liquid discharge device 3 may be connected through a hose.

[0033] The liquid injection device 1 can automatically extract the liquid sample, and then inject the extracted liquid sample into the liquid storage pool 23 of the ablation cell 2 through the liquid injection port 21 and the first channel 24 of the ablation cell 2 to achieve automatic injection of the liquid sample in the ablation cell 2. Then, the laser can emit a laser beam to perform laser ablation on the liquid sample in the ablation cell 2, and the generated aerosol particles can be blown into the laser ablation inductively coupled plasma mass spectrometer by auxiliary gases such as helium to achieve the analysis of the liquid sample.

[0034] After the analysis of the liquid sample is completed, the waste liquid discharge device 3 can discharge the remaining liquid sample in the liquid storage pool 23 and the first channel 24. Specifically, it can be discharged from the liquid discharge port 22 through the second channel 25.

[0035] After the remaining liquid sample is discharged, the liquid injection device 1 can also automatically extract the washing liquid, and inject the extracted washing liquid into the storage pool 23 of the ablation cell 2 through the liquid injection port 21 and the first channel 24 of the ablation cell 2, and clean the first channel 24 and the storage pool 23 during this process. During the process of cleaning the first channel 24 and the storage pool 23 with the washing liquid, the waste liquid discharge device 3 can also discharge the washed washing liquid from the drain port 22 through the second channel 25, thereby realizing the automatic cleaning of the first channel 24 and the storage pool 23 after the liquid sample analysis, so that the analysis of the remaining liquid samples can be directly carried out subsequently without manual cleaning.

[0036] By applying the technical solution of this embodiment, the liquid injection port 21 and the drain port 22 inside the ablation cell 2 are integrated in the same pipeline in the vertical direction (finally integrated on the first channel 24), and are communicated with the bottom of the storage pool 23, and the position of the liquid injection port 21 is lower than the position of the drain port 22 in the vertical direction, which is beneficial to fully discharge the air in the storage pool 23 and the first channel 24 during the liquid sample injection process, thereby solving the technical problem that the residual air in the pipeline floats in the form of bubbles and affects the laser ablation effect. In addition, the system integrates functions such as liquid sample injection, ablation cell 2 cleaning, waste liquid discharge, etc., can realize test requirements such as online real-time replacement of different liquid samples, automatic cleaning of the ablation cell 2, and timely discharge of waste liquid, omits the offline artificial liquid sample injection and ablation cell 2 cleaning links, makes the liquid sample analysis process more automated and simplified, and has stronger operability on the premise of improving the liquid sample analysis efficiency.

[0037] In the embodiment of the present application, optionally, the system further includes a timing module 4, the liquid injection device 1 includes an automatic sampler 11 and an injection pump 12, and the automatic sampler 11 includes a sampling needle 111 and a liquid storage module 112; wherein, the sampling needle 111 of the automatic sampler 11 and the injection pump 12 are connected to the liquid injection port 21 through a three-way valve, and the sampling needle 111, the injection pump 12 and the liquid injection port 21 are respectively connected to the three-way valve through hoses; the injection pump 12 is used to extract liquid from the liquid storage module 112 of the automatic sampler 11 through the sampling needle 111, and the liquid is the liquid sample or the washing liquid; the timing module 4 is used to start timing when the injection pump 12 extracts liquid; the injection pump 12 is further used to inject the extracted liquid into the storage pool 23 through the liquid injection port 21 and the first channel 24 when the timing time of the timing module 4 reaches a first preset time interval, so that the liquid level in the storage pool 23 is in full contact with the lower surface of the covering on the storage pool 23.

[0038] In this embodiment, the system may further include a timing module 4. In addition, the liquid injection device 1 may include an autosampler 11 and an injection pump 12. The autosampler 11 may further include a sampling needle 111 and a liquid storage module 112. Here, the sampling needle 111 of the autosampler 11, the injection pump 12, and the liquid injection port 21 of the ablation cell 2 are respectively connected to one port of the three-way valve. Specifically, the sampling needle 111 may be connected to port A of the three-way valve through a hose, the injection pump 12 may be connected to port B of the three-way valve through a hose, and the liquid injection port 21 may be connected to port C of the three-way valve through a hose. The above hoses may specifically be silicone hoses. In the embodiment of the present application, the sampling needle 111 of the autosampler 11, the injection pump 12, and the liquid injection port 21 of the ablation cell 2 are connected by a three-way valve. Different liquid samples can be switched through the sampling needle 111, and the automatic extraction and injection of liquid samples can be achieved through the injection pump 12, which can greatly improve the injection efficiency and accuracy of liquid samples.

