Method and system for detecting the presence of a headspace vial

Abstract

Disclosed herein are methods and systems for detecting the presence of a headspace vial. In one embodiment, the system includes a sample probe, a fluid source in fluid communication with the sample probe, one or more pressure and flow sensors in fluid communication with the sample probe, and a processor. The processor is configured to (a) receive a first set of signals from one or more of the pressure and flow sensors and perform a draining process to remove the sample vial from the sample probe, receive a second set of signals from the one or more pressure and flow sensors during step (b), (d) detect whether the draining process is successful from the first and second sets of signals, and (e) initiate one or more actions selected from the group consisting of repairs and warnings in response to the detecting step.

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims the benefit of U.S. Patent Application No. 63 / 021,822, filed on May 8, 2020. The entire disclosure of this U.S. patent application is incorporated herein by reference and made a part hereof.

Background Art

[0002] In headspace gas chromatography, typically, first the contents of a sample vial are heated, then pressurized, and subsequently, the volatile contents are sampled. After sampling is complete, the vial is ejected or removed from the sample probe. However, the removal of the sample vial from the sample probe may not be successful, which may damage the gas chromatography system and the sample vial, etc.

[0003] Furthermore, after sampling, the vial is cooled back to its original room temperature. The contents of the vial may still be under pressure or may be partially in a vacuum. Depending on the contents of the vial, the vial may break and pose a danger.

Summary of the Invention

Problems to be Solved by the Invention

[0004] This specification discloses a method and system for sensing the presence of a headspace vial.

Means for Solving the Problems

[0005] In one aspect, a gas chromatography system can include a sample probe, a fluid source in fluid communication with the sample probe, a pressure sensor in fluid communication with the sample probe, and a processor. The processor (a) Performing a discharge process to remove a sample vial from a sample probe; (b) Receiving a set of signals from a pressure sensor; (c) Detecting whether the discharge process is successful from the set of signals; (d) Initiating one or more operations selected from the group consisting of repair and warning in response to the detection step configured to perform.

[0006] This aspect can include various embodiments. In one embodiment, the processor is further configured to determine a change in value within the set of signals in step (c) and determine from the change in value that the sample vial has been removed from the sample probe.

[0007] In another embodiment, the repair can further include ending the chromatography function when the processor detects that the discharge process has failed.

[0008] In another embodiment, reading the pressure value of the set of signals during step (a) can measure whether it is below a predetermined threshold, within a range of the predetermined threshold, or has reached atmospheric pressure when the discharge process is successful, and the predetermined threshold is determined by the processor from the vial volume, solvent composition, headspace composition, pressurized gas composition, flow path restriction, measured value of the flow rate or pressure of the test vial, or a combination thereof.

[0009] In another embodiment, the processor is further configured to determine in step (c) that no change in value has occurred within the set of signals and determine from the set of signals whether the removal of the sample vial from the sample probe has failed, whether the sample probe has become immobile within the septum of the sample vial, or whether the sample probe is clogged.

[0010] In another embodiment, the processor, in step (e), is further configured to control the vial actuator to bias the sample vial towards the sample probe or control the vial rack to bias in response to a determination that the discharge process has failed, and the biasing occurs in response to a determination that the discharge process has failed.

[0011] In another aspect, a gas chromatography system can include a sample probe, a fluid source in fluid communication with the sample probe, a pressure sensor in fluid communication with the sample probe, and a processor, the processor being configured to: (a) perform a discharge process to remove a sample vial from the sample probe; (b) flow fluid through the fluid source to the sample probe during step (a); (c) receive a set of signals from the pressure sensor during step (b); (d) detect from the set of signals whether the discharge process has been successful; and (e) initiate one or more operations selected from the group consisting of repair and warning in response to the detection step.

[0012] This aspect can include various embodiments. In one embodiment, the gas chromatography system can further include a flow sensor in fluid communication with the sample probe, and a portion of the set of signals is received from the flow sensor.

[0013] In another embodiment, the processor, in step (d), is further configured to determine a change in value within the set of signals and determine from the change in value that the sample vial has been removed from the sample probe.

[0014] In another embodiment, the processor, in step (d), is further configured to determine a rate of change within the set of signals, determine that the rate of change is less than a predetermined threshold, and determine that the discharge process has been successful.

[0015] In another embodiment, in step (d), the processor further determines a rate of change within a set of signals, determines whether the rate of change exceeds a predetermined threshold or is within a range of the predetermined threshold, and is configured to determine from the set of signals that the removal of the sample probe from the sample vial has failed.

[0016] In another embodiment, in step (d), the processor further determines a rate of change within a set of signals, determines that the rate of change exceeds a predetermined threshold, and is configured to determine from the set of signals that the sample probe is stuck within the septum of the sample vial or that the sample probe is clogged. Optionally, the processor can further determine the predetermined threshold from the composition of the fluid source, the composition of the sample in the sample vial, the volume of the sample vial, the measured value of the flow rate or pressure of the test vial, or a combination thereof.

[0017] In another embodiment, in step (e), the processor is further configured to control the vial actuator to bias the sample vial towards the sample probe or to control the vial rack to bias in response to a determination that the discharge process has failed, and the biasing occurs in response to a determination that the discharge process has failed.

[0018] In another embodiment, the gas chromatography system can further include a heater that thermally conducts with the sample vial, the heater is configured to generate a state in which the sample vial is heated, the processor further receives a first set of signals from the pressure sensor, determines an initial pressure of the sample vial in the heated state from the first set of signals, performs an extraction process on the contents of the sample vial, receives a second set of signals from the pressure sensor after the extraction process, determines a second pressure of the sample vial, and is configured to control a fluid source or an outlet in fluid communication with the sample vial to return the second pressure of the sample vial to the initial pressure.

[0019] In yet another aspect, a gas chromatography system can include a sample probe, a fluid source in fluid communication with the sample probe, a flow sensor in fluid communication with the sample probe, and a processor. The processor is configured to: (a) perform an ejection process to remove a sample vial from the sample probe; (b) receive a set of signals from the flow sensor; (c) detect from the set of signals whether the ejection process was successful; and (d) initiate one or more actions selected from the group consisting of repair and warning in response to the detection step.

[0020] This aspect can include various embodiments. In one embodiment, the processor is further configured in step (c) to determine a change in value within the set of signals and, from the change in value, determine that the sample vial has been removed from the sample probe.

[0021] In another embodiment, the system attempts to maintain a constant pressure level within the sample probe between step (a) and step (b).

[0022] In another embodiment, repair can further include the processor terminating the chromatography function if it detects that the ejection process has failed.

[0023] In another embodiment, the processor is further configured in step (c) to determine that no change in value has occurred within the set of signals and, from the set of signals, determine whether removal of the sample vial from the sample probe has failed, whether the sample probe has become stuck within the septum of the sample vial, or whether the sample probe is clogged.

[0024] In another embodiment, in step (e), the processor is further configured to control the vial actuator to urge the sample vial towards the sample probe or to control the vial rack to urge in response to a determination that the discharge process has failed, and the urging occurs in response to a determination that the discharge process has failed.

[0025] In yet another aspect, a gas chromatography system can include a sample probe, a fluid source in fluid communication with the sample probe, a flow sensor in fluid communication with the sample probe, and a processor, and the processor is configured to: (a) perform a discharge process to remove a sample vial from the sample probe; (b) flow fluid through the fluid source to the sample probe; (c) receive a set of signals from the flow sensor during step (b); (d) detect from the set of signals whether the discharge process has been successful; and (e) initiate one or more operations selected from the group consisting of repair and warning in response to the detection step.

