Standard value transfer quality control method and system for ozone-depleting substances and fluorine-containing greenhouse gases
Patent Information
- Application Number
- CN202611069827.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-17
- Publication Date
- 2026-10-09
AI Technical Summary
在现有技术中，上级标准气体（如J-255）随使用逐渐消耗，而观测网络和站点数量持续扩大，原有体系标准气体供给能力无法满足增长需求
[0014]根据本发明所涉及的臭氧层消耗物质与含氟温室气体的标准量值传递质控方法及系统，因为包括：步骤S1，以环境空气为底气，在标气罐中制备浓度为北半球本底浓度的二级标准气体，并为每瓶二级标准气体分配唯一识别码（ID），录入制备日期及初始浓度定值；步骤S2，每间隔第一预定周期将每瓶二级标准气体两两互比一次，采用交替进样序列，每间隔第二预定周期将二级标准气体与三级标准气体进行一次国际比对；步骤S3，基于二级标准气体的互比结果计算各成分的相对标准偏差或浓度偏差，当超出预设阈值时判定为漂移，对漂移成分进行量化校正，当二级标准气体压强低于第一压强阈值时移除二级标准气体；步骤S4，以二级标准气体为基准对三级标准气体进行多轮标定，结合初始标定值-站点使用值-返标值三段数据进行漂移判断，采用线性校正因子或返标值对三级标准气体浓度进行回溯校正；步骤S5，以三级标准气体为基准对四级标准气体每周标定一次，以标定浓度均值作为四级标准气体最终浓度值，依据四级标准气体最终浓度值的变化判断漂移并决定四级标准气体的更换时机，所以，本发明的臭氧层消耗物质与含氟温室气体的标准量值传递质控方法及系统建立了从二级到四级标气的完整传递、定期互校、漂移检测与数据校正机制，并通过计算机系统进行数据存储，实现全流程的自动化漂移判断、计算与校正，显著提升了量值传递的精度、效率和可靠性。
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Figure CN122882685A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of atmospheric environmental monitoring and standard gas measurement technology, specifically to a method and system for quality control of standard value transfer of ozone-depleting substances and fluorinated greenhouse gases. Background Technology
[0002] In atmospheric observations of ozone-depleting substances (ODS) and halogenated greenhouse gases, standard value transfer is a crucial step in ensuring data accuracy, comparability, and traceability. The current mainstream technical approach is led by the internationally authoritative observation organization AGAGE (Advanced Global Atmospheric Gases Experiment). AGAGE provides calibrated tertiary standard gases (such as J-255) to institutions with calibration capabilities. These institutions use high-precision analytical instruments (such as ODS5Pro) to generate quaternary standard gases based on these tertiary standard gases, which are then distributed to various observation stations (such as Xichong Station and Dongtan Station). Each station uses the quaternary standard gas as its working standard gas to measure ODS and halogenated greenhouse gases in ambient air. However, in current technologies, the primary standard gas (such as J-255) is gradually consumed, while the observation network and the number of stations continue to expand, making the existing standard gas supply capacity unable to meet the growing demand. The entire system is highly dependent on the standard gases provided by AGAGE, lacking independent higher-level standard gas benchmarks, resulting in insufficient long-term scalability and independent controllability. The transfer chain is singular and lacks systematic comparison: the downward transfer process of standard gases lacks systematic two-way comparison and drift (changes in the component concentration of standard gases over time during storage or use) quantitative correction mechanisms, especially for the long-term stability cross-calibration of secondary standard gas sequences and the drift backtracking correction of tertiary / quaternary standard gases during use. Summary of the Invention
[0003] This invention was made to solve the above-mentioned problems, and its purpose is to provide a method and system for quality control of standard value transfer of ozone-depleting substances and fluorinated greenhouse gases.
[0004] This invention provides a quality control method for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases, characterized by the following steps: Step S1, using ambient air as the base gas, preparing secondary standard gases at the Northern Hemisphere background concentration in standard gas cylinders, assigning a unique identification code to each secondary standard gas cylinder, and recording the preparation date and initial concentration value; Step S2, comparing each secondary standard gas cylinder pairwise at a first predetermined interval using an alternating injection sequence, and performing an international comparison between the secondary standard gases and tertiary standard gases at a second predetermined interval; Step S3, calculating the relative standard deviation or concentration deviation of each component based on the comparison results of the secondary standard gases. When the pressure exceeds the preset threshold, it is determined to be drift. The drift component is quantitatively corrected. When the pressure of the secondary standard gas is lower than the first pressure threshold, the secondary standard gas is removed. Step S4: The tertiary standard gas is calibrated multiple times based on the secondary standard gas. The drift is judged by combining the three segments of data: initial calibration value, station usage value, and return calibration value. The concentration of the tertiary standard gas is retrospectively corrected by using a linear correction factor or return calibration value. Step S5: The quaternary standard gas is calibrated once a week based on the tertiary standard gas. The average calibrated concentration is used as the final concentration value of the quaternary standard gas. The drift is judged based on the change of the final concentration value of the quaternary standard gas, and the timing of replacing the quaternary standard gas is determined.
