Novel device for carrying out carbonate C and O isotope analysis by utilizing GasBench

Abstract

The utility model belongs to the technical field of C and O isotope detection pretreatment by utilizing stable gas isotopes, and discloses a novel device for analyzing C and O isotopes of carbonate by utilizing GasBench, which comprises a PP (polypropylene) material container, a rubber band, a baffle, a support component, a sample tube, a sample frame and an electromagnet. According to a phosphoric acid adding method, the phosphoric acid storage device is small in design and low in cost, phosphoric acid is pre-added into the storage device through an injector before FLUSH, the phosphoric acid is put into the bottom of a sample bottle containing a sample, carbon dioxide in a sample tube is removed through the FLUSH process, an electromagnet is started in a centralized mode, a baffle is opened, the phosphoric acid is added, the phosphoric acid reacts with the sample, and carbon dioxide is generated.

Description

Technical Field

[0001] The utility model belongs to the technical field of pretreatment for C and O isotope detection by using stable gas isotopes, and particularly relates to a novel device for carbonate C and O isotope analysis by using GasBench. Background Technique

[0002] The stable isotope technique has various special functions such as tracing, integration, and indication. In terms of the breadth of its impact on technology, perhaps only modern electronics and data processing can be compared with the stable isotope technique. It has improved people's ability to observe and identify things to the molecular level, opening up a new way for people to understand the world. In China, the stable isotope technique has been widely applied in research fields such as geology, agriculture, ecology, environment, food traceability, etc., as well as for exploring the paleoclimate and the living environment of ancient humans, etc.

[0003] For different measurement items, different peripherals can be selected, such as an elemental analyzer (EA), a gas chromatograph (GC), and a multi-purpose online gas preparation system (Gas Bench) to perform pretreatment on samples.

[0004] In fields such as the study of the ancient ocean carbon cycle, paleoclimate, and stratigraphic correlation, reliable carbonate carbon and oxygen isotope analysis methods are crucial. The sample preparation process in carbonate carbon and oxygen isotope analysis is to extract carbonate ions in the form of carbon dioxide and measure the carbon and oxygen isotope composition using a gas stable isotope mass spectrometer. Different sample preparation methods have different requirements for sample properties and sample amounts, and the accuracy of the analysis results also varies. Therefore, the sample preparation method is very important in the analysis and testing of carbonate carbon and oxygen isotopes. Currently, the sample preparation methods for carbonate carbon and oxygen isotopes include: combustion method of elemental analyzer, laser ablation method, and phosphoric acid decomposition method. Due to certain limitations of the first two methods, the current sample preparation method for determining carbonate δ 13 C, δ 18 O is mainly the phosphoric acid decomposition method. The phosphoric acid decomposition sample preparation method can be divided into: traditional offline method for preparing CO 2 , which enters the gas stable isotope mass spectrometer for analysis and determination through a dual-channel injection system, and online preparation of CO 2 coupled with a continuous flow gas stable isotope mass spectrometer.

[0005] Traditional phosphoric acid decomposition sample preparation:

[0006] Use helium to purge the sample tube containing carbonate with helium to remove carbon dioxide in the sample tube. Manually add anhydrous phosphoric acid to the bottom of the sample tube using a syringe. In a heatable sample tray, phosphoric acid reacts with the carbonate sample to generate carbon dioxide. Through the carrier gas, use a water trap to remove water, and separate CO 2 from impurity gases to achieve CO2 Determination of carbon and oxygen isotopes of gases.

[0007] There are several problems with this method:

[0008] ① Since the sample tube is under positive pressure after FLUSH, and the phosphoric acid is anhydrous phosphoric acid with extremely high viscosity, it is very difficult to add manually, resulting in serious waste, large consumption, and time-consuming and laborious.

[0009] ② Air is easily introduced during the process of adding phosphoric acid using a syringe, resulting in inaccurate detection data.