[0026] This aspect can include various embodiments. In one embodiment, the gas chromatography system can further include a pressure sensor in fluid communication with the sample probe, and a portion of the set of signals is received from the pressure sensor.

[0027] In another embodiment, in step (e), the processor is further configured to control the vial actuator to urge the sample vial towards the sample probe or to control the vial rack to urge in response to a determination that the discharge process has failed, and the urging occurs in response to a determination that the discharge process has failed. BRIEF DESCRIPTION OF THE DRAWINGS

[0028]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Embodiments for Carrying Out the Invention

[0029] To more fully understand the nature and desired objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings. In each of the drawings, like reference numerals indicate corresponding parts.

[0030] [Definitions] The present invention is most clearly understood by reference to the following definitions.

[0031] In this specification, the singular forms also include the plural forms unless the context clearly dictates otherwise.

[0032] Unless otherwise specified or apparent from the context, the term "about" as used in this specification is understood to be within the normal acceptable range in the relevant technical field, for example within two standard deviations of the average value. "About" can be understood to be within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise apparent from the context, all numerical values described in this specification are to be considered as being preceded by the term "about".

[0033] The terms "composed of", "consisting of", "including", "having", etc. used in this specification and the claims may have meanings according to the interpretations of the terms "comprises", "comprising", "containing", "having", etc. under the US Patent Law, and may mean "including".

[0034] Unless otherwise specified or apparent from the context, the term "or" as used in this specification is understood to have an inclusive meaning.

[0035] The term "set" used in this specification and the claims may include one or more things therein.

[0036] The scope shown in the specification of this application is understood to represent all values within that scope. For example, the range of 1 to 50 is understood to include any number, combination of numbers, or sub-range from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 (including fractions thereof, except where clearly defined from the context).

[0037] [Gas Chromatography System] The method described in the specification of this application can be implemented by a gas chromatography system, and the system described in the specification of this application can be part of a gas chromatography system. Figure 1 shows an exemplary gas chromatography system. A gas chromatography system can inject, vaporize, separate, and detect the components of a sample. The flow of fluid through this system is depicted by a single-line arrow such as arrow 175. However, those skilled in the art will understand that the invention described in the specification of this application is not limited to the specific embodiments of the gas chromatography system depicted in Figure 1, nor to the embodiments of the specific components described in Figures 2 to 8, and that the invention described in the specification of this application can be implemented by various gas chromatography systems and various system designs. For example, a gas chromatography system can include one or more samplers, injection ports, columns, detectors, valves, gas control devices, and heaters, etc.

[0038] [Sample Source] The headspace sample source 105 can include any sample composed of volatile components that partially vaporize and establish an equilibrium with the less volatile ambient environment. Based on typical temperatures involved in the analysis of headspace samples, a significant number of chemical analytes can be utilized as the sample source 105. In some cases, the sample source 105 can be stored in a vial or container, etc. before extraction of the source. The vial or container can be sealed (substantially airtight) by pressing a septum against the container using a cap, or can be sealed substantially airtight using other methods. The headspace sampler 120 receives the sample source 105 and establishes an equilibrium between the volatile portion of the sample contained within the sample source 105 and the less volatile components within the sample source 105. The seal of the sample source 105 in the equilibrium state can be pierced by a syringe, needle, or other sample probe to create a conduit for transferring an aliquot of the volatile portion of the headspace within the sample source 105 to the gas chromatograph 180. In the gas chromatograph 180, the aliquot is separated into its individual components for identification and / or quantification (i.e., fixation or quantification or both).

[0039] The headspace sampler 120 can optionally include an apparatus for retrieving stored samples and positioning samples withdrawn from a container. By way of example, FIG. 6 depicts a vial sampling mechanism for a sample including a rack 605 for positioning a sample vial 610 adjacent to a sample probe 615. In this example, the rack 605 is a circular carousel that operates (activates) in a rotational and orthogonal direction with respect to the length of the probe 615. However, one of ordinary skill in the art will understand that other forms of retrieving and / or positioning (i.e., retrieving or positioning or both) a sample vial for sample extraction, such as a linear rack or other robotic system for handling vials, can be implemented within the scope of this system. Further, the rack 605 can include a set of cartridges, each of which can hold a sample vial.

[0040] The headspace sampler 120 can also include a heating element (e.g., a resistive (ohmic or joule) heater) for controlling the temperature of the sample before and / or during extraction (i.e., before or during extraction or both). For example, the entire rack 605 can be housed within a heated area. In headspace gas chromatography analysis, the sample probe can extract a sample through the headspace of a vial containing the sample. Optionally, a headspace for sampling can be generated by increasing the temperature of a liquid or solid sample within the sample vial. The heating element can do this by increasing the temperature of the sample source 105. In other cases, the sample can be present in the gas phase at room temperature, so heating of the sample vial may not be necessary. Normal temperatures range from ambient temperature to 300° C.

[0041] To extract a sample from a sample vial for analysis and, as part of the extraction process, the carousel 605 can be rotated until the sample vial 610 is positioned alongside the sample probe 615. Next, the actuator 620 can operate towards the sample probe 615. In some cases, the actuator 620 can include a lifter rod having a predetermined length, and the longitudinal direction of the lifter rod is parallel to the longitudinal direction of the sample probe 615. However, those skilled in the art will understand that other types of actuators can be used that operate towards and / or away from the sample probe (i.e., towards or away from the sample probe or both). When the actuator 620 operates towards the sample probe 615, the actuator 620 can pass through the cavity at the bottom of the cartridge holding the sample vial 610 and force the sample vial 610 towards the sample probe 615. The sample probe 615 can penetrate the upper part of the sample vial 610 (e.g., pass through the septum of the vial 610), allowing the sample probe 615 to access the contents contained in the sample vial 610. Note that this is only one embodiment of a mechanism for accessing the contents contained in a sample vial with a sample probe. This operation can be performed with additional mechanisms including various combinations such as a motor, a motion converting device, etc. Further, instead of moving the sample vial and keeping the sample probe stationary, the relative motion between the sample probe and the sample vial can be generated by moving both the sample vial and the sample probe or by moving the sample probe while keeping the sample vial stationary.

[0042] The headspace sampler 120 can include a series of flow paths connected to the gas source 110 and the gas chromatograph 180. The flow paths provide a fluid communication path for extracting a certain amount of sample from the sample source and transferring the extracted sample to the gas chromatograph for analysis. Further, a proportional valve, a switching valve, and / or a 6-port valve (i.e., a proportional valve, a switching valve, or a 6-port valve or all of them) can be used to control which flow path is connected at any given time. An exemplary headspace sampler flow path is depicted in FIG. 2.

[0043] The embodiment of the headspace sampler flow path illustrated in FIG. 2 can include various inlet / outlet paths. For example, the headspace sampler can include a flow path connected to the outlet 205, a flow path connected to the vial pressurized gas source 210, a flow path connected to the carrier gas source 215, a flow path connected to the transfer line 220, and a flow path connected to the sample probe 225. The vial pressurized gas source 210 and the carrier gas source 215 may be part of the gas source 110 of FIG. 1. One or more of these flow paths may include a sample loop such as the sample loop 230. Alternatively, instead of or in addition to the sample loop, a sample trap may be provided.