[0039] The autosampler 11 may further include a sampling needle 111 and a liquid storage module 112. The liquid storage module 112 may be used to store different liquid samples, washing solutions, etc. In the specific application process, the injection pump 12 may extract the required liquid from the liquid storage module 112 through the sampling needle 111 of the autosampler 11. For example, when analyzing a liquid sample, the liquid sample to be analyzed may be extracted; when cleaning the liquid storage tank 23 and the first channel 24 in the ablation cell 2, the washing solution may be extracted. At the same time, the timing module 4 may start timing when the injection pump 12 extracts the liquid. When the timing time of the timing module 4 reaches the first preset time interval, the injection pump 12 may also inject the extracted liquid into the first channel 24 through the liquid injection port 21 and enter the liquid storage tank 23 through the first channel 24. When the liquid level in the liquid storage tank 23 is in full contact with the lower surface of the covering on the liquid storage tank 23, the injection pump 12 stops injecting the liquid. Here, regardless of whether the extracted liquid is a liquid sample or a washing solution, the volume of the liquid extracted by the injection pump 12 is determined based on the fact that the liquid level in the liquid storage tank 23 is in full contact with the lower surface of the covering on the liquid storage tank 23 after being injected into the liquid storage tank 23.

[0040] It should be noted that the first preset time interval can be determined according to the volume V1 of the liquid storage tank 23, the volume V2 of the first channel 24, and the volume V3 of the connecting hose. V3 can be determined according to the actual structure among the injection pump 12, the sampling needle 111, and the three-way valve. As long as it is ensured that the finally extracted liquid volume V can achieve that after injecting the liquid with volume V into the liquid storage tank 23, the liquid level in the liquid storage tank 23 can be in full contact with the lower surface of the covering on the liquid storage tank 23. The first preset time interval can be calculated by dividing the volume V by the extraction volume of the injection pump 12 per unit time. For example, the first preset time interval can be obtained by dividing the volume V by the extraction volume of the injection pump 12 per unit time. The key to realizing automatic and accurate (liquid sample volume) sampling in the embodiments of the present application lies in clearly defining in advance the volume V1 of the liquid storage tank 23, the volume V2 of the first channel 24, and the volume V3 of the connecting hose, and setting the single liquid sample extraction amount and injection amount of the injection pump 12 according to these parameters. The purpose of accurate sampling is to control the liquid level of the liquid sample in the liquid storage tank 23 to always remain at a constant position, ensuring that the liquid level of the liquid sample is always in full contact with the inner surface of the covering on the liquid storage tank 23 after each automatic sampling. If accurate sampling fails to be achieved, it may cause the phenomenon that the liquid level of the liquid sample does not contact the inner surface of the upper covering, the contact is insufficient, or there is excessive contact and the liquid sample overflows from under the covering or the pressure stabilizing holes (if any) of the covering under the action of pressure. These are all not conducive to the focusing of the laser beam on the liquid sample or the subsequent cleaning of the ablation cell 2, thus affecting the analysis effect. It should be noted that the covering on the liquid storage tank 23 covers the top of the liquid storage tank 23 and can play a role in assisting focusing, preventing the liquid sample from splashing during the laser ablation process, and reducing the evaporation intensity of the liquid sample during the laser ablation process of the liquid sample.

[0041] In the embodiments of the present application, the first preset time interval is calculated, and based on the first preset time interval, it is ensured that the injection pump 12 extracts the required volume of liquid through the sampling needle 111, and then these liquids can be immediately injected into the liquid storage tank 23, which can improve the injection efficiency of the liquid. In addition, through the injection pump 12, very accurate liquid extraction can be achieved, ensuring that after subsequent injection into the liquid storage tank 23, the liquid level in the liquid storage tank 23 is in full contact with the lower surface of the covering on the liquid storage tank 23, which is conducive to improving the subsequent analysis effect of the liquid sample.

[0042] In the embodiments of the present application, optionally, the automatic sampler 11 further includes a control module 113. The liquid storage module 112 includes at least two storage units, and each storage unit corresponds to a unit identifier. The control module 113 is configured to receive a sampling instruction, determine the unit identifier corresponding to the storage unit where the liquid to be sampled is located based on the sampling instruction, and control the sampling needle 111 to move to the position of the storage unit corresponding to the unit identifier.

[0043] In this embodiment, the auto-sampler 11 may further include a control module 113. The liquid storage module 112 may include two or more storage units for storing at least one liquid sample and washing solution, so as to realize the automatic injection of the liquid sample and the automatic cleaning of the ablation cell 2. Each storage unit may correspond to a unit identifier, and the unit identifier may be in one-to-one correspondence with the storage unit. When the liquid sample and the washing solution are respectively placed in different storage units, the unit identifier of the storage unit where each liquid is located may be recorded, so that when a certain liquid needs to be extracted subsequently, the corresponding storage unit can be directly found according to the unit identifier. Here, the storage unit may be a centrifuge tube or the like.