[0010] ③ Phosphoric acid is likely to remain on the polytetrafluoro sample bottle gasket, and the automatic injection needle is likely to be blocked during injection.

[0011] Fully automatic carbonate preparation device:

[0012] The Thermo Kiel IV fully automatic carbonate preparation device can be selected. It has fully automated operation and high analysis accuracy, and is suitable for isotope mass spectrometry analysis of trace carbonate samples. The storage, transfer, and chemical reactions of 102% phosphoric acid are carried out under temperature control conditions. During the phosphoric acid acidification process, CO is generated in a diaphragm-free reaction bottle. 2 , and the generated water and non-condensable gases are removed from the CO gas phase by the first trap. 2 Before transferring the CO gas to the micro-volume box, the gas pressure of CO can be measured; if necessary, the sample amount of CO gas can be adjusted by diffusion dilution. The pure and dry CO in the micro-volume box is precisely measured by the gas isotope mass spectrometry host through a dual-channel comparison. 2 Before transferring the CO gas to the micro-volume box, the gas pressure of CO can be measured; if necessary, the sample amount of CO gas can be adjusted by diffusion dilution. The pure and dry CO in the micro-volume box is precisely measured by the gas isotope mass spectrometry host through a dual-channel comparison. 2 Before transferring the CO gas to the micro-volume box, the gas pressure of CO can be measured; if necessary, the sample amount of CO gas can be adjusted by diffusion dilution. The pure and dry CO in the micro-volume box is precisely measured by the gas isotope mass spectrometry host through a dual-channel comparison. 2 Before transferring the CO gas to the micro-volume box, the gas pressure of CO can be measured; if necessary, the sample amount of CO gas can be adjusted by diffusion dilution. The pure and dry CO in the micro-volume box is precisely measured by the gas isotope mass spectrometry host through a dual-channel comparison. 2 The pure and dry CO in the micro-volume box is precisely measured by the gas isotope mass spectrometry host through a dual-channel comparison.

[0013] The purchase price of this device is expensive, about 700,000 yuan, and various problems are likely to occur during use.

[0014] The sealing gasket is prone to deformation, resulting in a high leak rate value; the position of the turntable deviates; due to the characteristics of pure phosphoric acid, the acid valve chamber is likely to have residues; the rubber acid tube is repeatedly squeezed and deformed, resulting in too slow an acid drip rate and shutdown; the potentiometer of the Bellow gas sampler is also prone to problems.

[0015] Through the above analysis, the problems and defects of the existing technology are as follows:

[0016] (1) The sealing gasket is prone to deformation, resulting in a high leak rate value; the position of the turntable deviates; due to the characteristics of pure phosphoric acid, the acid valve chamber is likely to have residues.

[0017] (2) The rubber acid tube is repeatedly squeezed and deformed, resulting in too slow an acid drip rate and shutdown; the potentiometer of the Bellow gas sampler is also prone to problems. Summary of the Utility Model

[0018] In view of the problems existing in the prior art, the present utility model provides a novel device for analyzing carbonate C and O isotopes using GasBench.

[0019] The present utility model is implemented as follows. A novel device for analyzing carbonate C and O isotopes using GasBench includes:

[0020] A PP (polypropylene) material container, a rubber band, a baffle, a support member, a sample tube, a sample rack, and an electromagnet;

[0021] A rubber band is provided outside the PP material container; a baffle is provided at the bottom of the PP material container; a support member is provided at the bottom of the baffle; the PP material container is provided inside the sample tube; the PP material container is provided inside the sample rack; an electromagnet is fixed to the bottom inside the sample rack by screws.

[0022] Further, the PP material container is provided inside the sample tube;

[0023] Further, the PP material container is provided inside the sample rack;

[0024] Further, an electromagnet is fixed to the bottom inside the sample rack by screws.

