CN110794067A - Sample preparation device and sample preparation method for carbonate carbon-oxygen isotope micro-area analysis - Google Patents
Sample preparation device and sample preparation method for carbonate carbon-oxygen isotope micro-area analysis Download PDFInfo
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Abstract
The invention discloses a sample preparation device and a method for carbonate carbon-oxygen isotope micro-area analysis, wherein a phosphoric acid capillary micro sample injector and a carbonate sample pool are arranged; the side surface of the cavity of the carbonate sample pool is respectively provided with a helium gas inlet and a carbon dioxide gas outlet, and the top cover is provided with a micro-injection needle opening; the outlet of the phosphoric acid capillary microsyringe injects phosphoric acid into a sample in the carbonate sample pool through a micro-injection needle, and the carbon dioxide outlet is connected with a carbon-oxygen isotope tester; the sample frame is arranged on the electric control triaxial sample table, and the bottom of the sample frame is provided with a temperature control plate. The invention adopts a micro-injection needle to inject phosphoric acid micro-droplets to react with a carbonate sample, collects the gas generated by the reaction to carry out carbon-oxygen isotope analysis, simultaneously considers higher spatial resolution and data accuracy and realizes micro-area in-situ analysis; the device has low cost and simple structure.
Description
Technical Field
The invention relates to a sample preparation device and a sample preparation method for carbonate carbon-oxygen isotope micro-area analysis.
Background
Carbon-oxygen isotope research is an important means for researching carbonate (rock), and a micro-area in-situ analysis method is the leading edge and trend of geological research. A conventional method for carbon-oxygen isotope analysis of carbonate (rock) is the phosphoric acid method (McCree,1950) by reacting phosphoric acid with carbonate minerals to produce CO2Gas is sent into a mass spectrometer for analysis; the data obtained by the method is stable and simple and convenient to operate, but the method requires the separation and crushing of the mineral and rock to be detected, has large required sample amount and low spatial resolution, and obviously cannot meet the requirements of the current micro-area in-situ analysis. And the method can not effectively distinguish microstructures such as the period, the girdle and the like of the carbonate mineral in the sample to be detected, and a mixed carbon-oxygen isotope value is often obtained, which also does not meet the requirement of the current fine research.
Although the micro-drilling sampling method can improve the spatial resolution (hundreds of microns) to a certain extent and reduce the sample dosage (dozens of micrograms), the operation is too complicated, the spatial resolution is limited by the diameter of a drill bit, and the sampling work cannot be carried out on smaller minerals and structures. Can not meet the current requirements of micro-area analysis.
Laser probe analysis is a micro-area analysis method commonly used in recent years, and can remarkably improve the spatial resolution (dozens of micrometers) of the test. The high-energy laser beam is used for denudating a mineral measuring point to be measured, and micro-area in-situ sampling analysis is realized. The method can be used with a microscope, and facilitates selective analysis according to the mineral stage and structure of the sample. At present, the infrared laser probe is mainly used for carbonate (rock)The carbon-oxygen isotope research is carried out, and the basic principle is that a sample is heated by a high-energy infrared laser beam to decompose carbonate to generate CO2Gas, collecting CO2The gas was subjected to mass spectrometry to obtain a carbon-oxygen isotope value. The method has high spatial resolution (tens of microns) and is enough to satisfy the carbon-oxygen isotope research of a micro structure. However, this method relies on carbonate decomposition (CaCO)3＝CaO+CO2) To measure the CO generated2The carbon-oxygen isotope value of (a) is that the carbon isotope is not fractionated in the process, but the oxygen isotope is fractionated to influence the analysis result. Delta measured by the method13The C analysis precision (1 sigma) can reach 0.22-0.24 per mill, which is close to the analysis precision of phosphoric acid method, but delta18The O analysis precision is 0.38-0.57 per mill, which is different from the phosphoric acid method (Vancanfu, etc., 2014). The reason for the influence on the accuracy of oxygen isotope analysis may be that the temperature effect caused by high temperature during laser ablation causes oxygen isotope fractionation (Huangjunhua et al, 2001; He Daizhan, 2003), and a part of the oxygen fractionation enters CaO, resulting in a large difference between the measured value and the measured value by the phosphoric acid method. This fractionation is temperature dependent and, although corrected to some extent, current corrections use a constant number of corrections (Sharp, 1992; Smalley et al, 1992; huangjunhua et al, 2001; he dao qing, 2003) and the isotopic fractionation mechanism is not clear and it is difficult to accurately correct the isotopic fractionation problem using this method. And the method has higher cost and is limited by the instrument condition.
