Laser freezing denudation device and method for non-solid sample
Through the design of a liquid nitrogen-cooled laser ablation device and a multifunctional sample slot, the problems of controllable ablation and matrix effect in fluid inclusion analysis in LA-ICP-MS technology are solved, efficient and accurate detection of non-solid samples is achieved, the accuracy and sensitivity of experimental results are improved, and the operation process is simplified.
Patent Information
- Application Number
- CN202410313595.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-19
- Publication Date
- 2025-09-19
AI Technical Summary
The existing laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) technology has problems with controlled ablation and matrix effects in fluid inclusion analysis. The freezing pool device is large and difficult to match, the freezing temperature is high and it lacks light transmittance, which affects the accuracy of experimental results. The drying of biological tissue sections leads to sample contamination and uneven notches, and the process of synthesizing inclusion standards is complex and inconsistent.
A liquid nitrogen-cooled laser cryoablation device with adjustable sample position is provided. The device includes a sample pool body, a heat sink, a temperature sensing line, a liquid nitrogen inlet pipeline, a silver stage, and a sample moving device. This device enables precise temperature control and light transmission observation of the sample. A multifunctional sample slot and a quartz liquid dish are used for sample detection, simplifying the sample standardization process.
It achieves efficient and accurate detection of non-solid samples, reduces the cooling temperature and increases the cooling rate, reduces the matrix effect, improves the accuracy and sensitivity of the experimental results, simplifies the operation process, and reduces costs.
Smart Images

Figure CN120668428A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of laser ablation-inductively coupled plasma mass spectrometry detection, and in particular to a laser cryoablation device and method for non-solid samples. Background Art
[0002] Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) offers advantages such as rapid analysis, a wide range of analyzable elements, minimal matrix effects, and the need for no sample pretreatment. It is therefore suitable for detailed analysis of micro-areas, trace amounts, and element isotopes. This technique is currently widely used in rock and mineral analysis and can be used to analyze changes in mineral composition and structure. LA-ICP-MS can determine the rare earth element, trace element, and isotopic composition of fluid inclusions and rock minerals, thereby determining their origin and evolution. Currently, laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) has been widely used in in situ microanalysis of solids and is increasingly being used in biological research and analysis of fluid inclusion composition.
[0003] LA-ICP-MS is relatively mature for mineral composition analysis. However, in fluid inclusion analysis, to slow the release of fluid inclusions and allow the mass spectrometer to collect more reliable signals, LA-ICP-MS needs to address the issues of controlled erosion and matrix effects. To address controlled erosion, researchers have continuously improved the sample erosion process and parameters, and also modified the freezing pool. To address matrix effects, researchers have attempted to use synthetic inclusions as standards. However, the synthetic inclusion process is complex, time-consuming, and labor-intensive, and there is no guarantee that the resulting solution will be completely consistent with the actual solution.
[0004] At the same time, for elemental analysis of biological tissue sections, the most common experimental method currently involves drying frozen tissue sections and then performing laser ablation. This drying process can easily lead to sample contamination. Furthermore, after drying, some biological tissue sections (such as plant tissue sections) may develop uneven surfaces due to dehydration, leading to inaccurate experimental results. Semiconductor cryocells have been invented, but their freezing temperature is high (-30°C), the freezing rate is slow, and they lack light transparency, making observation difficult.