[0044] Various sensors and valves can be incorporated into the flow paths of the headspace sampler. The incorporated sensors and valves can assist in the control and management of the flow within the headspace sampler. For example, sensors and valves (not shown) can control the flow of carrier gas to the carrier gas source 215. A flow rate sensor 240, a pressure sensor 245, and a proportional valve (PV1) 250 can be connected to the flow path connected to the vial pressurized gas source 210. Various types of flow rate sensors 240 including a thermal mass flow rate sensor can be used.

[0045] Furthermore, switching valve 255 can connect the flow path connected to vial pressurization source 210 to six-port valve 265. Proportional valve (PV2) 260 can connect the flow path connected to outlet 205 to six-port valve 265 and / or vial pressurized gas source 210 (i.e., six-port valve 265 or vial pressurized gas source 210 or both of them). With these valves and the valves described above, and further with the six-port valve, the introduction and extraction of various gases into the headspace sampler can be controlled.

[0046] One or more components of the flow path, such as sample probe 225, six-port valve 265, sample loop 230, and / or transfer line 220 (i.e., sample probe 225, six-port valve 265 or sample probe 230 or all of them) may be heated. The normal temperature range is from ambient temperature to 300°C.

[0047] The headspace sampler can, in some cases, pressurize the sample vial before extracting the sample. The normal pressure ranges from ambient pressure to 75 psig (517 kPa). The vial pressurization flow path is illustrated in FIG. 3. During the pressurization stage, the six-port valve and each valve depicted in FIG. 2 can be oriented to connect the sample probe to vial pressurized gas source 210. Pressurized gas can flow into the flow path (e.g., through sample loop 310 and six-port valve 315) and into the sample vial through sample probe 320. This gas flow can increase the pressure of the sample vial and the connected flow path. Representative gases used to pressurize the vial include helium and nitrogen. Furthermore, the carrier gas can flow into the gas chromatograph through the flow path connected to transfer line 305.

[0048] Then, the headspace sampler 120 can implement a sample loop filling flow path, an example of which is depicted in FIG. 4. The 6-port valve 415 can be oriented to connect the sample probe 420 to the outlet, and can be set to a pressure lower than that of the vial (e.g., atmospheric pressure). By exhausting the sample probe, the sample can be extracted from the sample vial into the sample loop flow path 410. Alternatively, the sample probe can also extract the sample from the sample vial into the trap. When exhausting from the headspace in the sample vial into the sample loop, the pressure in the sample vial can be reduced. Further, the transfer line 405 can be connected to the carrier gas inlet via the 6-port valve 415.

[0049] And, the headspace sampler 120 can implement an injection flow path exemplified in FIG. 5. The 6-port valve 515 can be oriented to connect the carrier gas source to the transfer line 505 via the sample loop 510. Representative carrier gases include hydrogen, helium, nitrogen, and argon-methane. By flowing the carrier gas into the flow path, the sample in the sample loop 510 can be forced into the transfer line 505. The sample can flow from the transfer line 505 to a gas chromatograph (GC) for analysis, such as the gas chromatograph 180 in FIG. 1. In some cases, the 6-port valve can also be oriented to connect the sample probe 520 to the outlet (e.g., the outlet 205 in FIG. 2). In such a case, the outlet can exhaust the sample vial connected to the sample probe (e.g., set the pressure in the headspace of the vial to ambient pressure, or to a pressure lower than the pressure reached during sampling of the headspace of the vial).

[0050] [Column] The separation of sample components can be performed in column 135 of gas chromatograph 180. The inner surface of column 135 can have a coating film (e.g., stationary phase) that interacts differently with different sample components. This interaction may not be chemical in nature but rather physical in nature (e.g., adsorption, "solvation," sieving, etc.). Representative columns include those with an appropriate polymer film coated on the wall of a capillary tube (e.g., length 5 - 100 m, diameter 0.1 - 0.5 mm). Also, the column can contain particles that interact directly with the sample or particles that interact with the sample by coating on the particles. In either case, when the sample components pass through the column, certain components interact more strongly with the stationary phase than other components and are retained for a longer time. In this way, the sample components are carried by the carrier gas to the detector side of column 135, but the elution times are different due to differences in the interaction with the stationary phase.

[0051] [Column Temperature Control] (For example, via the column temperature control device 140 of gas chromatograph 180), by controlling the temperature of column 135, the interaction between the sample components and the column can be adjusted. Depending on the sample, it may contain components that interact minimally with column 135 at a given temperature and components that are retained permanently at the same temperature. Therefore, the column temperature control device 140 accurately (and reproducibly) controls the column temperature while the sample components are moving through column 135. Such temperature control may include increasing the temperature of column 135 during elution of the sample. When the last component has eluted from the column, the temperature can be returned to the starting temperature before the next sample is introduced. Depending on the sample, the desired starting temperature may be below room temperature, or the desired starting temperature may be room temperature or near room temperature. And for another sample, the desired starting column temperature may be higher than room temperature.

[0052] [Detector] The separated components of the sample can be received or identified by the detector 145 of the gas chromatograph 180. The detector 145 can change an electrical signal when some or all of the sample components elute from the column 135.

[0053] [Signal processing device and data analysis device] The signal processing device 150 can receive the electrical signal generated by the detector 145 and process the signal. The signal processing device 150 can be an analog-to-digital converter that converts the analog output of the detector 145 into a digital signal that can be used by the data analysis device 155. The data analysis device 155 can convert the gas chromatography signal received from the signal processing device 150 into the quantification and calibration of compounds. In some cases, the signal processing device 150 and / or the data analysis device (i.e., the signal processing device 150 or the data analysis device or both of them) can be provided outside the gas chromatograph 180.

[0054] [Input / output device] The input / output device 165 can receive the input from the gas chromatography system and / or display the output from the gas chromatography system (i.e., receive the input from the gas chromatography system or display the output from the gas chromatography system or both of them). The input / output device 165 can be an analog switch, a keyboard, and a display. Alternatively, the input of the set value and the monitoring of the system can also be performed on an external computer using appropriate software. In some cases, the input / output device 165 can be housed on various components of the headspace sampler or the gas chromatograph, or can be provided outside the chromatograph.

[0055] [Control system] The control system 160 can be an electronic device programmed to control the operation of the gas chromatography system to obtain a desired result. The control system 160 may be programmed to autonomously execute the gas chromatography regimen without the need for input (from a feedback device or the user), or it may accept such input. The principle of the method of using feedback (such as a temperature sensor) to adjust the operation of components is described, for example, in "Karl Johan Astrom & Richard M. Murray, Feedback Systems: An Introduction for Scientists & Engineers (2008)".

[0056] The control system 160 can be an arithmetic device such as a microcontroller (available, for example, with ARDUINO (registered trademark) or IOIO (trademark)), a general-purpose computer (such as a personal computer or PC), a workstation, a mainframe computer system, etc. An exemplary control system is shown in FIG. 8. The control system 800 can include a processor device (such as a central processing unit or "CPU") 802, a memory device 804, a storage device 806, a user interface 808, a system bus 810, and a communication interface 812.

[0057] The processor 802 can be any type of processing device as long as it can execute instructions and process data.

[0058] The memory device 804 can be any type of memory device including any one or more of random access memory ("RAM"), read only memory ("ROM"), flash memory, electrically erasable programmable read only memory ("EEPROM"), etc.