[0005] The standard value transfer quality control method for ozone-depleting substances and fluorine-containing greenhouse gases provided by the present invention may also have the following features: wherein the first predetermined period is half a year and the second predetermined period is one year; in the comparison of secondary standard gases, each bottle of secondary standard gas is used as a sample gas and injected six times; multi-round calibration refers to three rounds of calibration, with six injections in each round of calibration.
[0006] The standard value transfer quality control method for ozone-depleting substances and fluorine-containing greenhouse gases provided by the present invention may also have the following feature: wherein the first pressure threshold is 40% to 60% of the initial pressure of the secondary standard gas.
[0007] The standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases provided by this invention may also have the following features: the initial calibration value is the result of the first calibration using the secondary standard gas, the site usage value is the result of comparing the tertiary standard gas with the original tertiary standard gas, and the recalibration value is the recalibration result of the tertiary standard gas returning to the central laboratory for 1-2 rounds of recalibration.
[0008] The standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases provided by the present invention may also have the following feature: when the pressure of the tertiary standard gas is lower than the recalibration threshold, recalibration is performed, and the recalibration threshold is 100 psi.
[0009] The standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases provided by this invention may also have the following feature: the drift judgment and correction algorithm may be one or more combinations of linear regression trend analysis, three-point comparison method, and exponential smoothing method.
[0010] The standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases provided by this invention may also have the following characteristics: the preparation frequency of secondary standard gas is 1 to 2 bottles per year, and the international comparison object is a tertiary standard gas traceable to the AGAGE network.
[0011] This invention provides a quality control system for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases, used to implement the quality control method for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases as described above. It features the following components: a standard gas management database module for storing metadata and concentration data of secondary, tertiary, and quaternary standard gases, and establishing transfer relationships between standard gases at each level; an input and update module for automatically or manually inputting and updating the concentration values and preparation / calibration metadata of standard gases at each level; and a core algorithm and judgment module for internally configuring secondary, tertiary, and quaternary standard gases respectively... The corresponding drift judgment and correction algorithm is configured as follows: for secondary standard gases, drift judgment and removal are performed based on the cross-comparison results; for tertiary standard gases, drift judgment is performed by combining the three segments of data: initial calibration value, site usage value, and return calibration value, and the concentration of tertiary standard gases is retrospectively corrected using a linear correction factor or return calibration value; for quaternary standard gases, correction is performed based on the linear drift slope criterion; the user interaction and alarm module is used to differentiate and alarm the drift components and correction results identified in the drift judgment, and to provide a manual operation interface for operators to modify the standard gas setpoints based on the actual situation, and the manual modification records are automatically stored in the standard gas management database module.
[0012] The standard value transfer quality control system for ozone-depleting substances and fluorinated greenhouse gases provided by this invention may also have the following feature: in the core algorithm and judgment module, when calibrating secondary or tertiary standard gases, the concentration values of their associated lower-level standard gases are simultaneously and automatically corrected.