There is also a laser sampling and phosphoric acid method combined test method (fangchang, 2014), the principle is: the sample is degraded into aerosol by ultraviolet laser, the aerosol is transported by carrier gas through a quartz filter membrane, the degraded carbonate microparticles (20ug) are collected by the quartz filter membrane, and then the quartz filter membrane with the collected carbonate microparticles is reacted with phosphoric acid to determine the carbon-oxygen isotope value of the carbonate microparticles. The method can avoid oxygen isotope fractionation caused by thermal effect in the laser ablation process, and the test precision is close to that of the test result of the traditional phosphoric acid method. However, the method is complicated to operate, sample loss and pollution in the sample transfer process cannot be guaranteed, the method is high in cost, and the method is difficult to implement in a common laboratory.
In addition, the development of the microinjection system is mature at present, and the injection flow of the microinjector (pump) on the market can reach the injection precision of several nanoliters per minute. However, the technology is mainly applied to the biological field at present, and the geological field is not applied at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a sample preparation device for carbonate carbon-oxygen isotope micro-area analysis, which adopts a micro-injection needle to inject phosphoric acid micro-droplets to react with a carbonate sample, collects gas generated by the reaction to perform carbon-oxygen isotope analysis, and has the advantages of higher spatial resolution and data accuracy, low device cost and simple structure.
The purpose of the invention is realized by the following technical scheme: a sample preparation device for carbonate carbon-oxygen isotope micro-area analysis comprises a phosphoric acid capillary micro-sample injector and a carbonate sample pool;
the carbonate sample cell comprises a cavity and a top cover, wherein a helium gas inlet and a carbon dioxide gas outlet are respectively arranged on the side surface of the cavity, and a micro-injection needle opening for passing through a micro-injection needle is arranged on the top cover; the outlet of the phosphoric acid capillary microsyringe injects phosphoric acid into a sample in the carbonate sample pool through a microscopic injection needle, and the carbon dioxide outlet is connected with a carbon-oxygen isotope tester through a carbon dioxide outlet pipe; the helium gas inlet is connected with an external helium source through a helium gas inlet pipe, and valves are arranged on the helium gas inlet pipe, the carbon dioxide gas outlet pipe and the microinjection needle;
an electrically-controlled triaxial sample table is arranged in the carbonate sample pool, a sample rack for placing samples is arranged on the electrically-controlled triaxial sample table, and a temperature control plate is arranged at the bottom of the sample rack; the temperature control plate sequentially comprises a thin silver plate with a hole in the center, a polyimide heating film with a hole in the center and a temperature probe, the polyimide heating film is attached to the lower part of the thin silver plate, and the sample frame is tightly pressed on the thin silver plate through an elastic sheet; the temperature probe is contacted with the thin silver plate and is used for detecting the temperature of the thin silver plate, and the temperature probe and the polyimide heating film are respectively connected with the controller through leads;
and quartz windows for transmitting light and observing the reaction condition in the sample cell are arranged in the middle of the top cover and the base of the cavity.
Further, the phosphoric acid capillary microsyringe is positioned obliquely above the hydrochloride sample cell, and the micro-injection needle is obliquely arranged.
Further, a carbon dioxide purification device for purifying carbon dioxide, such as an alcohol-liquid nitrogen cold trap, a gas chromatography apparatus or an isotope mass spectrometer with a chromatographic column, such as an MAT 253 stable isotope ratio mass spectrometer, is arranged between the carbon dioxide gas outlet and the carbon-oxygen isotope tester.