[0044] When the user wants to analyze a certain liquid sample or wants to clean the ablation cell 2, an injection instruction may be sent through an external device or a control device in the liquid injection device 1. When the control module 113 of the auto-sampler 11 receives the injection instruction, it can determine the unit identifier corresponding to the storage unit where the liquid to be injected is located according to the injection instruction, and determine the specific position of the storage unit indicated by the unit identifier in the liquid storage module 112, and control the injection needle 111 to move from the current position to this position to realize the automatic injection of the liquid to be injected. In the embodiment of the present application, different liquid samples and washing solutions can be switched through the control module 113 and the injection needle 111, which is simple and convenient.

[0045] In the embodiment of the present application, optionally, a first one-way valve 13 is provided on the connecting hose between the injection needle 111 and the three-way valve, and a second one-way valve 14 is provided on the connecting hose between the three-way valve and the liquid injection port 21.

[0046] In this embodiment, a first one-way valve 13 may also be provided on the connecting hose between the injection needle 111 and the three-way valve, and a second one-way valve 14 may be provided on the connecting hose between the three-way valve and the liquid injection port 21. By providing the first one-way valve 13 and the second one-way valve 14 in the embodiment of the present application, the extraction process and the injection process of the liquid sample can be isolated from each other and do not interfere with each other.

[0047] In the embodiment of the present application, optionally, the waste liquid discharging device 3 includes a peristaltic pump 31 and a waste liquid storage module 32; wherein, the peristaltic pump 31 is connected to the liquid discharge port 22 and the waste liquid storage module 32 through a hose; the timing module 4 is further configured to start timing when the extracted liquid is a liquid sample and the injection pump 12 stops operating; the peristaltic pump 31 is configured to discharge the remaining liquid sample to the waste liquid storage module 32 through the second channel 25 and the liquid discharge port 22 when the timing time of the timing module 4 reaches a second preset time interval, and the second preset time interval is determined based on the analysis time of the liquid sample.

[0048] In this embodiment, the waste liquid discharging device 3 may include a peristaltic pump 31 and a waste liquid storage module 32. One side of the peristaltic pump 31 may be connected to the liquid discharge port 22 of the ablation cell 2 through a hose, and the other side may be connected to the waste liquid discharge module through a hose. Here, the hose may be a silicone tube.

[0049] When the liquid pumped by the syringe pump 12 is a liquid sample, if the syringe pump 12 stops operating, it means that the liquid sample has been completely injected. This is because the liquid pumping and injection processes of the syringe pump 12 are continuous. After the syringe pump 12 stops operating, the timing module 4 may start timing again (the first time was when the syringe pump 12 started pumping the liquid sample). When the timing time reaches the second preset time interval, it indicates that the laser ablation of the liquid sample is completed, and there is no need to obtain the aerosol particles of the liquid sample from the liquid storage tank 23. At this time, the peristaltic pump 31 may discharge the liquid sample through the second channel 25 and the liquid discharge port 22 into the waste liquid storage module 32 to achieve the automatic discharge of the remaining liquid sample. Here, the second preset time interval may be determined according to the analysis time of the liquid sample. By setting the second preset time interval in this embodiment of the present application, the automatic discharge effect after the laser ablation of the liquid sample can be achieved, which is beneficial to improving the automation degree of the entire process.

[0050] In this embodiment of the present application, optionally, the timing module 4 is further configured to restart timing after the liquid drawn is a cleaning solution and the timing time reaches the first preset time interval; the peristaltic pump 31 is further configured to discharge the cleaned cleaning solution through the second channel 25 and the liquid discharge port 22 into the waste liquid storage module 32 when the restarted timing time of the timing module 4 reaches the third preset time interval, and the third preset time interval is determined based on the liquid injection time of the syringe pump 12.

[0051] In this embodiment, when the liquid pumped by the syringe pump 12 is a cleaning solution, the timing module 4 starts timing during the liquid pumping. When the timing time reaches the first preset time interval, the syringe pump 12 starts injecting the drawn cleaning solution into the liquid storage tank 23. At the same time, the timing module 4 may restart timing. When the timing time of the restarted timing of the timing module 4 reaches the third preset time interval, it indicates that the cleaning solution has been completely injected into the liquid storage tank 23. At this time, the liquid level in the liquid storage tank 23 has fully contacted the inner surface of the covering on the liquid storage tank 23. Then, the peristaltic pump 31 can be controlled to operate to discharge the cleaning solution in the liquid storage tank 23 through the second channel 25 and the liquid discharge port 22 into the waste liquid storage device. Here, the third preset time interval may be determined according to the liquid injection time of the syringe pump 12. By setting the third preset time interval in this embodiment of the present application, the technical effect of automatically discharging the cleaning solution after cleaning the first channel 24 and the liquid storage tank 23 can be achieved, which is beneficial to improving the automation degree of the entire process.