[0059] The memory device 806 can be any data storage device that reads from and writes to any removable and / or embedded (i.e., removable or embedded or both) optical, magnetic, and / or magneto-optical (i.e., optical, magnetic, or magneto-optical or all of them) storage media, etc. (for example, hard disks, compact disc read-only memory "CD-ROM", rewritable CD "CDRW", digital versatile disc ROM "DVD-ROM", DVD-RW, etc.). The memory device 806 can also include a controller / interface for connecting to the system bus 810. Thus, the memory device 804 and the memory device 806 are also suitable for storing not only data but also instructions for programs processed to be executed on the processor 802.

[0060] The user interface 808 may include a touch screen, a control panel, a keyboard, a keypad, a display, or any other type of interface, and each interface can be connected to the system bus 810 via the interface / adapter of the corresponding input / output device.

[0061] The communication interface 812 can be adapted and configured to communicate with any type of external device or with other components of the gas chromatography system. As an example, the double-line arrow such as arrow 170 in FIG. 1 shows the electronic communication between the control system 160 and other components of the gas chromatography system. Further, the communication interface 812 can be adapted and configured to communicate with any system or network, such as one or more computing devices on a local area network ("LAN"), a wide area network ("WAN"), the Internet, etc. The communication interface 812 can be connected directly to the system bus 810 or via an appropriate interface.

[0062] The control system 800 is thus capable of performing processing, either by itself and / or in cooperation with one or more additional devices (i.e., either by itself or in cooperation with one or more additional devices or both), including algorithms for controlling the components of the gas chromatography system according to the present invention. The control system 800 can be programmed, or commanded, to perform these processes according to any communication protocol and / or programming language (i.e., communication protocol or programming language or both) on any platform. Thus, each process can be implemented not only as data, but also as instructions stored in the memory device 804 and / or storage device 806 (i.e., memory device 804 or storage device 806 or both), or as instructions received at the user interface 808 and / or communication interface 812 for execution on the processor 802.

[0063] In some cases, the control system of the headspace sampler and the control system of the gas chromatograph may be the same control system or different control systems, and the control system may be housed in the headspace sampler, the gas chromatograph, or both, or in an external device.

[0064] [Removal of Sample Vial] After the sample is extracted from the sample vial by performing an extraction process, the gas chromatography system can attempt to remove the sample vial from the sample probe. As described above, FIG. 6 depicts that by moving the sample vial 610 upward by the actuator 620, the sample probe 615 can access the contents of the sample vial 610. FIG. 7 depicts the successful removal of the sample vial 610 from the sample probe 615. The actuator 620 can operate to move away from and separate from the sample probe 615. In some cases, the actuator 620 can operate at a predetermined speed and descend under control to separate from the sample probe 615. Further, the sample probe 615 can include a compression spring (shown in FIG. 7). When the sample probe 615 is in a position to access the contents of the sample vial 610 (e.g., as shown in FIG. 6), the compression spring can be compressed. When the actuator 620 retreats to separate from the sample probe 615, the compression spring can extend. This extension begins to generate a force that moves away and separates from the sample probe 615, thereby forcibly separating the sample vial 610 from the sample probe 615. FIG. 7 is a diagram showing the compression spring 625 in the extended mode. Further, those skilled in the art will understand that the compression springs depicted in FIGS. 6 and 7 are merely examples of means for removing the sample vial within the sample vial holder, and that other forms (e.g., gravity, elastomers, pistons, fluid bladders, Belleville washers, etc.) that provide a force to move away and separate from the sample probe can be used by the gas chromatography system described in the present specification.

[0065] However, in some cases, it may not be possible to remove the sample vial from the sample probe. For example, the opening of the sample probe may get caught inside the headspace of the sample vial or inside the septum of the sample vial. This is thought to be due to friction between the sample probe and the septum, insufficient ejector spring force, friction between the vial and surrounding components, alignment problems such as misalignment of the vial rack, or other reasons. In some cases, the removal of the sample vial from the sample probe may be partial (e.g., the vial is partially returned and repositioned inside the carousel cartridge). In the exemplary mechanism of FIG. 7, even if the sample vial 610 becomes immovable on the sample probe, the actuator 620 can still fully retract to its rest position. Therefore, simply sensing the position of the lifter rod with a position sensor known in the art such as an encoder is insufficient to determine whether the sample vial has been removed from the sample probe. Because in a conventional system, it is not possible to recognize that the removal of the vial from the probe has failed, and normal system processing (e.g., preparing the system for another chromatography run, attempting to bias another sample vial against the sample probe, etc.) continues, there is a possibility that such a failed removal attempt may cause serious problems in the gas chromatography system. If the failure of the removal is not detected, ultimately, problems such as damage to the gas chromatography system, breakage of the vial, and the need for additional maintenance may occur.

[0066] [Detection of the presence of the headspace vial] A gas chromatography system can be configured to sense whether a sample vial is present on a sample probe. After a sample is extracted from the sample vial, the gas chromatography system can utilize fluid parameter sensors in the flow path to detect parameter values within each flow path. Thereafter, the gas chromatography system can identify from the sensed parameter values whether the vial remains on the sample probe, whether the removal of the vial from the probe was successful, etc. In some cases, the gas chromatography system can further be configured with a headspace sampler (e.g., a 6-port valve, a switching valve, a proportional valve, etc.) to connect the sample probe to one of the configured flow paths such as the vial pressurization flow path depicted in FIG. 3. The following examples are based on the physical components and flow paths depicted in FIGS. 1 and 2. However, those skilled in the art will understand that the invention described in this specification can also be implemented by various gas chromatography systems, particularly systems with different flow path configurations and positions or presence / absence of fluid parameter sensors. For example, the techniques described in this specification can be implemented in a system including a pressure sensor and / or a flow rate sensor (i.e., a pressure sensor or a flow rate sensor or both) in fluid communication with the sample probe.

[0067] [Flow path configuration] The sensors of the gas chromatography system can monitor the pressure and / or flow rate (i.e., pressure or flow rate or both) within the flow path of the headspace sampler. The headspace sampler can be configured such that at least one of the pressure sensor or the flow rate sensor of the gas chromatography system can access the flow path connected to the sample probe. For example, in FIG. 2, the headspace sampler is configured to open the switching valve 255 such that the flow rate sensor 240 and / or the pressure sensor 245 (i.e., the flow rate sensor 240 or the pressure sensor 245 or both) can measure the pressure and / or flow rate (i.e., pressure or flow rate or both) within the flow path fluidly connected to the sample probe.

[0068] According to the above example, a headspace sampler is configured, and the pressure and flow rate of the gas in the flow path connected to the sample probe can be changed by using the proportional valve 250 and / or the proportional valve 260 in FIG. 2 (that is, the proportional valve 250 or the proportional valve 260 or both of them). Feedback from sensors such as the flow rate sensor 240 and the pressure sensor 245 can be used for valve control.

[0069] [Verification of the presence of vials by passive air pressure monitoring] The gas chromatography system can detect whether the removal of the vial from the probe 225 is successful by performing measurements during the vial discharge process.

[0070] After taking out the sample from the sample vial or after aborting the sample extraction, the gas chromatography system can attempt to discharge the sample vial from the sample probe. For example, as described above with reference to FIGS. 6 and 7, the lifter rod can operate to move away from the sample probe.