Further, a flow meter is arranged at the helium gas inlet.
Furthermore, an acid needle protective cover for preventing the micro-injection needle from being pressed and broken when the micro-injection needle is contacted with a sample is arranged on the periphery of the micro-injection needle; and the inner surface and the outer surface of the micro-injection needle are both provided with a gold-plated layer or a Teflon coating for preventing phosphoric acid from corroding the micro-injection needle.
Furthermore, the carbonate sample pool is of a cuboid structure, and a helium gas inlet and a carbon dioxide gas outlet are respectively arranged on two opposite side surfaces of the carbonate sample pool; wherein, the helium gas inlet is arranged below the sample, and the carbon dioxide gas outlet is arranged above the sample.
The invention also provides a sample preparation method for carbonate carbon-oxygen isotope micro-area analysis, which comprises the following steps:
s1, setting parameters: setting reaction temperature and reaction time according to carbonate minerals, selecting phosphoric acid injection amount according to the required erosion diameter, and setting helium gas flow rate;
s2, point selection is carried out, and the operation is as follows:
s21, placing the carbonate mineral sample on a sample rack, and covering a top cover to ensure the sample pool to be sealed;
s22, aligning a tele lens to a quartz window on the top cover to find a point to be measured;
s23, after finding the point to be measured, switching to a short-focus lens, operating the Z axis of the sample holder to focus, so that the acid outlet of the micro-injection needle is positioned above the point to be measured, and the micro-injection needle keeps a distance of 5um from the sample
S24, recording the X, Y, Z coordinates at the moment;
s25, switching to a telephoto lens, returning to the step S22, and observing a plurality of points to be measured;
s3, carrying out acid injection reaction, comprising the following steps:
s31, vacuumizing: closing a helium gas inlet, a carbon dioxide gas outlet and a microinjection needle injection port, starting a vacuum pump to evacuate air in the sample pool, wherein the vacuum degree is higher than 2 Pa;
s32, filling helium, introducing the helium into the sample cell, and closing the helium after the sample cell is filled with the helium;
s33, preheating, heating the sample to a set temperature by using a heating plate, and heating phosphoric acid in the phosphoric acid capillary micro-injector to the set temperature;
s34, acid injection: the sample stage automatically moves the point location to the lower part of the micro-injection needle according to the stored point location information, and the micro-injection needle injects 100% phosphoric acid to the measuring point according to the set acid injection amount to perform full reaction;
s35, collecting CO2Gas: after the reaction is finished, opening a carbon dioxide gas outlet valve and a helium gas inlet valve, and pushing the generated carbon dioxide gas out of the sample cell through helium;
s36, purifying the collected carbon dioxide;
and S37, automatically moving the sample to the next position by the sample stage according to the program control, returning to the step S31, and analyzing other measuring points.
The invention has the beneficial effects that: the invention adopts the micro-injection needle to inject the phosphoric acid micro-droplets to react with the carbonate sample, collects the gas generated by the reaction to carry out carbon-oxygen isotope analysis, simultaneously considers higher spatial resolution and data accuracy and realizes the micro-area in-situ analysis; the device can be arranged on a microscope, and a tester can select points for testing according to testing requirements; the phosphoric acid probe and the full-automatic sample pool are controlled by a computer, the automation of the test process can be realized, the test efficiency is improved, and the error caused by manual operation is reduced; compared with a laser ablation system, the device has low cost and simple structure, and is easy to refit and upgrade in a conventional carbon-oxygen isotope laboratory.