[0013] The role and effect of invention
[0014] The standard value transfer quality control method and system for ozone-depleting substances and fluorinated greenhouse gases according to the present invention includes: Step S1, using ambient air as the base gas, preparing a secondary standard gas with a concentration equal to the background concentration in the Northern Hemisphere in a standard gas cylinder, assigning a unique identification code (ID) to each secondary standard gas cylinder, and recording the preparation date and initial concentration value; Step S2, comparing each secondary standard gas cylinder pairwise once every first predetermined period using an alternating injection sequence, and performing an international comparison between the secondary standard gas and a tertiary standard gas every second predetermined period; Step S3, calculating the relative standard deviation or concentration deviation of each component based on the comparison results of the secondary standard gases, determining drift when it exceeds a preset threshold, quantifying and correcting the drifted components, and removing the secondary standard gas when the pressure of the secondary standard gas is lower than a first pressure threshold; Step S4, using the secondary standard gas as the base gas... The standard gas is used as a reference to perform multiple rounds of calibration on the third-level standard gas. Drift judgment is made by combining three segments of data: initial calibration value, station usage value, and return calibration value. The concentration of the third-level standard gas is retrospectively corrected using a linear correction factor or return calibration value. In step S5, the fourth-level standard gas is calibrated once a week using the third-level standard gas as a reference. The average calibrated concentration is used as the final concentration value of the fourth-level standard gas. Drift is judged based on the change of the final concentration value of the fourth-level standard gas, and the timing of replacement of the fourth-level standard gas is determined. Therefore, the standard value transfer quality control method and system of the present invention for ozone-depleting substances and fluorinated greenhouse gases establishes a complete transfer, periodic mutual calibration, drift detection and data correction mechanism from the second-level to the fourth-level standard gas. Data is stored through a computer system to realize the automated drift judgment, calculation and correction of the whole process, which significantly improves the accuracy, efficiency and reliability of value transfer. Attached Figure Description
[0015] Figure 1 This is a schematic flowchart of the standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0016] Figure 2 This is an operational flowchart of the standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0017] Figure 3 This is a schematic diagram of the module of the standard value transfer quality control system for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0018] Figure 4 This is a schematic diagram of the module working principle of the standard value transfer quality control system for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention. Detailed Implementation
[0019] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication between two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.
[0020] To make the technical means, creative features, objectives and effects of this invention easy to understand, the following embodiments, in conjunction with the accompanying drawings, specifically illustrate the standard value transfer quality control method and system for ozone-depleting substances and fluorinated greenhouse gases of this invention.
[0021] Example
[0022] Figure 1 This is a schematic flowchart of the standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0023] like Figure 1 As shown, this embodiment provides a quality control method for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases, including:
[0024] Step S1: Using ambient air as the base gas, prepare a secondary standard gas with a concentration equal to the background concentration in the Northern Hemisphere in a standard gas cylinder, assign a unique identification code (ID) to each secondary standard gas cylinder, and record the preparation date and initial concentration value.
[0025] Step S2: Each bottle of secondary standard gas is compared pairwise once every first predetermined period using an alternating injection sequence. Each second predetermined period, the secondary standard gas is compared internationally with the tertiary standard gas.
[0026] The secondary standard gas is prepared at a frequency of 1-2 bottles per year, and the international comparison object is the tertiary standard gas that can be traced back to the AGAGE network.
[0027] Step S3: Calculate the relative standard deviation or concentration deviation of each component based on the comparison results of the secondary standard gas. If the deviation exceeds the preset threshold, it is determined to be a drift. Quantitative correction is performed on the drifting component. When the pressure of the secondary standard gas is lower than the first pressure threshold, the secondary standard gas is removed.
[0028] The first pressure threshold is 40% to 60% of the initial pressure of the secondary standard gas.
[0029] Step S4: Using the secondary standard gas as a reference, perform multiple rounds of calibration on the tertiary standard gas. Combine the three data segments of initial calibration value, station usage value, and return calibration value to determine drift. Use a linear correction factor or return calibration value to retrospectively correct the concentration of the tertiary standard gas.
[0030] Among them, the initial calibration value is the result of the first calibration using the secondary standard gas, the site usage value is the result of the comparison between the tertiary standard gas and the original tertiary standard gas, and the recalibration value is the recalibration result of the tertiary standard gas returning to the central laboratory for 1-2 rounds of recalibration.
[0031] Recalibration is performed when the pressure of the third-level standard gas is lower than the recalibration threshold, which is 100 psi.
[0032] Step S5: Using the third-level standard gas as a reference, the fourth-level standard gas is calibrated once a week. The average calibrated concentration is used as the final concentration value of the fourth-level standard gas. The drift is judged based on the change of the final concentration value of the fourth-level standard gas, and the timing of replacing the fourth-level standard gas is determined.
[0033] In this embodiment, the first predetermined period is six months and the second predetermined period is one year; in the comparison of secondary standard gases, each bottle of secondary standard gas is used as a sample gas and injected six times; multi-round calibration refers to three rounds of calibration, with six injections in each round of calibration.
[0034] The drift judgment and correction algorithm can be one or more combinations of linear regression trend analysis, three-point comparison method, and exponential smoothing method.