[0005] In the current laser freezing cell technology, the following problems still need to be solved: 1) The freezing cell device is large in size and it is difficult to match it with different models of laser sample cells; 2) The freezing temperature of the semiconductor freezing cell is relatively high (the temperature range is -30℃~110℃), which cannot meet the rapid freezing requirements of high-salinity fluid inclusions and special samples in the calcium chloride system; 3) Some sample cells cannot be observed through light, which cannot meet the observation of fluid inclusions and the internal structure of organisms; 4) The window of the freezing table that can be observed through light has a great impact on the freezing effect, and the temperature control accuracy is limited, resulting in large errors in the experimental results; 5) The problem of standard samples in the fluid inclusion testing process. The process of synthesizing inclusions as standard samples is not only complicated, time-consuming and labor-intensive, but also cannot fully guarantee that the synthesized solution is completely consistent with the actual ratio solution. Summary of the Invention
[0006] The present invention aims to provide a laser cryoablation device and method for non-solid samples. Specifically, it provides a liquid nitrogen-cooled laser cryoablation device and method with adjustable sample position. This device, which involves a sample pool for laser ablation of fluid inclusions in organisms, fluids, and rocks, aims to address the problems of existing laser cryoablation devices. This device effectively controls sample temperature, improving the data quality of fluid inclusion and biological sample testing. It also provides a highly efficient and direct method for elemental isotope analysis of formation water and trace solutions without pretreatment. The instrumentation and experimental equipment employed in this invention are low-cost, offering enhanced economical efficiency and operability.
[0007] To achieve the above object, the present invention provides the following technical solutions:
[0008] The present invention provides a laser ablation freezing device for non-solid samples, the device comprising: a sample pool body, a heat dissipation end, a temperature sensing line, a liquid nitrogen inlet pipeline, a silver stage, a sample moving device and a multifunctional sample slot; wherein,
[0009] The heat dissipation end, the temperature sensing line and the liquid nitrogen inlet pipeline are sequentially arranged side by side outside the sample cell body;
[0010] The silver stage and the multifunctional sample slot are arranged inside the sample cell body;
[0011] The rotatable part of the sample moving device is arranged outside the sample cell body;
[0012] The silver stage is connected to the heat dissipation end, the temperature sensing line and the liquid nitrogen inlet pipeline.
[0013] Furthermore, the device also includes a sample cover; the sample cover is provided with a glass skylight according to the size of the multifunctional sample slot and the silver stage.
[0014] Furthermore, the heat dissipation end is directly connected to a radiator, the radiator is connected to a temperature controller, and the radiator is used for discharging liquid nitrogen and controlling the temperature of the silver stage.
[0015] Furthermore, the temperature sensing line is directly connected to a temperature controller, and the temperature controller is used to control the temperature of the silver stage.
[0016] Furthermore, the cold end liquid nitrogen inlet pipeline is directly connected to a liquid nitrogen tank, and the liquid nitrogen tank is used to cool the silver stage.
[0017] Furthermore, a central light-transmitting hole of the silver stage is provided on the silver stage, and the central light-transmitting hole of the silver stage is used for transmitting light to facilitate sample observation.
[0018] Furthermore, the sample moving device includes: a Y-axis longitudinal adjustment component, an X-axis lateral adjustment component and a sample loading end; wherein,
[0019] The rotatable parts of the Y-axis longitudinal adjustment component and the X-axis transverse adjustment component are arranged outside the sample pool body; the sample loading end is covered on the silver stage; the knobs of the Y-axis longitudinal adjustment component and the X-axis transverse adjustment component (14) and their adjustment components are used for the transverse and longitudinal movement of the sample loading end.
[0020] Furthermore, the multifunctional sample slot includes a multifunctional sample slot frame and a plurality of spring assemblies, wherein the plurality of spring assemblies are arranged inside the multifunctional sample slot frame.
[0021] The present invention also provides a laser ablation freezing method for non-solid samples, the method comprising the following steps:
[0022] Step S1: Prepare the rock sample into inclusion slices, and polish both sides;
[0023] Step S2, performing petrographic observation on the inclusion thin section, and marking the number, size and depth information of the fluid inclusions to be tested one by one;
[0024] Step S3: Cut the inclusion slice into small pieces, soak the slide in acetone, scan and record the relative positions of the fluid inclusions in the inclusion slice, test the uniform temperature, freezing point and initial melting temperature of the target fluid inclusions, and mark them one by one;
[0025] Step S4: Place the temperature-measured inclusion slice into the quartz wafer of the laser ablation freezing device. Place a solid standard sample in the multifunctional sample well. If required, a standard liquid can also be placed in a quartz half-well liquid carrier dish for freezing. Find and locate the fluid inclusion to be measured in the laser ablation software system.