[0071] After removing the sample from the sample vial, the gas chromatography system can pressurize the vial at a pressure other than ambient pressure at the start of the discharge process by increasing the pressure of the vial, decreasing the pressure of the vial, or making the pressure of the vial substantially the same as the pressure at the end of the loop filling. During the discharge process, parameters such as the pressure and / or flow rate of the fluid flowing through the flow path (i.e., pressure or flow rate or both) can be measured by a sensor connected to the flow path of the sample probe. In some cases, the gas chromatography system can then compare the measurements obtained during the discharge process when the vial is expected to still be present on the sample probe (e.g., around the start of the discharge process) with the measurements obtained during the discharge process when the vial is expected to have been removed from the sample probe (e.g., around the end of the discharge process). The point in time when the vial is expected to have been removed from the sample probe can be obtained based on the elapsed time since the attempt to start the discharge or the lifter position monitored by a position sensor such as an encoder. In other cases, the gas chromatography system can compare the measurements obtained during the discharge process when the vial is expected to have been removed from the sample probe (e.g., around the end of the discharge process) with a predetermined value or threshold (e.g., around ambient pressure). In other cases, the gas chromatography system can look for changes in the measurements during the discharge process (e.g., stepwise changes, changes exceeding a threshold, etc.). The measurements sensed by the sensor may depend on whether the discharge of the sample vial from the sample probe was successful. If the discharge of the vial from the sample probe was successful, the flow path fluidly connected to the sample probe will be open to atmospheric pressure rather than sealed within the pressurized vial.

[0072] For example, it is possible to fluidly connect a sample probe to a pressure sensor, substantially zero the gas flowing through the sample probe, and pressurize the vial to a pressure higher than the ambient pressure at the start of the discharge process. In the example of the flow path shown in FIG. 2, this can be done by closing the proportional valve 250 and the proportional valve 260, opening the switching valve 255, and orienting the 6-port valve 265 such that the sample probe is fluidly connected to the pressure sensor 245. If the removal of the sample vial from the sample probe is successful, the pressure sensor (e.g., pressure sensor 245) can sense a pressure change (e.g., a decreasing change) because the flow path fluidly connected to the sample probe is opened to the atmosphere. The initial value of the sensed parameter occurs during sensing when the vial is expected to still be present on the sample probe. This pressure change occurs because when the sample vial is removed from the sample probe, the pressure sensor transitions from a state where it is fluidly connected to the pressurized environment (headspace) inside the sample vial to a state where it is open to the atmosphere.

[0073] In another example, the sample probe can be fluidly connected to a flow sensor and a pressure sensor, a gas can be flowed through the sample probe, and the vial can be pressurized to a pressure other than ambient pressure at the start of the discharge process. The gas flow may be substantially constant. In the flow path of the example shown in FIG. 2, this can be done by opening the switching valve 255, optionally opening the proportional valve 260, and orienting the 6-port valve 265 such that the sample probe is fluidly connected to the pressure sensor 245 and the flow sensor 240. The flow through the flow path can be controlled by controlling the proportional valve 250 using the flow sensor 240. If the removal of the sample vial from the sample probe is successful, the pressure sensor (e.g., pressure sensor 245) can sense a pressure change (e.g., a decreasing change) because the flow path fluidly connected to the sample probe is open to atmospheric pressure. Here, the initial value of the sensed parameter occurs during sensing where the vial is expected to still be present on the sample probe (e.g., the sample probe is fluidly connected to the inside of the sample vial being pressurized). Because gas flows through the flow path, if there is a fluid restriction in the flow path between the pressure sensor 245 and the opening of the sample probe, the pressure sensed by the pressure sensor 245 may be higher than atmospheric pressure.

[0074] Alternatively, in another example, the sample probe can be fluidly connected to a flow sensor and a pressure sensor, and the pressure in the sample vial can be controlled to a set value during the discharge process. In the flow path of the example shown in FIG. 2, this can be done by closing the proportional valve 260, opening the switching valve 255, and orienting the 6-port valve 265 such that the sample probe is fluidly connected to the pressure sensor 245 and the flow sensor 240. The pressure in the sample vial fluidly connected to the sample probe can be controlled by using the proportional valve 250 to adjust the vial pressurizing gas according to the set value of the pressure sensor 245. If the removal of the sample vial from the sample probe is successful, the flow rate measured by the flow sensor 240 increases (e.g., an increasing change). This is because when the sample vial is removed from the sample probe, the flow path is opened to atmospheric pressure, and the controller attempts to maintain the pressure in the flow path connected to the sample probe. Here, the initial value of the sensed parameter occurs during sensing when the vial is expected to still be present on the sample probe (e.g., the sample probe is fluidly connected to the headspace in the pressurized sample vial). Depending on the pressure set value, the restrictions of the connecting flow path, and the viscosity of the gas, the headspace sampler may not be able to maintain the pressure set value. Also, in some cases, this may indicate that the discharge of the vial was successful.

[0075] If the ejection of the sample vial from the sample probe is not successful, the sensor can sense the static values of the parameters detected during the vial ejection process. Or, in an example where the flow rate to the vial during ejection is constant, the sensor can sense the increase in pressure up to the maximum value allowed by the system (for example, the maximum value applied during vial pressurization may be 75 psi, but the maximum value allowed by the system may be 100 psi). In another case, if the sample probe gets stuck within the septum of the sample vial or the sample probe becomes clogged, among the parameters sensed during the vial ejection process, the sensor can sense a substantially static value. Figures 9 to 11 are graphs showing the measured values of flow rate and pressure of a gas chromatography system implementing an example of the method described above. The measured values of flow rate and pressure are those of a flow path fluidly connected to the sample probe of the gas chromatography system. Figure 9 shows the case where the ejection of the sample vial is successful, Figure 10 shows the case where the ejection of the sample vial is not successful, and Figure 11 shows the case where the sample probe is clogged or the opening of the sample probe becomes immovable within the septum of the sample vial (for example, due to some septum or part of the sample remaining in the sample probe).

[0076] [Example of Successful Sample Vial Ejection] Figure 9 is a timing diagram showing the measured values of pressure and flow rate at the time of successful ejection of the sample vial according to an embodiment of the present invention. As described above, the gas chromatography system can connect the sample vial to the sample probe flow path and the vial pressurizing gas at events A and B to pressurize the contents within the sample vial. Then, the headspace sampler can fill the sample loop with the sample, such as by fluidly connecting the sample probe and the sample loop to the outlet as depicted at event C. At event D, the gas chromatography system can convey the contents of the sample loop to the transfer line and the gas chromatograph by fluidly connecting the sample loop to the carrier gas source.

[0077] In event E, the gas chromatography system can perform the discharge process of the sample vial. The system can configure the headspace sampler to close the proportional valves 250 and 260 in FIG. 2. Therefore, in the headspace sampler, there is no gas input value to the sensor fluidly connected to the sample probe, but there is a pressure exceeding atmospheric pressure in the sample vial at the start of the discharge process. When the sample vial is separated from the sample probe during event E, for example, using the pressure sensor 245 in FIG. 2, the gas chromatography system measures the pressure drop. Based on the pressure drop, the gas chromatography system can determine that the removal of the sample vial is successful and continue to operate in normal processing. In event F, the system can purge the sample probe and the outlet. Then, the system can purge only the sample probe in event G and start the standby mode in event H to wait for another sample vial.

[0078] [Example of a vial that has stopped working with the probe] FIG. 10 shows the measured values of pressure and flow rate at the time of failure of discharging the sample vial according to an embodiment of the present invention. The measured values shown in FIG. 10 relate to the situation where the sample vial remains on the sample probe after the discharge process performed by the headspace sampler.