[0025] First, for the phosphoric acid addition method of the present utility model, a small and low-cost phosphoric acid storage device is designed. Before FLUSH, phosphoric acid is pre-added to the storage device through a syringe and placed at the bottom of the sample bottle containing the sample. Through the FLUSH process, carbon dioxide in the sample tube is removed. The electromagnet is centrally activated, the baffle is opened, and phosphoric acid is added to react with the sample to generate carbon dioxide.

[0026] Through the application of the rubber band and electromagnet on the phosphoric acid storage device of the present utility model, the addition of phosphoric acid is controlled quickly and conveniently, greatly reducing the time and workload of manual acid addition, eliminating potential hand injuries to staff; avoiding the entry of air during the phosphoric acid addition process, improving the accuracy of sample analysis; at the same time, avoiding the residue of phosphoric acid on the sample bottle gasket during the addition process, avoiding the blockage of the automatic injection needle, and greatly extending the service life; it can achieve the unified addition of phosphoric acid for a large number (≤98 pieces) of samples, ensuring the consistency of analysis and detection; the phosphoric acid storage device is low-cost and reusable.

[0027] Second, compared with the prior art, the novel device for analyzing carbonate C and O isotopes using GasBench provided by the embodiments of the present utility model mainly solves the following technical problems and achieves remarkable technical progress:

[0028] 1. Improve the analysis accuracy and stability: By using a PP material container, which has excellent chemical and thermal stability, it can effectively reduce sample contamination and reaction interference during the analysis process, thus improving the accuracy and stability of isotope analysis.

[0029] 2. Simplify the operation and improve the efficiency: The device is reasonably designed. The combination of the sample tube and the sample rack makes the placement and removal of samples simple and convenient; it can quickly and easily control the addition of phosphoric acid, greatly reducing the time and workload of manual acid addition; at the same time, the introduction of an electromagnet enables the simultaneous addition of phosphoric acid to a large number of sample tubes, further simplifying the operation process and improving the efficiency.

[0030] 3. Enhance the safety and reliability: The use of rubber bands and baffles enhances the sealing and stability of the PP material container, preventing sample leakage or spillage during the analysis process and improving the safety of the analysis process. The design of the support components also enhances the stability of the entire device, reducing the risk of device damage or sample loss caused by external factors.

[0031] 4. Expand the applicable range: Due to the good chemical compatibility of the PP material container, the device can be applied to the analysis of more types of carbonate samples, expanding the applicable range of the device.

[0032] The utility model has obtained significant technological progress by optimizing the materials and structure of the device, improving the accuracy and stability of isotope analysis, simplifying the operation process, enhancing the safety and reliability, and expanding the applicable range. These improvements make the device have higher practical value and economic benefits in the field of carbonate C and O isotope analysis.

[0033] Third, as the creative auxiliary evidence of the claims of the utility model, it is also reflected in the following important aspects:

[0034] The expected benefits and commercial value after the transformation of the technical solution of the utility model are:

[0035] The technical solution of the utility model can quickly and easily control the addition of phosphoric acid, greatly reducing the time and workload of manual acid addition, eliminating potential hand injuries of staff; avoiding the entry of air during the phosphoric acid addition process, improving the accuracy of sample analysis; at the same time, avoiding the residue of phosphoric acid on the sample bottle gasket during the addition process, avoiding the blockage of the automatic injection needle, and greatly extending the service life; it can realize the unified addition of phosphoric acid to a large number (≤98 pieces) of samples, ensuring the consistency of analysis and detection; the phosphoric acid storage device has a low cost and can be reused.

[0036] (2) The technical solution of the utility model solves the technical problems that people have always been eager to solve but have never been successful in obtaining:

[0037] The technical solution of the present utility model solves the long-existing technical problem of difficult operation in adding phosphoric acid. The original technical solution was to add phosphoric acid after helium FLUSH. Due to the positive pressure condition and the viscous property of phosphoric acid, adding phosphoric acid has always been a key step in the pretreatment process of GasBench for detecting C and O isotopes.