[0026] Step S5: Cooling the silver stage and observing whether the inclusion flake is completely frozen, setting the ablation spot according to the size of the inclusion flake and the laser ablation power according to the type of host mineral;
[0027] Step S6: Set up a test sequence. The fluid inclusions in the same host mineral are set as a combined sequence, starting and ending with a solid material standard and a standard liquid. A set of solid material standards needs to be added before and after every ten unknown samples tested at most.
[0028] Step S7: After the test is completed and the element signal is obtained, a standard solution of known salinity is prepared according to the measured value of the solid material standard sample and the salinity converted from the mineral freezing point for component calibration.
[0029] The present invention also provides a laser ablation freezing method for non-solid samples, the method comprising the following steps:
[0030] Step S1: Prepare element isotope standard solution according to test requirements;
[0031] Step S2: placing the liquid sample to be tested and the standard solution into a quartz full-pore liquid-carrying dish, placing the standard sample into a multifunctional sample slot, and finding and calibrating the positions and numbers of the liquid sample to be tested and the standard solution in the laser ablation software system;
[0032] Step S3, cooling the silver stage to observe whether the liquid sample to be tested and the standard solution are completely frozen;
[0033] Step S4, setting laser ablation parameters of the liquid sample to be tested and the standard solution;
[0034] Step S5: Set the test sequence to test the standard sample and the standard solution twice before and after each test of eight unknown sample points;
[0035] Step S6: After the test is completed and the element signal is obtained, the corresponding fractionation coefficient is obtained according to the measured values of the standard sample and the standard solution and their standard values, and the fractionation correction is performed on the liquid sample to obtain the actual element isotope content of the liquid sample to be tested.
[0036] Technical effects and advantages of the present invention:
[0037] (1) The internal structure of the freezing pool of the present invention is clear, and the outer frame size can be adjusted according to different laser ablation sample slots. Not only can the knob on one side adjust the sample movement device in both the horizontal and vertical directions, but the silver stage and liquid nitrogen freezing also greatly reduce the cooling temperature and increase the cooling rate.
[0038] (2) The multifunctional sample trough and porous quartz liquid carrier of the present invention can simultaneously detect samples in different phases, such as solids, liquids, and fluid inclusions. This not only meets the requirements for solid standards such as NIST 612 that can be used for fluid inclusion testing, but also addresses the issue of matrix effects during fluid inclusion testing using the frozen solution method. Compared to synthetic inclusions, frozen standard solutions can be configured based on salinity data obtained from the freezing point, resulting in more accurate standard solution composition. The process is simple, time-saving, and economical.
[0039] (3) The present invention also enables the use of a cryo-based LA-ICP-MS method to test the elemental-isotopic composition of formation water and other fluids. Compared with traditional liquid injection methods, this method has the advantages of high sensitivity, greater convenience, and faster speed. This method not only requires a small sample amount but also does not require any pre-treatment, which is more in line with the requirements of safe production.
[0040] (4) The present invention can rapidly freeze biological samples to -196°C using liquid nitrogen, thereby maintaining the original activity of the biological samples during the biological detection process, making the test results more accurate.
[0041] Other features and advantages of the present invention will be described in the following description, and in part will become apparent from the description, or will be understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS
[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0043] Figure 1 This is a schematic structural diagram of a laser cryoablation device for non-solid samples according to the present invention;
[0044] Figure 2 This is a structural diagram of the multifunctional sample tank of the present invention;
[0045] Figure 3 Schematic diagram of the sample moving device of the present invention;
[0046] Attachment Figure 1 Markings: 1. Sample cover; 2. Glass skylight; 3. Sample cell body; 4. Heat dissipation end; 401. Radiator; 5. Temperature sensing line; 501. Temperature controller; 6. Liquid nitrogen inlet line from cold end; 601. Liquid nitrogen tank; 7. Silver stage; 8. Central light hole of silver stage; 9. Sample moving device; 10. Multi-function sample slot.