Drawings
FIG. 1 is a schematic structural diagram of a sample preparation device for carbonate carbon-oxygen isotope microanalysis according to the present invention;
FIG. 2 is a front view of a sample preparation device for carbonate carbon-oxygen isotope microanalysis in accordance with the present invention;
FIG. 3 is a side view of a sample preparation device for carbonate carbon-oxygen isotope micro-zone analysis in accordance with the present invention;
FIG. 4 is a top view of a sample preparation device for carbonate carbon-oxygen isotope microanalysis in accordance with the present invention;
FIG. 5 shows the erosion pit (scale bar diameter is 100um) formed by the dilute hydrochloric acid micro-droplet eroding carbonate (rock) sample;
description of the labeling: 1-phosphoric acid capillary microsyringe; 2-carbonate sample pool, 21-cavity, 22-top cover, 23-helium inlet, 24-carbon dioxide outlet and 25-micro injection needle opening; 3-carbon-oxygen isotope tester; 4-carbon dioxide purification device.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
As shown in fig. 1 to 4, a sample preparation device for carbonate carbon-oxygen isotope micro-zone analysis comprises a phosphoric acid capillary micro-injector 1 and a carbonate sample cell 2;
the carbonate sample cell 2 comprises a cavity 21 and a top cover 22, wherein the side surface of the cavity 21 is respectively provided with a helium gas inlet 23 and a carbon dioxide gas outlet 24, and the top cover 22 is provided with a micro-injection needle opening 25 for passing through a micro-injection needle; the outlet of the phosphoric acid capillary microsyringe 1 injects phosphoric acid into a sample in the carbonate sample pool through a micro-injection needle, and the carbon dioxide outlet 24 is connected with the carbon-oxygen isotope tester 3 through a carbon dioxide outlet pipe; the helium gas inlet is connected with an external helium source through a helium gas inlet pipe, and valves are arranged on the helium gas inlet pipe, the carbon dioxide gas outlet pipe and the microinjection needle;
an electrically controlled triaxial sample table is arranged in the carbonate sample pool 2, a sample rack for placing samples is arranged on the electrically controlled triaxial sample table, and a temperature control plate is arranged at the bottom of the sample rack; the temperature control plate sequentially comprises a thin silver plate with a hole in the center, a polyimide heating film with a hole in the center and a temperature probe (a small hole in the middle of the temperature control plate is used for transmitting light, and the small hole can transmit light when an instrument and a microscope are used together to achieve the purpose of observing a sample; the temperature probe is contacted with the thin silver plate and is used for detecting the temperature of the thin silver plate, and the temperature probe and the polyimide heating film are respectively connected with the controller through leads;
the middle parts of the cavity top cover 22 and the base are provided with quartz windows for transmitting light and observing the reaction condition in the sample cell.
Further, phosphoric acid capillary microsyringe 1 is located the oblique top in hydrochloride sample cell, and the microinjection needle slope sets up, and the microinjection needle that the slope set up can not shelter from the sample, more is favorable to observing the sample reaction condition.
Furthermore, a triaxial sample holder is arranged in the carbonate sample cell 2, and the sample is positioned on the triaxial sample holder.
Further, a carbon dioxide purification device 4 for purifying carbon dioxide, such as an alcohol-liquid nitrogen cold trap, a gas chromatography apparatus or an isotope mass spectrometer with a chromatography column, such as a MAT 253 stable isotope ratio mass spectrometer, is disposed between the carbon dioxide gas outlet 24 and the carbon-oxygen isotope tester 3.
Further, a flow meter is arranged at the helium inlet 21.
Furthermore, an acid needle protective cover for preventing the micro-injection needle from being pressed and broken when the micro-injection needle is contacted with a sample is arranged on the periphery of the micro-injection needle; and the inner surface and the outer surface of the micro-injection needle are both provided with a gold-plated layer or a Teflon coating for preventing phosphoric acid from corroding the micro-injection needle.
Further, the carbonate sample pool is of a cuboid structure, and a helium gas inlet 23 and a carbon dioxide gas outlet 24 are respectively arranged on two opposite side surfaces of the carbonate sample pool; wherein, a helium gas inlet 23 is arranged below the sample, and a carbon dioxide gas outlet 24 is arranged above the sample.
The sample injection method for carrying out carbonate (rock) micro-area and in-situ carbon-oxygen isotope test by using the device comprises the following steps: installing the sample meeting the test condition on a sample rack, selecting a point to be tested, injecting phosphoric acid on the surface of the sample through a phosphoric acid capillary microsyringe, and collecting the generated CO2The gas determines the carbon-oxygen isotope.