[0038] However, in this technical solution, phosphoric acid is added first, and the novel device is used to keep the sample from contacting phosphoric acid. After FLUSH, the reaction is carried out, which solves various problems in the process of adding phosphoric acid.

[0039] (3) The technical solution of the present utility model overcomes the technical prejudice:

[0040] The technical solution of the present utility model overcomes the traditional prejudice of adding phosphoric acid after FLUSH in the pretreatment process of GasBench for detecting C and O isotopes. With the novel device, phosphoric acid is added to the novel phosphoric acid storage device before FLUSH and does not contact the sample temporarily. After FLUSH, they contact and react. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 It is a structural diagram of a novel device for analyzing C and O isotopes of carbonates using GasBench provided by an embodiment of the present utility model.

[0042] Figure 2 It is a structural diagram of a baffle provided by an embodiment of the present utility model.

[0043] Figure 3 It is a diagram showing the baffle closed when the magnet is not energized during the FLUSH stage provided by an embodiment of the present utility model.

[0044] Figure 4 It is a diagram showing the baffle attracted and opened when the magnet is energized after FLUSH provided by an embodiment of the present utility model.

[0045] Figure 5 It is a schematic diagram of the overall experiment provided by an embodiment of the present utility model.

[0046] In the figure: 1. PP material container; 2. Rubber band; 3. Baffle; 4. Support member; 5. Sample tube; 6. Sample rack; 7. Electromagnet. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0047] In order to make the objectives, technical solutions and advantages of the present utility model clearer, the present utility model will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present utility model and are not used to limit the present utility model.

[0048] As Figures 1 - 5As shown in the figure, a new type of device for analyzing C and O isotopes of carbonate using GasBench provided by an embodiment of the present utility model includes:

[0049] A PP material container 1, a rubber band 2, a baffle 3, a support member 4, a sample tube 5, a sample rack 6, and an electromagnet 7.

[0050] A rubber band 2 is arranged inside the PP material container 1; a baffle 3 is arranged at the bottom of the PP material container 1; a support member 4 is arranged at the bottom of the baffle 3; the PP material container 1 is arranged inside the sample tube 5; the PP material container 1 is arranged inside the sample rack 6; an electromagnet 7 is fixed to the bottom inside the sample rack 6 by screws.

[0051] The PP material container 1 is arranged inside the sample tube 5 provided by an embodiment of the present utility model;

[0052] The PP material container 1 is arranged inside the sample rack 6 provided by an embodiment of the present utility model;

[0053] The electromagnet 7 is fixed to the bottom inside the sample rack 6 provided by an embodiment of the present utility model by screws.

[0054] The specific implementation of the present utility model:

[0055] ① Design a new type of phosphoric acid storage device

[0056] Design a PP material container with the maximum diameter slightly smaller than the inner diameter of the sample tube, which is composed of a rubber band 2, a baffle 3, a support member 4, etc. The baffle 3 is composed of a polytetrafluoro material and a stainless steel material.

[0057] ② Establish a new method for adding phosphoric acid using the device

[0058] Before the sample is flushed, add about 10 drops of pure phosphoric acid to the storage device using a dropper, and place the phosphoric acid storage device of the present utility model in the sample bottle to keep the phosphoric acid from flowing out;

[0059] After flushing, the electromagnet at the bottom of the sample bottle is energized. Under the action of the magnetic force of the magnet, the movable baffle opens, and the phosphoric acid drops into the bottom of the sample bottle and reacts with the sample.

[0060] Clearly and completely describe the technical solution of the utility model creation:

[0061] The present utility model adopts the following technical solutions:

[0062] ① Design a device for storing phosphoric acid with a size smaller than the inner diameter of the sample tube, made of PP, and composed of a rubber band 2, a baffle 3, and a support member 4. The inner side of the baffle is made of polytetrafluoro material, and the outer side is made of stainless steel material.

[0063] ② Under the tension of the rubber band 2, the baffle closes.