[0047] Attachment Figure 2 Markings: 11, multi-function sample slot frame; 12, spring assembly.
[0048] Attachment Figure 3 Markings: 13, Y-axis longitudinal adjustment assembly; 14, X-axis lateral adjustment assembly; 15, sample loading end; 16, quartz full-hole liquid loading dish; 17, quartz half-hole liquid loading dish; 18, quartz wafer. DETAILED DESCRIPTION
[0049] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0050] In order to solve the deficiencies of the prior art, the present invention discloses a laser ablation freezing device for non-solid samples. Figure 1 FIG. 1 is a schematic structural diagram of a laser cryoablation device for non-solid samples according to the present invention, as shown in FIG. Figure 1 As shown, the device includes: a sample cover 1, a glass skylight 2, a sample pool body 3, a heat dissipation end 4, a temperature sensing line 5, a cold end liquid nitrogen inlet pipeline 6, a silver stage 7, a central light-transmitting hole 8 of the silver stage, a sample moving device 9 and a multifunctional sample slot 10; wherein,
[0051] The heat dissipation end 4, the temperature sensing line 5 and the cold end liquid nitrogen inlet pipeline 6 are sequentially arranged side by side outside the sample cell body 3;
[0052] The silver stage 7 and the multifunctional sample slot 10 are arranged inside the sample cell body 3;
[0053] The rotatable part of the sample moving device 9 is arranged outside the sample cell body 3;
[0054] Furthermore, the heat dissipation end 4 is connected to the silver stage 7, the temperature sensing line 5 is connected to multiple positions of the silver stage 7, and the cold end liquid nitrogen inlet pipeline 6 is connected to the silver stage 7;
[0055] Furthermore, the heat dissipation end 4 is directly connected to the radiator 401, and the radiator 401 is used for discharging liquid nitrogen and controlling the temperature of the silver stage 7; the temperature sensing line 5 is directly connected to the temperature controller 501; the cold end liquid nitrogen inlet pipeline 6 is directly connected to the liquid nitrogen tank 601, and the liquid nitrogen tank 601 is used for cooling the silver stage 7; the radiator 401, the temperature controller 501 and the liquid nitrogen tank 601 are all arranged outside the sample pool body 3.
[0056] Specifically, the temperature control principle of the silver stage 7 is as follows:
[0057] (1) The radiator 401 is connected to the temperature controller 501. When the temperature of the silver stage 7 is not within the ideal range, the temperature controller 501 is used to set a suitable temperature, and the radiator 401 is used to further adjust and control the temperature of the silver stage 7. When the temperature control is not ideal, the exhaust volume of the heat dissipation end 4 can be increased.
[0058] Furthermore, the silver stage 7 is provided with a silver stage central light-transmitting hole 8, and the silver stage central light-transmitting hole 8 is used to transmit light to facilitate sample observation; the diameter of the silver stage central light-transmitting hole 8 is recommended to be less than 0.5 cm.
[0059] Further, Figure 3 Schematic diagram of the sample moving device of the present invention, as shown in Figure 3 As shown, the sample moving device 9 includes: a Y-axis longitudinal adjustment component 13, an X-axis lateral adjustment component 14 and a sample loading end 15; wherein,
[0060] The rotatable parts of the Y-axis longitudinal adjustment component 13 and the X-axis lateral adjustment component 14 are arranged on the outside of the sample pool body 3; the loading end 15 is covered on the silver stage 7, and the knobs of the X-axis lateral adjustment component 14 and the Y-axis longitudinal adjustment component 13 and their adjustment components can realize the lateral and longitudinal movement of the loading end 15.