[0079] Regarding events A, B, C, and D, it is as described above for FIG. 9.

[0080] In event E, the gas chromatography system can perform the discharge process of the sample vial. The system can configure the headspace sampler to close the proportional valves 250 and 260 in FIG. 2. During the discharge process, in the headspace sampler, there is no gas input value to the sensor fluidly connected to the sample probe, but there is a pressure exceeding atmospheric pressure in the sample vial. During the discharge process, since the sample vial remains on the sample probe, in the gas chromatography system, during the discharge process, the pressure in the flow path fluidly connected to the sample probe is substantially static pressure. Therefore, the gas chromatography system can identify the static pressure value of the flow path connected to the probe, for example, using the pressure sensor 245 in FIG. 2. Based on the static pressure measurement value (for example, a pressure value within a predetermined threshold, a pressure change rate within a range of a predetermined threshold, etc.), the gas chromatography system can determine that the sample vial remains on the sample probe and the vial discharge has failed. When the system continues the normal purge operations for events F, G, and H, the pressure measurement value increases because the sample probe is fluidly connected to the sample vial (for example, gas flows into a sealed space).

[0081] [Example where the probe is clogged or the probe cannot move within the septum] FIG. 11 shows the measured values of pressure and flow rate when the probe is clogged or the opening of the probe cannot move within the septum of the vial according to an embodiment of the present invention. The measured values shown in FIG. 11 relate to the situation where the sample probe is clogged or the opening of the sample probe cannot move within the septum of the vial during the discharge process performed by the gas chromatography system.

[0082] Events A, B, C, and D are as described above with respect to FIGS. 9 and 10.

[0083] In event E, the gas chromatography system can perform a process of discharging the sample vial. The system can configure the headspace sampler to close the proportional valves 250 and 260 in FIG. 2. During the discharging process, in the headspace sampler, there is no gas input value to the sensor fluidly connected to the sample probe, but there is a pressure exceeding atmospheric pressure in the sample vial. During the discharging process, because the sample probe is clogged or the opening of the sample probe cannot move within the septum of the vial, the pressure of the gas chromatography system is substantially static pressure. Therefore, the gas chromatography system can measure the static pressure value of the flow path connected to the probe using, for example, the pressure sensor 245 in FIG. 2. Based on the static pressure measurement value (such as a pressure value within a predetermined threshold range, a rate of change of pressure within a predetermined threshold range, etc.), the gas chromatography system can determine that the sample vial remains on the sample probe and the discharging of the vial has failed. Alternatively, this may also mean that the probe is clogged. When the system continues its normal operation for events F, G, and H, since the sample probe is not open to the atmosphere and the space within the system is limited, the pressure measurement value within the system increases. If the sample probe is clogged or the opening of the sample probe cannot move within the septum, compared with the case where the opening of the sample probe is caught in the internal space (headspace) of the sample vial, the space within the flow path connected to the sample probe is further restricted, so the pressure measurement value increases even faster (for example, the space of the flow path connected to the sample probe is the flow path between the pressure sensor 245 and the tip of the sample probe, and when the sample vial probe is clogged or the opening of the sample probe cannot move within the septum of the sample vial, the space within the sample vial is not included).

[0084] Furthermore, in some cases, a restriction test can be performed before connecting the sample vial to the sample probe to reduce the risk of probe clogging. For example, a gas chromatography system can flow gas through the sample probe and monitor the rate of change of the pressure of the sample probe. If the rate of pressure change exceeds a predetermined threshold value, the gas chromatography system can determine that the sample probe is clogged (for example, the rate of pressure change is higher compared to the case where the sample probe is not clogged and is open to the ambient environment). In other cases, the gas chromatography system can monitor the pressure value of the sample probe while flowing gas through the sample probe. If the pressure value exceeds a predetermined threshold value at a specific flow rate, the gas chromatography system can determine that the sample probe is clogged (for example, the sample probe reaches a higher pressure value compared to the case where the sample probe is not clogged and is open to the ambient environment). In yet another case, the gas chromatography system can monitor the steady backpressure generated from the standby flow. If the backpressure exceeds a predetermined threshold value, the gas chromatography system can determine that the sample probe is clogged.

[0085] If the gas chromatography system determines that the sample probe is not clogged (for example, through a restriction process), then the system can next connect the sample vial to the sample probe. If the sample probe is not clogged immediately before connecting to the vial, the likelihood of the sample probe clogging during sampling is low.

[0086] [Active pneumatic test for confirming the presence of the vial] Alternatively, to determine whether the discharge of the sample vial from the sample probe was successful, after it is expected that the vial has been discharged from the sample probe, the gas chromatography system can configure the headspace sampler to introduce pressurized gas into the flow path connected to the sample probe. This configuration can, in some cases, enable the evacuation of the sample vial to atmospheric pressure before attempting to remove the vial from the sample probe, and also provides the additional advantage of evacuating the vial once it has been discharged before discarding or handling it.

[0087] Before discharging the vial, the system may evacuate the vial to atmospheric pressure or another pressure lower than the final sampling pressure, leave the vial at the residual pressure from the sampling process, or increase, decrease, or leave unchanged the pressure within the vial compared to the end of the sampling process. The gas chromatography system can perform the vial discharge process and attempt to discharge the sample vial from the sample probe. During the vial discharge process after it is expected that the vial has been removed from the sample probe (based on, for example, the elapsed time since the start of the discharge attempt, the lifter position monitored by a sensor such as an encoder), the gas chromatography system can be configured to introduce vial pressurized gas into the connected flow path and cause it to flow through the sample probe. For example, the switching valve 255 of the flow path shown in FIG. 2 can be opened, and the proportional valve 250 can be used to control the gas flow rate through the sample probe or the pressure of the flow path connected to the sample probe. In some cases, the pressurized gas can be flowed through the flow path at a constant flow rate. One or more sensors (e.g., the pressure sensor 245 and the flow rate sensor 240 in FIG. 2) connected to the sample probe flow path can measure various parameters of the flow path, such as the flow rate and / or pressure (i.e., the flow rate or pressure or both).

[0088] One or more connected sensors can sense the rate of change of the pressure or flow rate in the connected flow path during the discharge process and while gas is flowing into the connected flow path. The rate of change of the measured parameter may be affected by whether the discharge of the sample vial from the sample probe was successful. For example, one or more sensors can measure a gradual increase (e.g., in the pressure value) when the discharge of the sample vial from the sample probe is successful. Alternatively, one or more sensors can measure a rapid increase (e.g., in the pressure value) when the discharge of the sample vial from the sample probe is not successful, such as when the sample probe is caught within the septum of the sample vial or when the sample probe is clogged. By performing a limit test before sampling the vial, situations where probe clogging occurs can be suppressed. These differences in the rate of change may depend on the space into which the gas flows.

[0089] For example, after it is predicted that the vial has been removed from the sample probe, the system can attempt to control the flow rate of the gas passing through the sample probe to a set value (such as by using the flow rate sensor 240 and the proportional valve 250), and can measure the pressure in the flow path connected to the sample probe (such as by using the pressure sensor 245 in FIG. 2). If the sample vial still remains on the sample probe, the sample probe is clogged, or it is caught in the septum of the vial, the gas will flow into the enclosed space (flow path, sample probe, and in some cases the vial - sample, etc.). Therefore, the sensed pressure will rise rapidly. Alternatively, if the removal of the sample vial is successful, the gas will flow out of the sample probe into the surrounding environment (i.e., a larger space). Therefore, the sensed pressure will increase more slowly (if measurable). Also, the value of the pressure after a certain time from the start of measurement can indicate whether the discharge of the vial was successful. For example, if the discharge of the vial is successful and the flow rate of the gas passing through the sample probe is constant, the pressure will rise to a value depending on the restriction between the pressure sensor and the outlet of the sample probe, the viscosity of the gas, and the flow rate. Alternatively, if the discharge of the sample vial is not successful, the pressure will rise to a higher value because gas flows into the enclosed system.