[0052] In an embodiment of the present application, optionally, the system further includes an extraction tube 5, and the ablation cell 2 further includes an exhaust port 26; wherein, one side of the extraction tube 5 is inserted into the ablation cell 2 through the exhaust port 26, and the other side is connected to a laser ablation inductively coupled plasma mass spectrometer. The horizontal distance between the tube opening of the extraction tube 5 inserted into the ablation cell 2 and the ablation point is 5 mm.

[0053] In this embodiment, the liquid laser ablation sampling system may further include an extraction tube 5, and the ablation cell 2 may further include an exhaust port 26. One side of the extraction tube 5 may be inserted into the ablation cell 2 through the exhaust port 26, and the other side of the extraction tube 5 may be connected to a laser ablation inductively coupled plasma mass spectrometer through a pipeline to realize quantitative analysis of the trace element composition of the liquid sample. It should be noted that the horizontal distance between the tube opening on one side of the extraction tube 5 inserted into the ablation cell 2 and the ablation point in the ablation cell 2 is 5 mm. The horizontal distance between the tube opening of the extraction tube 5 and the laser ablation point may affect the extraction efficiency of aerosol particles. As Figure 2 shown, when the horizontal distance between the tube opening of the extraction tube 5 and the ablation point is about 5 mm, its extraction efficiency is the highest. In addition, as Figure 3 shown, when the horizontal distance between the tube opening of the extraction tube 5 and the ablation point is either less than 5 mm or greater than 5 mm, the RSD of the signal intensity of multiple analyses of each element is greater than that at the 5 mm position, indicating that the horizontal distance between the tube opening of the extraction tube 5 and the ablation point not only affects the signal intensity of each element, but also affects the signal stability of multiple analyses of each element, thereby affecting the reliability of the test results. Through Figure 2 and Figure 3 data, it is appropriate that the horizontal distance between the tube opening of the extraction tube 5 and the ablation point is about 5 mm. Therefore, during the actual test process, the horizontal distance between the ablation point and the tube opening of the extraction tube 5 can be kept relatively fixed. By setting the horizontal distance between the tube opening of the extraction tube 5 in the ablation cell 2 and the ablation point to 5 mm in the embodiment of the present application, the extraction efficiency of aerosol particles can be greatly improved.

[0054] In an embodiment of the present application, optionally, the system further includes a helium gas source 6 and an inlet tube 7, and the ablation cell 2 further includes an air inlet 27; wherein, one side of the inlet tube 7 is connected to the helium gas source 6, and the other side is inserted into the ablation cell 2 through the air inlet 27. In the vertical direction, the air inlet 27 is lower than the exhaust port 26, and the bottom of the exhaust port 26 is at the same horizontal plane as the top of the covering on the liquid storage tank 23.

[0055] In this embodiment, the liquid laser ablation sampling system may further include a helium gas source 6 and an intake pipe 7. Additionally, the ablation cell 2 may further include an air inlet 27. One side of the intake pipe 7 is connected to the helium gas source 6, and the other side may be inserted into the ablation cell 2 through the air inlet 27 inside the ablation cell 2. Further, in the vertical direction, the position of the air inlet 27 may be lower than the position of the exhaust port 26. At the same time, the bottom of the exhaust port 26 and the top of the cover of the liquid storage tank 23 are set on the same horizontal plane. In the embodiment of the present application, the carrier gas flow path in the ablation cell 2 is designed in a stepped manner. The position of the air inlet 27 is set lower than the position of the exhaust port 26, and the bottom of the exhaust port 26 and the top of the cover of the liquid storage tank 23 are set on the same horizontal plane, which can prevent the high-speed carrier gas flow ejected from the air inlet 27 end from directly blowing the aerosol particles generated by laser ablation. The carrier gas introduced through the air inlet 27 gradually stabilizes after a climbing and expansion process, which is beneficial to improving the extraction efficiency of aerosol particles and shortening the background cleaning time. In the embodiment of the present application, specifically in the vertical direction, the position of the air inlet 27 may be set 2-3 cm lower than the position of the exhaust port 26.

[0056] In the embodiment of the present application, optionally, the cover is a quartz sheet provided with a pressure stabilizing hole, and the aperture of the pressure stabilizing hole is 1-3 mm.