[0061] The sample loading end 15 can be mounted with a quartz sample carrier, which includes a quartz full-hole liquid carrier 16, a quartz half-hole liquid carrier 17, or a quartz wafer 18. The quartz sample carrier must be in close contact with the surface of the silver stage 7 to ensure that the quartz sample carrier is in close contact with the pure silver stage surface to ensure heating efficiency and stability. In addition, the quartz full-hole liquid carrier 16 can be used to hold multiple liquid samples, the quartz half-hole liquid carrier 17 can be used to simultaneously hold inclusion flakes and standard solutions, and the quartz wafer 18 can be used to hold solid samples (such as inclusion flakes, biological samples, etc.).
[0062] Further, Figure 2 This is a structural diagram of the multifunctional sample tank of the present invention, as shown in FIG. Figure 2 As shown, the multifunctional sample slot 10 includes a multifunctional sample slot frame 11 and a plurality of spring assemblies 12, wherein the plurality of spring assemblies 12 are arranged inside the multifunctional sample slot frame 11. Since the conventional target sample size is 2.5 cm, in order to ensure that the target sample is stably supported on the spring assembly 12, the size of the spring assembly 12 is set to 2.5 cm. The spring assembly 12 can simultaneously install the target sample and the thin sheet sample.
[0063] The laser ablation freezing device is further provided with a sample cover 1 , which can be provided with a glass skylight 2 according to the size of the multifunctional sample tank 10 and the silver stage 7 to achieve sealing and light transmittance.
[0064] It should be noted that there are no special requirements for the materials of the various components of the above-mentioned laser cryoablation device for non-solid samples. Among them, the sample cover 1, the glass skylight 2, the sample pool body 3, the multifunctional sample tank 10 (including the multifunctional sample tank frame 11 and the spring assembly 12, the Y-axis longitudinal adjustment assembly 13, the X-axis lateral adjustment assembly 14 and the sample loading end) are made of alloy materials; the quartz full-hole liquid loading dish 16, the quartz half-hole liquid loading dish 17 and the quartz wafer 18 are made of quartz material; the silver stage 7 is made of silver material; the heat dissipation end 4, the radiator 401, the temperature sensing line 5, the temperature controller 501, the cold end liquid nitrogen inlet pipeline 6, and the liquid nitrogen tank 601 are made of general materials or can be directly purchased.
[0065] It is also worth mentioning that the size and related accessories of the above-mentioned laser cryo-ablation device for non-solid samples can be adjusted according to the sample pool of the corresponding laser. Among them, the size and position of the silver stage 7 can be adjusted, the position of the multi-functional sample slot 10 can be adjusted, and the length can also be adjusted, but the width remains fixed, so as to realize the replacement of the frozen sample pool and the room temperature sample pool without affecting the subsequent air inlet and outlet and testing operations.
[0066] Example:
[0067] The above-mentioned device of the present invention is now described in detail with reference to specific embodiments. The embodiments of the present invention provide a laser cryoablation method for non-solid samples, and specifically provide a LA-ICP-MS component analysis method for fluid inclusions and liquid samples by cryoablation; wherein,
[0068] A LA-ICP-MS composition analysis method for fluid inclusion cryo-denudation comprises the following steps:
[0069] Step S1: Prepare the rock sample into inclusion slices, wherein the thickness of the inclusion slices is 80 to 300 μm and both sides need to be polished.
[0070] Step S2: Conduct a detailed petrographic observation on the inclusion thin section, observe in detail the type, shape, color, gas-liquid ratio, occurrence and inclusion combination characteristics of the host mineral and the inclusions therein, and mark the number, size, depth and other information of the fluid inclusions to be tested one by one.
[0071] Step S3: Cut the inclusion slice into small pieces with a diameter of less than 2 cm; soak the slide with acetone, scan and record the relative position of the fluid inclusions in the slice, test the uniform temperature, freezing point and initial melting temperature of the target fluid inclusions and mark them one by one.
[0072] Step S4: Place the temperature-measured inclusion slice onto the quartz wafer 18 of the laser ablation freezing device. Place a target sample or a solid standard (e.g., NIST 612, SCA 17) in the multifunctional sample well 10. If required, a standard solution can also be placed in the quartz half-well liquid carrier 17 for freezing. Fine-tune the focus to ensure a clear image. Find and locate the fluid inclusion to be measured in the laser ablation software system.