Mainly comprises the steps of test parameter selection, point location selection, injection reaction and CO collection2And mass spectrometry.
The principle of the carbon-oxygen isotope test of the carbonate is as follows:
the micro-drop of phosphoric acid injected by the micro-injection needle reacts with the surface of the carbonate sample, and the CO released by the reaction is collected2The gas, after purification, was analyzed by an isotope mass spectrometer. The spatial resolution of the test is improved, and meanwhile, a result which is consistent with the test precision of the traditional phosphoric acid method is obtained.
The diameter of the glass micro-injection needle on the market at present can be from 0.1 to dozens of micrometers, the caliber of the device is selected to be 5 micrometers, the amount of the discharged phosphoric acid is controlled by a micro-injector, the diameter of the discharged phosphoric acid micro-droplet is 10-n00um, the acid needle and the cover plate are obliquely arranged at an angle of 30-45 degrees, the influence of the acid on the observation of a sample is reduced, and the acid needle is not easy to break when contacting the sample. The acid outlet is arranged at the tail end of the acid needle, and is adjusted to be positioned in the middle of the visual field and on the focal plane of the short-focus lens during installation. During the test, the phosphoric acid micro-droplets discharged by the acid needle form small droplets on the sample due to the surface tension of the liquid, and simultaneously react with the sample to generate CO2A gas. The matched microinjector technology is mature, and the microinjector (microinjection pump) on the market can meet the requirement of accurately injecting phosphoric acid micro-droplets. In addition, the hot phosphoric acid may cause some corrosion of the quartz needle, which can be solved by gold plating or teflon coating on the surface of the needle.
Fig. 5 shows an erosion pit formed by erosion of dilute hydrochloric acid micro-droplets on the surface of a hydrochloride (rock) sample, wherein the erosion pit is circular, the diameter is 10-n00um, the depth is about 10um, the erosion of acid is mainly based on the pit bottom, the bottom of the ablation pit is flat, and the erosion pit is spatially in a shape of a 'dish'. The erosion pits have different characteristics for different samples, and the acid preferentially erodes the sample along the cleavage (c) and microfractures (d) to exhibit differential erosion, but generally to a more uniform extent, which may result in negligible isotopic fractionation and inhomogeneity.
Currently, laser probe analysis methods require minimal sample requirements, typically about 20ug of carbonate rock sample, to generate sufficient CO2Gas (ca. 2uL) was used for mass spectrometry (He Tao Qing, 2003). In the invention, taking calcite as an example, the diameter of an effective erosion pit formed by the reaction of phosphoric acid micro-droplets is 30-400um, the depth is about 10um, theoretically, the consumption sample amount is 20-3680ug, and 0.006-1.1uL of phosphoric acid is consumed, which is enough to generate enough CO2And gas, which meets the test requirements. In addition, because the method consumes a very small amount of samples, the analysis of one point can be realized in a short time, and the test efficiency is improved.