[0035] Figure 2 This is an operational flowchart of the standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0036] like Figure 2 As shown, the specific operation process is as follows:
[0037] Each year, 1-2 bottles of secondary standard gas are prepared using ambient air as the base gas in standard ODS standard gas cylinders, with a pressure of approximately 850 psi and a concentration consistent with the background concentration in the Northern Hemisphere. Metadata such as the unique identifier (ID), preparation date, and initial concentration of the newly prepared standard gas can be automatically / manually entered into the "Secondary Standard Gas Management Interface" of the Ozone Depleting Substances and Fluorine-Containing Greenhouse Gases Standard Value Transfer Quality Control System 100.
[0038] Subsequently, cross-comparisons and international comparisons were conducted, with all secondary standard gases being cross-compared every six months. Each pair of gases was mutually calibrated using an alternating injection sequence of "std-tank-std-tank-...", with each bottle used as a sample gas and injected six times. At least once a year, a comparison was made with tertiary standard gases traceable to AGAGE.
[0039] Based on the results of multiple cross-comparisons and existing built-in judgment algorithms (e.g., if the calculated relative standard deviation (RSD) or concentration deviation of a certain component exceeds a preset threshold, the standard gas is automatically marked as "suspected drift"), the drift amount of the drifting component is automatically calculated and corrected according to the drift correction formula, and the corresponding component is marked to remind the staff. If the drift does not conform to the norm and is difficult to correct, the drifting standard gas is removed from the secondary standard gas comparison library and specially marked.
[0040] When the pressure inside the ODS standard gas tank is lower than 40% to 60% of the initial pressure (set according to requirements), the Ozone Depleting Substances and Fluorine-Containing Greenhouse Gas Standard Value Transfer Quality Control System 100 automatically updates the status of the standard gas to "retired" and will no longer be included in subsequent comparison and transfer tasks.
[0041] The tertiary standard gas was then calibrated using the newly prepared secondary standard gas. Each bottle was calibrated three times, with six injections per round. The concentration was taken as the average of the three rounds, and the relative standard deviation of the three rounds' averages was used as the calibration accuracy. The results and accuracy of the initial calibration using the secondary standard gas were entered into the ozone-depleting substances and fluorinated greenhouse gases standard value transfer quality control system 100 and recorded as the "initial calibration value".
[0042] Before the Level 3 standard gas is delivered to the site, it is compared with the existing Level 3 standard gas to form a "site usage value." The comparison result and the site usage value are entered into the Ozone Depleting Substances and Fluorinated Greenhouse Gases Standard Value Transfer Quality Control System 100. Before the pressure falls below the recalibration threshold (100 psi), the gas is returned to the central laboratory for 1-2 rounds of recalibration (6 injections per round), and the recalibration results are entered into the system. Based on the recorded "initial calibration value - site usage value - recalibration value," and combined with the set criteria, the system automatically identifies drift and corrects it using the built-in correction method, while automatically indexing the derived Level 4 standard gas data.
[0043] Each site is calibrated weekly using a level-three standard gas. Four samples are injected per cycle, and the average value is taken as the result for that cycle. The long-term calibration average is the final value. Weekly calibration results are entered into the system. The system automatically determines whether there is drift based on changes in long-term, multiple results, and replaces and corrects the observation results as necessary, marking the changes accordingly.
[0044] For secondary standard gases, cross-comparison can be performed quarterly or annually. For tertiary standard gases, recalibration can be performed on every calibration attempt or only when calibration anomalies occur. The number of cross-comparison injections for secondary standard gases can be 4 or 8. The number of calibration rounds for tertiary standard gases can be 2 or 4, with 4-8 injections per round. The exit threshold for secondary standard gases can be 40%–60%. The recalibration threshold for tertiary standard gases can be 80 psi–100 psi.
[0045] Figure 3 This is a schematic diagram of the module of the standard value transfer quality control system for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0046] like Figure 3 As shown, this embodiment provides a standard value transfer quality control system 100 for ozone-depleting substances and fluorinated greenhouse gases, used to implement the standard value transfer quality control method for ozone-depleting substances and fluorinated greenhouse gases as described above, including: a standard gas management database module 1, an input and update module 2, a core algorithm and judgment module 3, and a user interaction and alarm module 4.
[0047] Standard gas management database module 1 is used to store metadata and concentration data of secondary, tertiary, and quaternary standard gases, and to establish the transfer relationship between standard gases at each level.
[0048] The input and update module 2 is used to automatically or manually input and update the concentration values and preparation / calibration metadata of standard gases at all levels.