[0090] In some cases, after the sample vial is expected to be removed from the sample probe, the pressure in the flow path fluidly connected to the sample probe can be controlled so as to reach a pressure set value, and the flow rate of the gas required to achieve this set value can be measured (for example, by monitoring the flow rate sensor 240 in FIG. 2). In such a case, the gas chromatography system can increase the flow rate of the flowing gas until the pressure set value is reached (for example, by monitoring the pressure value from a pressure sensor connected to the flow path of the sample probe, such as the pressure sensor 245 in FIG. 2). When the pressure set value is reached, at that time, the gas chromatography system can identify the flow rate required to reach the pressure set value. Depending on the set pressure, the restrictions of the connected flow path, and the viscosity of the gas, the headspace sampler may not be able to achieve the set pressure. In some cases, this may indicate that the discharge of the vial was successful. If the discharge of the sample vial is not successful and the sample probe is still fluidly connected to the sample vial, the flow rate required to achieve the pressure set value is less than that when the discharge of the sample vial from the sample probe was successful. By way of example, if the discharge is not successful, the flow rate may be substantially zero.

[0091] Furthermore, alternatively, the system can identify the time required to reach the pressure set value. If the discharge process is successful, it may take longer to reach the set pressure than when the discharge process fails at the same flow rate. From this monitored value, the system can identify whether the discharge of the vial from the sample probe was successful.

[0092] Figures 12 to 14 are graphs showing the measured values of the flow rate and pressure of a gas chromatography system in which the above-described measurement example was carried out. The measured values of the flow rate and pressure are those of a flow path fluidly connected to a sample probe of the gas chromatography system. Figure 12 shows the case where the discharge of the sample vial is successful, Figure 13 shows the case where the discharge of the sample vial is not successful, and Figure 14 shows the case where the sample probe is clogged, respectively.

[0093] [Example of successful vial discharge] Figure 12 is a diagram showing the measured values of the pressure and flow rate at the time of successful discharge of the sample vial according to an embodiment of the present invention. As described above, the gas chromatography system can connect the sample vial to the sample probe flow path and the vial pressurizing gas and pressurize the contents in the sample vial in Events A and B. The headspace sampler can then fill the sample loop with the sample by, for example, fluidly connecting the sample probe to the discharge port (depicted in Event C). In Event D, the gas chromatography system can transport the contents of the sample loop to the transfer line and the GC column by fluidly connecting the sample loop to the carrier gas source. Optionally, in Event D, the system can also evacuate the vial to the pressure set value or pressurize the vial to the set value.

[0094] In event E, the gas chromatography system can perform a process of discharging the sample vial. The system can attempt to remove the sample vial from the sample probe. During the discharging process after the vial is expected to be removed from the sample probe, the gas chromatography system can flow gas through the flow path connected to the sample probe. Since the discharge of the vial from the sample probe is successful, the pressure rises to a value based on the restriction of the flow path between the pressure sensor and the outlet of the sample probe, the gas viscosity, and the flow rate. The pressure value can be lower than the pressure value when the sample probe is still present within the sample vial. In event F, the system can purge the sample probe and the discharge port. Thereafter, the system can purge the sample probe in event G and start the standby mode to wait for another sample vial in event H.

[0095] [Example where the vial stops moving on the probe] FIG. 13 is a graph showing measured values of pressure and flow rate at the time of failure of discharging the sample vial according to an embodiment of the present invention. The measured values shown in FIG. 13 relate to the situation where the sample vial remains on the sample probe during and after the discharging process performed by the gas chromatography system with the opening of the sample probe being fluidly connected to the internal space (headspace) of the sample vial.

[0096] Events A, B, C, and D are as described above with respect to FIG. 12.

[0097] In event E, the gas chromatography system can perform a process of discharging the sample vial. During the discharging process after the vial is expected to be removed from the sample probe, the gas chromatography system can flow gas through the flow path connected to the probe. Since the sample vial remains on the sample probe, the flow path is connected to a predetermined space (e.g., the space of the sample vial). As the gas flows through the flow path, the pressure inside the flow path rises more significantly than when the sample probe is open to the ambient environment. Therefore, the gas chromatography system can identify that the pressure value of the flow path connected to the probe is rising. The gas chromatography system can determine that the sample vial remains on the sample probe and the discharging process has failed based on the rate of pressure rise with respect to the flow rate or the reached pressure. When the system continues its normal operation for events F, G, H, since the gas flows within a predetermined space in the system, the measured pressure value increases.

[0098] [Examples of a clogged probe or a probe that has become immobile within the septum] FIG. 14 is a diagram showing measured values of pressure and flow rate when the probe is clogged, according to an embodiment of the present invention. The measured values shown in FIG. 14 relate to a situation where the sample probe is clogged or the opening of the sample probe has become immobile within the septum of the vial during the discharging process performed by the gas chromatography system.

[0099] Events A, B, C, D are as described above with reference to FIGS. 12 and 13.

[0100] In event E, the gas chromatography system can perform the discharge process of the sample vial. The system can attempt to remove the vial from the sample probe. During the discharge process after the vial is expected to be removed from the sample probe, the gas chromatography system can flow pressurized gas into the flow path connected to the probe. Due to the sample probe being clogged or the opening of the sample probe becoming immovable within the septum of the vial, the flow path is fluidly connected to a predetermined space (a space even smaller than when the opening of the sample probe is immovable within the internal space of the sample vial). Since gas flows through the flow path, the pressure within the flow path rises at a higher rate than when the sample probe is open to the ambient environment or when the opening of the sample probe is immovable within the internal space of the sample vial. Therefore, the gas chromatography system can identify that the pressure value of the flow path connected to the probe is rising. The gas chromatography system can determine from the pressure rise rate or the reaching pressure for a specific flow rate that the sample probe is clogged or immovable within the septum of the vial and that the discharge process has failed. When the system continues its normal operation for events F, G, and H, the space within the system is restricted, so the measured pressure value rises within the system.

[0101] Note that since the space included in the flow path is smaller than the situation where the opening of the probe remains within the sample vial, in the case of a probe that is clogged or caught by the septum, the pressure rises more quickly. Similarly, when controlling to a pressure set value, the flow rate and / or time (i.e., flow rate or time or both) required for the system to reach the predetermined pressure set value will also be less in the case of a probe that is clogged or caught by the septum compared to the case where the opening of the sample probe remains within the space of the sample vial.

[0102] [Parameter Threshold] Before performing the discharge process, parameter thresholds can be determined by a gas chromatography system. In some cases, the parameter thresholds (e.g., thresholds for step changes, rate-of-change thresholds, etc.) can be determined based on different characteristics of the sample, sample vial, and / or headspace sampler (i.e., the sample, sample vial, headspace sampler, or all of them). For example, using the vial volume, solvent composition, headspace composition, pressurized gas composition, flow path restriction, etc., the thresholds used by the system to identify whether the discharge of the sample vial from the sample probe was successful can be determined. In some cases, a user of the gas chromatography system can input some of these characteristics. Alternatively, the gas chromatography system can determine (e.g., sense) some of these characteristics.