The invention relates to a sample preparation method for carbonate carbon-oxygen isotope micro-area analysis, which comprises the following steps:
s1, setting parameters: setting reaction temperature and reaction time according to carbonate minerals (natural gas industry standard SY/T6039-94 (carbonate rock carbon-oxygen isotope determination phosphoric acid method) Table A1 gives reference time and temperature), selecting phosphoric acid injection amount according to required erosion diameter, and setting helium gas flow rate;
s2, point selection is carried out, and the operation is as follows:
s21, placing the carbonate mineral sample on a sample rack, and covering a top cover to ensure the sample pool to be sealed;
s22, aligning a tele lens to a quartz window on the top cover to find a point to be measured;
s23, after finding the point to be measured, switching to a short-focus lens, operating the Z axis of the sample holder to focus, so that the acid outlet of the micro-injection needle is positioned above the point to be measured, and the micro-injection needle keeps a distance of 5um from the sample;
s24, recording the X, Y, Z coordinates at the moment;
s25, switching to a telephoto lens, returning to the step S22, and observing a plurality of points to be measured;
s3, carrying out acid injection reaction, comprising the following steps:
s31, vacuumizing: closing a helium gas inlet, a carbon dioxide gas outlet and a microinjection needle injection port, starting a vacuum pump to evacuate air in the sample pool, wherein the vacuum degree is higher than 2 Pa;
s32, filling helium, introducing the helium into the sample cell, and closing the helium after the sample cell is filled with the helium;
s33, preheating, heating the sample to a set temperature by using a heating plate, and heating phosphoric acid in the phosphoric acid capillary micro-injector to the set temperature;
s34, acid injection: the sample stage automatically moves the point location to the lower part of the micro-injection needle according to the stored point location information, and the micro-injection needle injects 100% phosphoric acid to the measuring point according to the set acid injection amount to perform full reaction;
s35, collecting CO2Gas: after the reaction is finished, opening a carbon dioxide gas outlet valve and a helium gas inlet valve, and pushing the generated carbon dioxide gas out of the sample cell through helium; if the reaction rate is high, gas collection can be started immediately after acid injection so as to improve the experimental efficiency and realize online real-time test;
s36, purifying the collected carbon dioxide;
and S37, automatically moving the sample to the next position by the sample stage according to the program control, returning to the step S31, and analyzing other measuring points.
Sample preparation and requirements:
1. the sample contains carbonate minerals, and has less pores and low permeability;
2. the sample is ground into a sheet with a specified size, the fir glue sheet is used, the sample needs mirror polishing, the surface is required to be flat and smooth and has no scratch, and in addition, glue is not injected when the sample is ground. Milling into conventional wrap sheets is recommended.
3. Considering that organic adhesives such as fir glue outgas under vacuum and affect the analysis results, the sample sheet was soaked with acetone or absolute ethanol, detached from the slide and washed.
4. The sample is dried without pollution.
After the reaction at each sampling point is finished, enough time is left for introducing carrier gas to lead residual CO in the system2And discharging, and then carrying out the next testing point test to prevent the testing result from being influenced. After each 5 stations are analyzed, the standards can be analyzed to correct and monitor the data.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (8)
1. A sample preparation device for carbonate carbon-oxygen isotope micro-area analysis is characterized by comprising a phosphoric acid capillary micro-sample injector (1) and a carbonate sample pool (2);
the carbonate sample cell (2) comprises a cavity (21) and a top cover (22), wherein a helium gas inlet (23) and a carbon dioxide gas outlet (24) are respectively arranged on the side surface of the cavity (21), and a micro-injection needle opening (25) for passing through a micro-injection needle is arranged on the top cover (22); an outlet of the phosphoric acid capillary microsyringe (1) injects phosphoric acid to a sample in the carbonate sample pool through a micro-injection needle, and a carbon dioxide outlet (24) is connected with the carbon-oxygen isotope tester (3) through a carbon dioxide outlet pipe; the helium gas inlet is connected with an external helium source through a helium gas inlet pipe, and valves are arranged on the helium gas inlet pipe, the carbon dioxide gas outlet pipe and the microinjection needle;
an electrically-controlled triaxial sample table is arranged in the carbonate sample pool (2), a sample rack for placing samples is arranged on the electrically-controlled triaxial sample table, and a temperature control plate is arranged at the bottom of the sample rack; the temperature control plate sequentially comprises a thin silver plate with a hole in the center, a polyimide heating film with a hole in the center and a temperature probe, the polyimide heating film is attached to the lower part of the thin silver plate, and the sample frame is tightly pressed on the thin silver plate through an elastic sheet; the temperature probe is contacted with the thin silver plate and is used for detecting the temperature of the thin silver plate, and the temperature probe and the polyimide heating film are respectively connected with the controller through leads;
and quartz windows for transmitting light and observing the reaction condition in the sample cell are arranged in the middle of the cavity top cover (22) and the base.