[0049] The core algorithm and judgment module 3 is used to build drift judgment and correction algorithms for secondary, tertiary, and quaternary standard gases, respectively. It is configured to: perform drift judgment and removal for secondary standard gases based on cross-comparison results; perform drift judgment for tertiary standard gases by combining three segments of data: initial calibration value, station usage value, and return calibration value, and perform retrospective correction of the concentration of tertiary standard gases using a linear correction factor or return calibration value; and perform correction for quaternary standard gases based on the linear drift slope criterion.
[0050] In the core algorithm and judgment module 3, the concentration values of the associated lower-level standard gases are automatically corrected simultaneously during the calibration of secondary or tertiary standard gases.
[0051] User interaction and alarm module 4 is used to differentiate and alarm the drift components and correction results identified in the drift judgment, and provides a manual operation interface for operators to modify the standard gas setpoints based on the actual situation. The manual modification records are automatically stored in the standard gas management database module.
[0052] Figure 4 This is a schematic diagram of the module working principle of the standard value transfer quality control system for ozone-depleting substances and fluorinated greenhouse gases in an embodiment of the present invention.
[0053] like Figure 4As shown, the input and update module 2 automatically or manually writes the standard gas ID, concentration, pressure, and injection sequence results into the standard gas management database module 1 of the data layer. The core algorithm and judgment module 3, based on three built-in criteria and correction methods, distributes the computational tasks to three levels: RSD / deviation threshold judgment for secondary standard gases, initial-use-re-standard deviation judgment for tertiary standard gases, and long-term slope judgment for quaternary standard gases. The judgment and correction results at each level are synchronously updated to the standard gas management database module 1 of the data layer. The data layer uniformly stores the correlation network data, metadata, comparison values, and correction history of secondary / tertiary / quaternary standard gases, providing data reading support for the core algorithm module 3 and opening up data query and statistical capabilities to the user interaction and alarm module 4. The user interaction and alarm module 4 displays drift marker records through a visual interface and triggers alarm reminders. It also supports manual modification of entries. Manually modified records are automatically saved back to the standard gas management database module 1. Drift events and final correction results are also fed back to the criterion system of the core algorithm and judgment module 3, completing the iterative optimization of the entire chain.
[0054] The role and effect of the embodiments
[0055] The standard value transfer quality control method and system for ozone-depleting substances and fluorinated greenhouse gases according to the present invention includes: Step S1, using ambient air as the base gas, preparing a secondary standard gas with a concentration equal to the background concentration in the Northern Hemisphere in a standard gas cylinder, assigning a unique identification code (ID) to each secondary standard gas cylinder, and recording the preparation date and initial concentration value; Step S2, comparing each secondary standard gas cylinder pairwise once every first predetermined period using an alternating injection sequence, and performing an international comparison between the secondary standard gas and a tertiary standard gas every second predetermined period; Step S3, calculating the relative standard deviation or concentration deviation of each component based on the comparison results of the secondary standard gases, determining drift when it exceeds a preset threshold, quantifying and correcting the drifted components, and removing the secondary standard gas when the pressure of the secondary standard gas is lower than a first pressure threshold; Step S4, using the secondary standard gas as the base gas... The standard gas is used as a reference to perform multiple rounds of calibration on the third-level standard gas. Drift judgment is made by combining three segments of data: initial calibration value, station usage value, and return calibration value. The concentration of the third-level standard gas is retrospectively corrected using a linear correction factor or return calibration value. In step S5, the fourth-level standard gas is calibrated once a week using the third-level standard gas as a reference. The average calibrated concentration is used as the final concentration value of the fourth-level standard gas. Drift is judged based on the change of the final concentration value of the fourth-level standard gas, and the timing of replacement of the fourth-level standard gas is determined. Therefore, the standard value transfer quality control method and system of the present invention for ozone-depleting substances and fluorinated greenhouse gases establishes a complete transfer, periodic mutual calibration, drift detection and data correction mechanism from the second-level to the fourth-level standard gas. Data is stored through a computer system to realize the automated drift judgment, calculation and correction of the whole process, which significantly improves the accuracy, efficiency and reliability of value transfer.
[0056] This embodiment also enables the independent and continuous provision of working standard gas for the ever-expanding observation network by independently preparing secondary standard gas.
[0057] This embodiment also periodically compares the secondary standard gas with the internationally authoritative tertiary standard gas to ensure that the data is traceable to international benchmarks.
[0058] Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.