[0073] Step S5: Cool the silver stage 7 using the temperature controller 501 and observe whether the inclusion flakes and / or the standard solution are completely frozen. It is recommended to freeze them to around -90°C. Set the ablation spot according to the size of the inclusion flakes and the laser ablation power according to the type of host mineral. If you are unsure, adjust the power from small to large and set the minimum ablation power to the ablation power. Set the laser ablation frequency to 5-10 Hz.
[0074] Step S6: Set the test sequence. The fluid inclusions in the same host mineral are set as a combined sequence, which begins and ends with a solid material standard (such as NIST612, SCA17) and a standard solution. A set of solid material standards needs to be added before and after every ten unknown samples tested.
[0075] Step S7: After the test is completed and the element signal is obtained, the composition calibration is performed based on the measured value of the solid material standard (such as NIST612, SCA17) and the proportion of the known salinity standard solution and the salinity converted from the mineral freezing point.
[0076] A method for analyzing components of a liquid sample by cryo-denudation LA-ICP-MS comprises the following steps:
[0077] Step S1: Prepare element isotope standard solution according to test requirements.
[0078] Step S2: Place the liquid sample and standard solution in the quartz full-well liquid carrier 16, and place NIST610, NIST612 or other standard samples in the multifunctional sample slot 10. Fine-tune the focus to make the image clear, and find and calibrate the position and number of the liquid sample and standard solution in the laser ablation software system.
[0079] Step S3: Lower the temperature of the silver stage 7 via the temperature controller 501 and observe whether the liquid sample to be tested and the standard solution are completely frozen. It is recommended to freeze them to about -90°C.
[0080] Step S4, setting laser ablation parameters: the spot is set to 10-100 μm, the ablation power of the frozen solution is set to 1.5-4 J, the ablation power of the NIST61X series standard is set to 2-4 J, and the frequency is 5-10 Hz.
[0081] Step S5, setting the test sequence: before and after each test of eight unknown sample points, repeat the test twice of the standard sample NIST612 and twice of the laboratory-proportioned standard solution (for material calibration).
[0082] Step S6: After the test is completed and the element signal is obtained, the corresponding fractionation coefficient is obtained according to the measured values of the standard sample and the standard solution and their standard values, and the fractionation correction is performed on the test sample to obtain its actual element isotope content.
[0083] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A laser ablation freezing device for non-solid samples, characterized in that: The device comprises: a sample pool body (3), a heat dissipation end (4), a temperature sensing line (5), a cold end liquid nitrogen inlet pipeline (6), a silver stage (7), a sample moving device (9) and a multifunctional sample slot (10); wherein, The heat dissipation end (4), the temperature sensing line (5) and the cold end liquid nitrogen inlet pipeline (6) are sequentially arranged side by side outside the sample cell body (3); The silver stage (7) and the multifunctional sample slot (10) are arranged inside the sample cell body (3); The rotatable part of the sample moving device (9) is arranged outside the sample cell body (3); The silver loading platform (7) is connected to the heat dissipation end (4), the temperature sensing line (5) and the cold end liquid nitrogen inlet pipeline (6).
2. The laser ablation freezing device for non-solid samples according to claim 1, characterized in that: The device further comprises a sample cover (1); the sample cover (1) is provided with a glass skylight (2) according to the size of the multifunctional sample slot (10) and the silver stage (7).
3. A laser ablation freezing device for non-solid samples according to claim 1 or 2, characterized in that: The heat dissipation end (4) is directly connected to the radiator (401), and the radiator (401) is connected to the temperature controller (501). The radiator (401) is used for liquid nitrogen discharge and temperature control of the silver stage (7).
4. The laser ablation freezing device for non-solid samples according to claim 1, characterized in that: The temperature sensing line (5) is directly connected to a temperature controller (501), and the temperature controller (501) is used for controlling the temperature of the silver loading platform (7).