[0057] In this embodiment, the covering on the liquid storage pool 23 may specifically be a quartz sheet provided with pressure stabilizing holes, and the aperture of the pressure stabilizing holes (holes for maintaining the pressure stability inside and outside the liquid storage pool 23) is 1-3 mm. The quartz sheet covers the top of the liquid storage pool 23 and plays a role in assisting focusing, preventing the liquid sample from splashing during the laser ablation process, and reducing the volatilization intensity of the liquid sample. In this application, in order to balance the air pressure inside and outside the liquid storage pool 23 during the liquid sample injection process and the waste liquid discharge process to prevent the quartz sheet from breaking due to the pressure difference inside and outside the liquid storage pool 23, holes (i.e., pressure stabilizing holes) are opened at any position where the quartz sheet contacts the liquid surface, and the aperture is preferably about 1-3 mm. If the aperture is too large, it may exacerbate the volatilization of the liquid sample; if the aperture is too small, it is not conducive to balancing the air pressure in the liquid storage pool 23. In terms of sealing the liquid sample, using a quartz sheet has more advantages than using a sealing film. In the prior art, a sealing film is used to completely seal the Teflon microporous plate containing the liquid sample. This film pasting method requires the operator to have certain film pasting experience. Otherwise, it is very easy to cause the liquid sample to overflow, be contaminated with each other, or the inner surface of the sealing film does not contact the liquid surface of the liquid sample well, which is not conducive to laser focusing and affects the ablation effect. In this application, the quartz sheet is directly pasted and fixed on the top of the liquid storage pool 23, eliminating the film pasting process and making the process simpler and easier to implement. In addition, using a quartz sheet instead of a sealing film can shorten the duration of the entire test process and improve work efficiency. Because the laser can directly ablate the liquid sample through the micropores on the quartz sheet, without having to break through the sealing film before analyzing each liquid sample like a sealing film and then ablating the liquid sample. This not only saves the time consumed in the process of the laser breaking through the sealing film, but also omits the film pasting process that is not easy to operate. Therefore, this design not only shortens the duration of the test process, but also simplifies the operation process.

[0058] In the embodiment of this application, optionally, the cross-sectional shape of the liquid storage pool 23 in the target cross-section is a funnel shape, and the target cross-section is a cross-section perpendicular to the placement plane of the ablation pool 2 and passing through the center of the liquid storage pool 23.

[0059] In this embodiment, as Figure 4As shown, the cross-sectional shape of the liquid storage pool 23 on the target cross-section can be set to a funnel shape. By setting the cross-sectional shape of the liquid storage pool 23 on the target cross-section to a funnel shape, the effects of efficient waste liquid discharge and efficient cleaning of the liquid storage pool 23 can be achieved. The liquid storage pool 23 integrates the first channel 24, the second channel 25, and the liquid storage pool 23, reducing the cleaning volume, improving the cleaning efficiency, and avoiding the interference to the liquid sample analysis process caused by the untimely discharge of waste liquid. The ablation cell 2 of the embodiment of the present application adopts a funnel structure design, which has the characteristics of integrating the first channel 24, the second channel 25, and the liquid storage pool 23. Compared with the design form of separating the liquid sample tank and the waste liquid tank in the prior art, it not only simplifies the design structure of the ablation cell 2, but also makes the sampling system easier to clean. At the same time, it can also avoid the problems such as untimely discharge, incomplete discharge, and waste liquid volatilization in the ablation cell 2 from affecting the test results of liquid samples.

[0060] Further, as Figure 1 a specific implementation of the system, the embodiment of the present application provides another liquid laser ablation sampling system, as Figure 5 shown, the system includes:

[0061] a liquid injection device 1, an ablation cell 2, a waste liquid discharge device 3, a timing module 4, an extraction tube 5, a helium gas source 6, and an intake pipe 7.

[0062] Among them, the ablation cell may include a liquid injection port 21, a liquid discharge port 22, and a liquid storage pool 23. The liquid injection port 21 of the ablation cell 2 is communicated with the bottom end of the liquid storage pool 23 through the first channel 24, and the liquid discharge port 22 and the first channel 24 may be communicated through the second channel 25. In addition, in the vertical direction, the position of the liquid injection port 21 of the ablation cell 2 may be lower than the position of the liquid discharge port 22.

[0063] The liquid injection device 1 may include an autosampler 11 and an injection pump 12. The autosampler 11 may further include a sampling needle 111 and a liquid storage module 112. Here, the sampling needle 111 of the autosampler 11, the injection pump 12, and the liquid injection port 21 of the ablation cell 2 are respectively connected to one port of a three-way valve. During specific application, the injection pump 12 may extract the required liquid from the liquid storage module 112 through the sampling needle 111 of the autosampler 11. Meanwhile, the timing module 4 may start timing when the injection pump 12 extracts the liquid. When the timing time of the timing module 4 reaches the first preset time interval, the injection pump 12 may also inject the extracted liquid into the first channel 24 through the liquid injection port 21 and enter the storage pool 23 through the first channel 24. When the liquid level in the storage pool 23 is in full contact with the lower surface of the cover on the storage pool 23, the injection pump 12 stops injecting the liquid. The autosampler 11 may further include a control module 113. The liquid storage module 112 may include two or more storage units for storing at least one liquid sample and washing solution, so as to realize the automatic injection of the liquid sample and the automatic cleaning of the ablation cell 2. In addition, a first one-way valve 13 may be provided on the connecting hose between the sampling needle 111 and the three-way valve, and a second one-way valve 14 may be provided on the connecting hose between the three-way valve and the liquid injection port 21.