[0064] ③ Inject a certain amount of phosphoric acid into the storage device with a syringe. Place the entire phosphoric acid storage device at the bottom of the sample tube 5 with the sample added, and tightly cap the sample bottle.

[0065] ④ Place the sample tube 5 on the multi-purpose online gas preparation system (Gas Bench) and FLUSH to drive out the air in the tube.

[0066] ⑤ Energize the electromagnet 7 at the bottom of the sample rack 6 to generate magnetic force, attract the baffle 3 of the phosphoric acid storage device, open the baffle, and under the action of gravity, the phosphoric acid drops onto the bottom sample for reaction to generate CO 2 。

[0067] Compared with the prior art, what results does the present utility model adopt or what advantages and effects does it have due to those, such as performance improvement, cost reduction, etc.:

[0068] The phosphoric acid addition method of the present utility model designs a small and low-cost phosphoric acid storage device. Before FLUSH, phosphoric acid is pre-added to the storage device with a syringe and placed at the bottom of the sample bottle containing the sample. The carbon dioxide in the sample tube is removed through the FLUSH process. The electromagnet is centrally turned on to open the baffle, and the phosphoric acid is added to react with the sample to generate carbon dioxide.

[0069] Through the application of the rubber band and electromagnet on the phosphoric acid storage device, the present utility model quickly and conveniently realizes the control of phosphoric acid addition, greatly reduces the time and workload of manual acid addition, eliminates potential hand injuries of the staff; avoids the entry of air during the phosphoric acid addition process, improves the accuracy of sample analysis; at the same time, avoids the residue of phosphoric acid on the sample bottle gasket during the addition process, avoids the blockage of the automatic sampling needle, and greatly extends the service life; can realize the unified addition of phosphoric acid to a large number (≤98 pieces) of samples, ensuring the consistency of analysis and detection; the phosphoric acid storage device has a low cost and can be reused.

[0070] Compared with the method configured with a fully automatic carbonate preparation device, the equipment purchase cost is greatly saved, and the failures and problems caused by the components of the fully automatic carbonate preparation device are avoided, as shown in Table 1.

[0071] Table 1 Comparison of the use effects of the present utility model and the fully automatic carbonate preparation device

[0072] Serial number Item Before improvement The present utility model 1 Cost (equipment and device purchase cost) About 700,000 yuan 100 yuan 2 Phosphoric acid addition time (98 pieces) 98 min 10 min 3 Sealing washer failure Possible 0 4 Turntable position deviation Possible 0 5 Easy residue in acid valve chamber Possible 0 6 Failure caused by deformation of rubber acid pipe Possible 0 7 Potentiometer of gas sample storage device Possible 0

[0073] The design of the new device for carbon and oxygen isotope analysis of carbonates using GasBench described in the embodiments of the present utility model aims to provide an effective and stable way to process and analyze the carbon and oxygen isotopes in carbonate samples. The following are the functions of each component and the working principle of the overall device:

[0074] PP material container 1: Used to hold and protect carbonate samples. (PP may be polypropylene) The material has good chemical stability and will not react with the samples, ensuring the purity and integrity of the samples.

[0075] Elastic band 2: Used to fix or seal the PP material container to ensure that the samples will not spill or be contaminated during processing and analysis.

[0076] Baffle 3: Set at the bottom of the container to support the samples, prevent the samples from moving inside the container, and maintain the stability of the samples.

[0077] Supporting component 4: Located below the baffle to provide additional stability and support to ensure the stability of the entire device during operation.

[0078] Sample tube 5: Provides an external protection and positioning structure for the PP material container, allowing the samples to be easily inserted into the GasBench analysis system.

[0079] Sample rack 6: Used to store and fix the PP material container to ensure its position is fixed and not disturbed during analysis.

[0080] Electromagnet 7: Fixed to the bottom of the sample rack by screws, used to control the movement or fixation of the container by magnetism, can be remotely operated, reducing manual intervention, thus avoiding potential contamination or sample loss.