Claims
1. A quality control method for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases, characterized in that, include: Step S1: Using ambient air as the base gas, prepare a secondary standard gas with a concentration equal to the background concentration in the Northern Hemisphere in a standard gas cylinder, assign a unique identification code to each bottle of the secondary standard gas, and record the preparation date and initial concentration value. Step S2: Each bottle of the secondary standard gas is compared pairwise once every first predetermined period using an alternating injection sequence; and the secondary standard gas is compared internationally with the tertiary standard gas once every second predetermined period. Step S3: Calculate the relative standard deviation or concentration deviation of each component based on the comparison results of the secondary standard gas. When the deviation exceeds a preset threshold, it is determined to be a drift. Quantitative correction is performed on the drifting component. When the pressure of the secondary standard gas is lower than the first pressure threshold, the secondary standard gas is removed. Step S4: Using the secondary standard gas as a reference, the tertiary standard gas is calibrated in multiple rounds. The drift is judged by combining the three segments of data: initial calibration value, station usage value, and return calibration value. The concentration of the tertiary standard gas is retrospectively corrected by using a linear correction factor or the return calibration value. Step S5: Using the third-level standard gas as a reference, the fourth-level standard gas is calibrated once a week. The average calibrated concentration is used as the final concentration value of the fourth-level standard gas. The drift is judged based on the change of the final concentration value of the fourth-level standard gas, and the timing of replacing the fourth-level standard gas is determined.
2. The method for quality control of standard value transfer of ozone-depleting substances and fluorine-containing greenhouse gases according to claim 1, characterized in that: in, The first predetermined period is six months, and the second predetermined period is one year; in the comparison of the secondary standard gases, each bottle of the secondary standard gas is used as a sample gas and injected six times; the multi-round calibration refers to three rounds of calibration, with six injections in each round of calibration.
3. The method for quality control of standard value transfer of ozone-depleting substances and fluorine-containing greenhouse gases according to claim 1, characterized in that: in, The first pressure threshold is 40% to 60% of the initial pressure of the secondary standard gas.
4. The method for quality control of standard value transfer of ozone-depleting substances and fluorinated greenhouse gases according to claim 1, characterized in that: in, The initial calibration value is the result of the first calibration using the secondary standard gas; the station usage value is the result of comparing the tertiary standard gas with the original tertiary standard gas; and the recalibration value is the recalibration result of the tertiary standard gas returning to the central laboratory for 1-2 rounds of recalibration.
5. The method for quality control of standard value transfer of ozone-depleting substances and fluorinated greenhouse gases according to claim 4, characterized in that: in, Recalibration is performed when the pressure of the third-level standard gas is lower than the recalibration threshold, which is 100 psi.
6. The method for quality control of standard value transfer of ozone-depleting substances and fluorine-containing greenhouse gases according to claim 1, characterized in that: in, The drift judgment and correction algorithm can be one or more combinations of linear regression trend analysis, three-point comparison method, and exponential smoothing method.
7. The method for quality control of standard value transfer of ozone-depleting substances and fluorine-containing greenhouse gases according to claim 1, characterized in that: in, The secondary standard gas is prepared at a frequency of 1 to 2 bottles per year, and the international comparison object is a tertiary standard gas traceable to the AGAGE network.
8. A quality control system for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases, used to implement the quality control method for the transfer of standard values of ozone-depleting substances and fluorinated greenhouse gases as described in claims 1-7, characterized in that, include: The standard gas management database module is used to store metadata and concentration data of the secondary standard gas, the tertiary standard gas, and the quaternary standard gas, and to establish the transfer relationship between the standard gases at each level; The input and update module is used to automatically or manually input and update the concentration values and preparation / calibration metadata of standard gases at all levels; The core algorithm and judgment module, which incorporates drift judgment and correction algorithms for the secondary, tertiary, and quaternary standard gases respectively, is configured to: determine and remove drift for the secondary standard gas based on cross-comparison results; determine drift for the tertiary standard gas by combining three segments of data: initial calibration value, station usage value, and return calibration value, and perform retrospective correction on the concentration of the tertiary standard gas using a linear correction factor or return calibration value; and correct the quaternary standard gas based on a linear drift slope criterion. The user interaction and alarm module is used to differentiate and alarm the drift components and correction results identified in the drift judgment, and provides a manual operation interface for operators to modify the standard gas setpoints based on the actual situation. The manual modification records are automatically stored in the standard gas management database module.
9. The standard value transfer quality control system for ozone-depleting substances and fluorinated greenhouse gases according to claim 8, characterized in that: in, In the core algorithm and judgment module, during the calibration of the secondary standard gas or the tertiary standard gas, the concentration value of its associated lower-level standard gas is automatically and synchronously calibrated.