[0064] The waste liquid discharge device 3 may include a peristaltic pump 31 and a waste liquid storage module 32. One side of the peristaltic pump 31 may be connected to the liquid discharge port 22 of the ablation cell 2 through a hose, and the other side may be connected to the waste liquid discharge module through a hose.

[0065] The liquid laser ablation sampling system may further include an extraction tube 5. In addition, the ablation cell 2 may further include an exhaust port 26. One side of the extraction tube 5 may be inserted into the ablation cell 2 through the exhaust port 26, and the other side of the extraction tube 5 may be connected to a laser ablation inductively coupled plasma mass spectrometer through a pipeline to realize the quantitative analysis of the trace element composition of the liquid sample. It should be noted that the horizontal distance between the pipe orifice on the side where the extraction tube 5 is inserted into the ablation cell 2 and the ablation point in the ablation cell 2 is 5 mm (such as Figure 6 the distance d in the figure).

[0066] The liquid laser ablation sampling system may further include a helium gas source 6 and an inlet pipe 7. In addition, the ablation cell 2 may further include an air inlet 27. One side of the inlet pipe 7 is connected to the helium gas source 6, and the other side may be inserted into the ablation cell 2 through the air inlet 27 in the ablation cell 2. In addition, in the vertical direction, the position of the air inlet 27 may be lower than the position of the exhaust port 26. Meanwhile, the bottom of the exhaust port 26 and the top of the cover of the storage pool 23 are set on the same horizontal plane.

[0067] Such as Figure 6As shown, the cover on the liquid storage pool 23 can specifically be a quartz sheet provided with a pressure stabilizing hole.

[0068] Furthermore, as Figure 1 a specific implementation of the system, an embodiment of the present application provides a liquid laser ablation sampling method, which is applied to the liquid laser ablation sampling system described in any one of the above, as Figure 7 shown, the method includes:

[0069] Step 101, the liquid injection device extracts a liquid sample and injects the liquid sample into the liquid storage pool of the ablation cell through the liquid injection port of the ablation cell and the first channel, where the first channel is the connection channel between the liquid injection port and the bottom end of the liquid storage pool;

[0070] Step 102, after the liquid sample is analyzed, the waste liquid discharge device discharges the liquid sample through the second channel and the liquid discharge port of the ablation cell, where the second channel is the connection channel between the liquid discharge port and the first channel;

[0071] Step 103, the liquid injection device extracts a cleaning solution and injects the cleaning solution into the liquid storage pool through the liquid injection port and the first channel to clean the first channel and the liquid storage pool;

[0072] Step 104, when cleaning the first channel and the liquid storage pool, the waste liquid discharge device discharges the cleaned cleaning solution through the second channel and the liquid discharge port.

[0073] Optionally, the liquid injection device includes an autosampler and an injection pump, and the autosampler includes a sampling needle and a liquid storage module; wherein, the sampling needle of the autosampler and the injection pump are connected to the liquid injection port through a three-way valve, and the sampling needle, the injection pump, and the liquid injection port are respectively connected to the three-way valve through hoses; Step 101 or Step 103 includes:

[0074] The injection pump extracts a liquid from the liquid storage module of the autosampler through the sampling needle, and the liquid is the liquid sample or the cleaning solution;

[0075] The timing module starts timing when the injection pump extracts the liquid;

[0076] When the timing time of the timing module reaches a first preset time interval, the injection pump injects the extracted liquid into the liquid storage pool through the liquid injection port and the first channel, so that the liquid level in the liquid storage pool is in full contact with the lower surface of the cover on the liquid storage pool.

[0077] Optionally, the automatic sample injector further includes a control module, the liquid holding module includes at least two holding units, and each of the holding units corresponds to a unit identifier; the method further includes:

[0078] The control module receives an injection instruction, determines a unit identifier corresponding to a holding unit where the liquid to be injected is located based on the injection instruction, and controls the injection needle to move to a holding unit position corresponding to the unit identifier.

[0079] Optionally, a first one-way valve is provided on the connecting hose between the injection needle and the three-way valve, and a second one-way valve is provided on the connecting hose between the three-way valve and the liquid injection port.

[0080] Optionally, the waste liquid discharge device includes a peristaltic pump and a waste liquid holding module; wherein the peristaltic pump is connected to the liquid discharge port and the waste liquid holding module via a hose; step 102 includes:

[0081] The timing module starts timing when the extracted liquid is a liquid sample and the syringe pump stops running;

[0082] When the timing time of the timing module reaches a second preset time interval, the peristaltic pump discharges the remaining liquid sample into the waste liquid holding module through the second channel and the drain port. The second preset time interval is determined based on the analysis time of the liquid sample.