[0081] Sample preparation and loading: The carbonate samples are first placed in the PP material container. An elastic band is used to ensure the sealing of the container, and then the container is placed on the sample rack. A corresponding PP material container is also set inside the sample tube.

[0082] Sample positioning and fixation: The sample rack is designed to accommodate multiple sample containers to improve the analysis efficiency. The electromagnet is used to fix or release the PP material container during operation to ensure the stable position of the samples during analysis.

[0083] Analysis process: When the GasBench system is started, gas needs to be extracted from the samples for isotope ratio analysis. Due to the chemical stability of the PP material, it will not react with the samples or affect the release of the gas. The use of the electromagnet reduces the need for the operator to directly contact the samples, reducing the risk of sample contamination.

[0084] Data collection and processing: Once the gas in the samples is released and collected, GasBench will analyze the carbon and oxygen isotope ratios in the gas to provide detailed information about the sample composition.

[0085] With this design, this embodiment not only improves the efficiency and safety of sample processing, but also ensures the integrity of the sample and the accuracy of the analysis when performing carbonate isotope analysis. This method is particularly suitable for scientific research and industrial applications that require high precision and high repeatability.

[0086] Compared with the traditional phosphoric acid addition technology, this technical solution has the following advantages, as shown in Table 1.

[0087] Table 1 Comparison of the use effects of the present utility model and the traditional phosphoric acid decomposition method for sample preparation

[0088] Serial number Item Before improvement The present utility model 1 Phosphoric acid addition time 2 min / piece 10 s / piece 2 Possibility of phosphoric acid residue on PTFE sample bottle gasket Possible 0 3 Lint - free paper for wiping phosphoric acid Needed Not needed 4 Possibility of injection needle blockage due to phosphoric acid Possible 0 5 Possibility of introducing air and affecting test data Possibility 0 6 Possibility of phosphoric acid being added to the sample bottle wall Possibility 0

[0089] Compared with the method equipped with a fully automatic carbonate preparation device, it greatly saves the equipment purchase cost and avoids the failures and problems caused by the components of the fully automatic carbonate preparation device, as detailed in Table 2.

[0090] Table 2 Comparison of the use effects of the present utility model and the fully automatic carbonate preparation device

[0091] Serial number Item Before improvement The present utility model 1 Cost (equipment and device purchase cost) About 700,000 yuan 100 yuan 2 Phosphoric acid addition time (98 pieces) 98 min 10 min 3 Sealing washer failure Possible 0 4 Turntable position deviation Possible 0 5 Easy residue in acid valve chamber Possible 0 6 Failure caused by deformation of rubber acid pipe Possible 0 7 Potentiometer of gas sample storage device Possible 0

[0092] As described above, the above are only the specific embodiments of the present utility model, but the protection scope of the present utility model is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present utility model, any modifications, equivalent replacements, and improvements made within the spirit and principle of the present utility model shall be covered by the protection scope of the present utility model.

Claims

1. A novel carbonate C and O isotope analysis device using GasBench, characterized in that: include: PP container, rubber band, baffle, support parts, sample tube, sample rack, electromagnet; A rubber band is arranged in the PP material container; a baffle is arranged at the bottom of the PP material container; a supporting component is arranged at the bottom of the baffle; a PP material container is arranged in the sample tube; a PP material container is arranged in the sample rack; an electromagnet is fixed at the bottom of the sample rack by screws.

2. The novel carbonate C and O isotope analysis device using GasBench as claimed in claim 1, characterized in that: A PP material container is arranged in the sample tube.

3. The novel carbonate C and O isotope analysis device using GasBench as claimed in claim 1, characterized in that: A PP material container is arranged in the sample rack.

4. The novel carbonate C and O isotope analysis device using GasBench as claimed in claim 1, characterized in that: An electromagnet is fixed on the bottom of the sample rack by screws.

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