5. The laser ablation freezing device for non-solid samples according to claim 1, characterized in that: The cold end liquid nitrogen inlet pipeline (6) is directly connected to a liquid nitrogen tank (601), and the liquid nitrogen tank (601) is used to cool the silver stage (7).
6. The laser ablation freezing device for non-solid samples according to claim 1, characterized in that: The silver stage (7) is provided with a silver stage central light-transmitting hole (8), and the silver stage central light-transmitting hole (8) is used for transmitting light to facilitate sample observation.
7. The laser ablation freezing device for non-solid samples according to claim 1, characterized in that: The sample moving device (9) comprises: a Y-axis longitudinal adjustment component (13), an X-axis transverse adjustment component (14) and a sample loading end (15); wherein, The rotatable parts of the Y-axis longitudinal adjustment component (13) and the X-axis lateral adjustment component (14) are arranged outside the sample pool body (3); the sample loading end (15) is covered on the silver stage (7); the knobs of the Y-axis longitudinal adjustment component (13) and the X-axis lateral adjustment component (14) and their adjustment components are used for the lateral and longitudinal movement of the sample loading end (15).
8. The laser ablation freezing device for non-solid samples according to claim 1, characterized in that: The multifunctional sample slot (10) comprises a multifunctional sample slot frame (11) and a plurality of spring assemblies (12), wherein the plurality of spring assemblies (12) are arranged inside the multifunctional sample slot frame (11).
9. A laser ablation freezing method for non-solid samples, said method using the apparatus according to claims 1-8, characterized in that: The method comprises the following steps: Step S1: Prepare the rock sample into inclusion slices, and polish both sides; Step S2, performing petrographic observation on the inclusion thin section, and marking the number, size and depth information of the fluid inclusions to be tested one by one; Step S3: Cut the inclusion slice into small pieces, soak the slide in acetone, scan and record the relative positions of the fluid inclusions in the inclusion slice, test the uniform temperature, freezing point and initial melting temperature of the target fluid inclusions, and mark them one by one; Step S4: Place the temperature-measured inclusion slice into the quartz wafer (18) of the laser ablation freezing device, place a solid material standard sample in the multifunctional sample slot (10), and if a standard liquid is required, place it in the quartz half-hole liquid carrier (17) to be frozen, and find and locate the fluid inclusion to be measured in the laser ablation software system; Step S5, cooling the silver stage (7) and observing whether the inclusion flakes are completely frozen, setting the ablation spot according to the size of the inclusion flakes, and setting the laser ablation power according to the type of host mineral; Step S6: Set up a test sequence. The fluid inclusions in the same host mineral are set as a combined sequence, starting and ending with a solid material standard and a standard liquid. A set of solid material standards needs to be added before and after every ten unknown samples tested at most. Step S7: After the test is completed and the element signal is obtained, a standard solution of known salinity is prepared according to the measured value of the solid material standard sample and the salinity converted from the mineral freezing point for component calibration.
10. A laser ablation freezing method for non-solid samples, the method using the device according to claims 1-8, characterized in that: The method comprises the following steps: Step S1: Prepare element isotope standard solution according to test requirements; Step S2, placing the liquid sample to be tested and the standard solution into the quartz full-pore liquid-carrying dish (16), placing the standard sample into the multifunctional sample slot (10), and finding and calibrating the position and number of the liquid sample to be tested and the standard solution in the laser ablation software system; Step S3, cooling the silver stage (7) to observe whether the liquid sample to be tested and the standard solution are completely frozen; Step S4, setting laser ablation parameters of the liquid sample to be tested and the standard solution; Step S5: Set the test sequence to test the standard sample and the standard solution twice before and after each test of eight unknown sample points; Step S6: After the test is completed and the element signal is obtained, the corresponding fractionation coefficient is obtained according to the measured values of the standard sample and the standard solution and their standard values, and the fractionation correction is performed on the liquid sample to obtain the actual element isotope content of the liquid sample to be tested.