[0083] Optionally, step 104 includes:

[0084] The timing module restarts the timing after the liquid extracted is the washing liquid and the timing time reaches the first preset time interval;

[0085] When the retiming time of the timing module reaches a third preset time interval, the peristaltic pump discharges the cleaned washing liquid into the waste liquid holding module through the second channel and the drain port, and the third preset time interval is determined based on the liquid injection time of the injection pump.

[0086] Optionally, the system further comprises an extraction pipe, and the denudation tank further comprises an exhaust port;

[0087] One side of the extraction tube is inserted into the ablation pool through the exhaust port, and the other side is connected to the laser ablation inductively coupled plasma mass spectrometer. The horizontal distance between the tube opening of the extraction tube inserted into the ablation pool and the ablation point is 5 mm.

[0088] Optionally, the system further comprises a helium source and an air inlet pipe, and the denudation cell further comprises an air inlet;

[0089] Wherein, one side of the intake pipe is connected to the helium source, and the other side is inserted into the ablation cell through the air inlet. In the vertical direction, the air inlet is lower than the exhaust port, and the bottom of the exhaust port is at the same horizontal plane as the top of the covering of the liquid storage tank.

[0090] Optionally, the covering is a quartz sheet provided with pressure stabilizing holes, and the aperture of the pressure stabilizing holes is 1-3 mm.

[0091] Optionally, the cross-sectional shape of the liquid storage tank in the target cross-section is a funnel shape, and the target cross-section is a cross-section perpendicular to the placement plane of the ablation cell and passing through the center of the liquid storage tank.

[0092] It should be noted that for other corresponding descriptions of each functional unit involved in the liquid laser ablation sampling method provided in the embodiments of the present application, reference can be made to Figures 1 to 6 the corresponding description in the system, which will not be elaborated here.

[0093] The embodiments of the present application further provide a computer device, which can specifically be a personal computer, a server, a network device, etc. As Figure 8 shown, the computer device includes a bus, a processor, a memory, and a communication interface, and may further include an input / output interface and a display device. Among them, the processor of the computer device is used to provide computing and control capabilities. The memory of the computer device includes a non-volatile storage medium and an internal memory. The non-volatile storage medium stores an operating system, a computer program, and a database. The internal memory provides an environment for the operation of the operating system and the computer program in the non-volatile storage medium. The database of the computer device is used to store location information. The network interface of the computer device is used to communicate with an external terminal through a network connection. When the computer program is executed by the processor, the steps in the method embodiments are implemented.

[0094] Those skilled in the art can understand that Figure 8 the structure shown in

[0095] is only a block diagram of some structures related to the solution of the present application, and does not constitute a limitation on the computer device to which the solution of the present application is applied. The specific computer device may include more or fewer components than those shown in the figure, or combine some components, or have different component arrangements.

[0096] In one embodiment, a computer-readable storage medium is provided. The computer-readable storage medium may be non-volatile or volatile, and stores a computer program. When the computer program is executed by a processor, the steps in the above method embodiments are implemented.

[0097] It should be noted that the user information (including but not limited to user device information, user personal information, etc.) and data (including but not limited to data for analysis, stored data, displayed data, etc.) involved in this application are all information and data authorized by the user or fully authorized by all parties.

[0098] Those of ordinary skill in the art can understand that all or part of the processes in the methods of the above embodiments can be completed by instructing relevant hardware through a computer program. The computer program can be stored in a non-volatile computer-readable storage medium. When the computer program is executed, it can include the processes of the embodiments of the above methods. Among them, any reference to a memory, database, or other medium used in the embodiments provided in this application can include at least one of non-volatile and volatile memories. Non-volatile memory can include read-only memory (ROM), magnetic tape, floppy disk, flash memory, optical memory, high-density embedded non-volatile memory, resistive random access memory (ReRAM), magnetoresistive random access memory (MRAM), ferroelectric random access memory (FRAM), phase change memory (PCM), graphene memory, etc. Volatile memory can include random access memory (RAM) or external cache memory, etc. By way of illustration and not limitation, RAM can be in various forms, such as static random access memory (SRAM) or dynamic random access memory (DRAM), etc. The databases involved in the embodiments provided in this application can include at least one of relational databases and non-relational databases. Non-relational databases can include distributed databases based on blockchain, etc., and are not limited thereto. The processors involved in the embodiments provided in this application can be general-purpose processors, central processors, graphics processors, digital signal processors, programmable logic devices, data processing logics based on quantum computing, etc., and are not limited thereto.

[0099] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0100] The above-described embodiments merely represent several implementation manners of the present application. The description thereof is relatively specific and detailed, but it should not be construed as a limitation to the patent scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all fall within the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the appended claims.