2. The sample preparation device for carbonate carbon-oxygen isotope micro-area analysis according to claim 1, wherein the phosphoric acid capillary microsyringe (1) is positioned obliquely above the hydrochloride sample cell, and the microinjection needle is obliquely arranged.
3. The sample preparation device for carbonate carbon-oxygen isotope micro-area analysis according to claim 1, characterized in that a carbon dioxide purification device (4) for purifying carbon dioxide is arranged between the carbon dioxide outlet (24) and the carbon-oxygen isotope tester (3).
4. The sample preparation device for carbonate carbon-oxygen isotope micro-area analysis according to claim 1, wherein a flow meter is arranged at the helium gas inlet (21).
5. The sample preparation device for carbonate carbon-oxygen isotope micro-area analysis according to claim 1, wherein the periphery of the micro-injection needle is provided with an acid needle protective cover for preventing the micro-injection needle from being broken under pressure when contacting with the sample.
6. The sample preparation device for carbonate carbon-oxygen isotope micro-area analysis according to claim 1, wherein a gold-plated layer or a teflon coating for preventing phosphoric acid from corroding the micro-injection needle is arranged on the inner surface and the outer surface of the micro-injection needle.
7. The sample preparation device for carbonate carbon-oxygen isotope micro-area analysis according to claim 1, wherein the carbonate sample cell is of a rectangular parallelepiped structure, and a helium gas inlet (23) and a carbon dioxide gas outlet (24) are respectively arranged on two opposite side surfaces of the carbonate sample cell; wherein, the helium gas inlet (23) is arranged below the sample, and the carbon dioxide gas outlet (24) is arranged above the sample.
8. The method for preparing a sample for carbonate carbon-oxygen isotope micro-area analysis according to any one of claims 1 to 7, comprising the following steps:
s1, setting parameters: setting reaction temperature and reaction time according to carbonate minerals, selecting phosphoric acid injection amount according to the required erosion diameter, and setting helium gas flow rate;
s2, point selection is carried out, and the operation is as follows:
s21, placing the carbonate mineral sample on a sample rack, and covering a top cover to ensure the sample pool to be sealed;
s22, aligning a tele lens to a quartz window on the top cover to find a point to be measured;
s23, after finding the point to be measured, switching to a short-focus lens, operating the Z axis of the sample holder to focus, so that the acid outlet of the micro-injection needle is positioned above the point to be measured, and the micro-injection needle keeps a distance of about 5um from the sample
S24, recording the X, Y, Z coordinates at the moment;
s25, switching to a telephoto lens, returning to the step S22, and observing a plurality of points to be measured;
s3, carrying out acid injection reaction, comprising the following steps:
s31, vacuumizing: closing a helium gas inlet, a carbon dioxide gas outlet and a microinjection needle injection port, starting a vacuum pump to evacuate air in the sample pool, wherein the vacuum degree is higher than 2 Pa;
s32, filling helium, introducing the helium into the sample cell, and closing the helium after the sample cell is filled with the helium;
s33, preheating, heating the sample to a set temperature by using a heating plate, and heating the phosphoric acid in the phosphoric acid capillary micro-injector to the set temperature;
s34, acid injection: the sample stage automatically moves the point location to the lower part of the micro-injection needle according to the stored point location information, and the micro-injection needle injects 100% phosphoric acid to the measuring point according to the set acid injection amount for full reaction;
s35, collecting CO2Gas: after the reaction is finished, opening a carbon dioxide gas outlet valve and a helium gas inlet valve, and pushing the generated carbon dioxide gas out of the sample cell through helium;
s36, purifying the collected carbon dioxide;
and S37, automatically moving the sample to the next position by the sample stage according to the program control, returning to the step S31, and analyzing other measuring points.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112557496A (en) * | 2020-11-20 | 2021-03-26 | 广东先导稀材股份有限公司 | Preparation method and application of needle-shaped sample for glow discharge mass spectrometry detection |
| CN114688224A (en) * | 2022-04-08 | 2022-07-01 | 成都理工大学 | Corrosion-resistant full-automatic injection pump system |
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