Claims

1. A liquid laser ablation sampling system, characterized in that, It includes a liquid injection device, an erosion cell, and a waste liquid discharge device; Among them, the erosion cell includes a liquid injection port, a liquid discharge port, and a liquid storage pool. The liquid injection port is connected to the bottom end of the liquid storage pool through a first channel. The liquid discharge port is connected to the first channel through a second channel. And in the vertical direction, the liquid injection port is lower than the liquid discharge port. The liquid injection port is connected to the liquid injection device, and the liquid discharge port is connected to the waste liquid discharge device; The liquid injection device is used to extract a liquid sample and inject the liquid sample into the liquid storage pool through the liquid injection port and the first channel; and, after the liquid sample is analyzed, extract a cleaning solution and inject the cleaning solution into the liquid storage pool through the liquid injection port and the first channel to clean the first channel and the liquid storage pool; The waste liquid discharge device is used to discharge the liquid sample through the second channel and the liquid discharge port after the liquid sample is analyzed; and, when cleaning the first channel and the liquid storage pool, discharge the cleaned cleaning solution through the second channel and the liquid discharge port.

2. The system according to claim 1, wherein The system further includes a timing module. The liquid injection device includes an autosampler and an injection pump. The autosampler includes a sampling needle and a liquid holding module; Among them, the sampling needle of the autosampler and the injection pump are connected to the liquid injection port through a three-way valve. The sampling needle, the injection pump, and the liquid injection port are respectively connected to the three-way valve through hoses; The injection pump is used to extract a liquid from the liquid holding module of the autosampler through the sampling needle. The liquid is the liquid sample or the cleaning solution; The timing module is used to start timing when the injection pump extracts a liquid; The injection pump is further used to inject the extracted liquid into the liquid storage pool through the liquid injection port and the first channel when the timing time of the timing module reaches a first preset time interval, so that the liquid level in the liquid storage pool is in full contact with the lower surface of the covering of the liquid storage pool.

3. The system according to claim 2, characterized in that, The autosampler further includes a control module. The liquid holding module includes at least two holding units, and each holding unit corresponds to a unit identifier; The control module is used to receive a sampling instruction, determine the unit identifier corresponding to the holding unit where the liquid to be sampled is located based on the sampling instruction, and control the sampling needle to move to the position of the holding unit corresponding to the unit identifier.

4. The system according to claim 2 or 3, characterized in that, A first one-way valve is provided on the connecting hose between the sampling needle and the three-way valve, and a second one-way valve is provided on the connecting hose between the three-way valve and the liquid injection port.

5. The system according to claim 2, wherein The waste liquid discharge device includes a peristaltic pump and a waste liquid holding module; Among them, the peristaltic pump is connected to the liquid discharge port and the waste liquid holding module through hoses; The timing module is further used to start timing when the extracted liquid is a liquid sample and the injection pump stops operating; The peristaltic pump is used to discharge the remaining liquid sample into the waste liquid storage module through the second channel and the liquid discharge port when the timing time of the timing module reaches a second preset time interval, and the second preset time interval is determined based on the analysis time of the liquid sample.

6. The system according to claim 5, wherein the timing module is further configured to restart timing after the liquid drawn is a washing liquid and the timing time reaches the first preset time interval; the peristaltic pump is further configured to discharge the washed washing liquid into the waste liquid storage module through the second channel and the liquid discharge port when the restarted timing time of the timing module reaches a third preset time interval, and the third preset time interval is determined based on the liquid injection time of the syringe pump.

7. The system according to claim 1, wherein The system further includes an extraction tube, and the ablation cell further includes an exhaust port; wherein one side of the extraction tube is inserted into the ablation cell through the exhaust port, and the other side is connected to a laser ablation inductively coupled plasma mass spectrometer, and the horizontal distance between the tube orifice of the extraction tube inserted into the ablation cell and the ablation point is 5 mm.

8. A liquid laser ablation sampling method, applied to the liquid laser ablation sampling system according to any one of claims 1 to 7, characterized in that, Comprising: The liquid injection device extracts a liquid sample and injects the liquid sample into the storage pool of the ablation cell through the liquid injection port and the first channel of the ablation cell, and the first channel is a connection channel between the liquid injection port and the bottom end of the storage pool; After the liquid sample is analyzed, the waste liquid discharge device discharges the liquid sample through the second channel and the liquid discharge port of the ablation cell, and the second channel is a connection channel between the liquid discharge port and the first channel; The liquid injection device extracts a washing liquid and injects the washing liquid into the storage pool through the liquid injection port and the first channel to clean the first channel and the storage pool; When cleaning the first channel and the storage pool, the waste liquid discharge device discharges the washed washing liquid through the second channel and the liquid discharge port.

9. A storage medium having a computer program stored thereon, characterized in that, The computer program, when executed by a processor, implements the method according to claim 8.

10. A computer device, comprising a storage medium, a processor, and a computer program stored on the storage medium and executable on the processor, wherein, The processor, when executing the computer program, implements the method according to claim 8.

Images