[0103] In some cases, it is not necessary to calculate the parameter threshold from the measured parameter value. For example, if there is no gas flowing in the flow path to which the probe is connected and the sample vial is pre-pressurized, if the discharge of the vial is successful, the pressure drops to ambient pressure regardless of the parameters of the vial.

[0104] In another case, the threshold can be calculated based on the measured parameter, or a test vial can be placed on the probe before the sampling process. Thereafter, the test vial can be discharged while measuring the flow rate and / or pressure (i.e., the flow rate or pressure or both). Then, the values of this flow rate and / or pressure (i.e., this flow rate or this pressure or both) can be used to determine the threshold. The user can confirm manually or by another part of the system that the test vial has been discharged (e.g., by sensing that the vial has finally returned to its storage location).

[0105] [System Repair] When a gas chromatography system detects that the ejection of a sample vial from a sample probe has failed, it can perform various repair processes. For example, the system can terminate the chromatography function, such as by preparing another sample vial for sampling. In some cases, the system can generate a notification and send it (e.g., via the control system of FIG. 1), and the notification includes information corresponding to the failed ejection attempt. In some cases, the lifter rods of FIGS. 6 and 7 can be configured to bias towards the sample probe, thereby re - biasing the compression spring 625 and releasing the sample vial during a second ejection attempt and / or preventing the sample vial from falling from the sample probe (i.e., either releasing the sample vial or the sample vial falling from the sample probe or both). In some cases, the rack of FIGS. 6 and 7 can be biased to rotate or vibrate, thereby gently tapping the sample vial 610 and releasing the sample vial 610. The ejection mechanism can have a function similar to tapping or re - engaging the sample vial, and those skilled in the art will understand that the examples listed above are not limiting in themselves.

[0106] [Pressure Restoration of Sample Vial] A gas chromatography system can be configured to restore the pressure of the sample vial after sample extraction. When the sample is loaded into the sample vial and the sample vial is sealed, the vial is typically at or near ambient temperature and ambient pressure. After placing the sample vial in the headspace sampler for sampling preparation, the sample vial can be heated to a high temperature. This can increase the pressure inside the sample vial, which is a sealed system. Before extracting the sample from the sample vial, the headspace sampler can connect the sample probe to a flow path provided with at least one connected sensor. For example, the system can connect the sample vial to the sample probe 225 of the flow path in FIG. 2, while closing the proportional valves 250 and 260 so that gas does not enter or exit the sample vial, and opening the switching valve 255 to fluidly connect the pressure sensor 245 to the sample probe 225. In some cases, before pressurizing the sample vial with the vial pressurizing gas and / or extracting the sample (i.e., pressurizing the sample vial with the vial pressurizing gas or extracting the sample or both), by placing the sample vial on the sample probe, the connected sensor can measure the pressure in the flow path, i.e., the pressure inside the sample vial.

[0107] Furthermore, after extraction, the gas chromatography system can also measure the pressure of the sample vial. For example, the same configuration used for measuring the vial parameters can be used to measure the parameters after extraction. Alternatively, a different configuration can be used for the measurement after extraction. The system can determine the difference in pressure of the sample vial after extraction relative to before extraction (e.g., via the control system of FIG. 1). Further, the system can flow a vial pressurizing gas or carrier gas into the sample vial to restore the pressure of the sample vial to the level before extraction. Alternatively, if the pressure after extraction is higher than the pressure before extraction, the system can exhaust gas from the sample vial to restore the pressure of the sample vial to the level before extraction. This can be done by monitoring the pressure value of the pressure sensor and identifying when the pressure value reaches the set pressure.

[0108] Thus, when the sample vial is removed from the location where it was heated and returned to near the temperature before analysis (e.g., room temperature), the pressure inside the sample vial can return to a level close to the ambient pressure. Since the pressure inside the sample vial is close to the ambient pressure, the force generated by the pressure difference can be minimized. This can reduce the risk that the septum of the vial bends or the sample vial is damaged due to the vial becoming structurally weak. Further, since this process can depend on the pressure inside the sample vial before and after extraction, the process can be performed regardless of the contents. This can eliminate errors by the user, such as accidentally entering parameters (gas composition, solvent composition, etc.) related to the sample.

[0109] [Equivalents] The preferred embodiments of the present invention have been described using specific terms, but such descriptions are merely illustrative and it will be understood that changes and modifications can be made without departing from the spirit of the following claims or the scope of the claims.

[0110] [Incorporation by Reference] All patents, published patent applications, and other references cited in this specification are hereby incorporated by reference in their entirety as part of this specification. Note that the description of the claims at the time of filing was as follows. Claim 1: A sample probe, A fluid source in fluid communication with the sample probe, A pressure sensor in fluid communication with the sample probe, A processor A gas chromatography system comprising, wherein the processor is configured to (a) perform a discharge process to remove a sample vial from the sample probe; (b) receive a set of signals from the pressure sensor; (c) detect from the set of signals whether the discharge process was successful; (d) initiate one or more operations selected from the group consisting of repair and warning in response to the detection step A gas chromatography system configured to perform. Claim 2: In step (c), the processor further determines a change in value within the set of signals, and determines from the change in value that the sample vial has been removed from the sample probe, The gas chromatography system according to claim 1, configured as such. Claim 3: The repair further includes terminating the chromatography function when the processor detects that the discharge process has failed, the gas chromatography system according to claim 1. Claim 4: Reading the pressure value among the set of signals measures whether, during step (a), when the discharge process is successful, it is below a predetermined threshold or within a range of the predetermined threshold, or has reached atmospheric pressure, and the predetermined threshold is determined by the processor from the volume of the vial, solvent composition, headspace composition, pressurized gas composition, flow path restriction, measured value of the flow rate or pressure of the test vial, or a combination thereof, the gas chromatography system according to claim 1. Claim 5: In step (c), the processor further determines that no change in value has occurred within the set of signals, and determines from the set of signals whether the removal of the sample vial from the sample probe has failed, whether the sample probe has become immovable within the septum of the sample vial, or whether the sample probe is clogged. The gas chromatography system according to claim 1, configured as such. Claim 6: In step (e), the processor further controls the vial actuator to urge the sample vial towards the sample probe in response to a determination that the discharge process has failed, or is configured to control the vial rack to urge, wherein the urging occurs in response to a determination that the discharge process has failed, the gas chromatography system according to claim 1. Claim 7: Further comprising a heater in thermal conduction with the sample vial, the heater being configured to generate a state in which the sample vial is heated, and the processor further receives a first set of signals from the pressure sensor, determines an initial pressure of the sample vial in the heated state from the first set of signals, performs an extraction process on the contents of the sample vial, receives a second set of signals from the pressure sensor after the extraction process, determines a second pressure of the sample vial, controls a fluid source or an outlet in fluid communication with the sample vial to return the second pressure of the sample vial to the initial pressure, The gas chromatography system according to claim 1, configured as such. Claim 8: A sample probe, a fluid source in fluid communication with the sample probe, a pressure sensor in fluid communication with the sample probe, and a processor A gas chromatography system comprising, wherein the processor (a) performing a discharge process to remove a sample - sample vial from the sample probe; (b) flowing fluid through the fluid source to the sample probe during step (a); (c) receiving a set of signals from the pressure sensor during step (b); (d) detecting whether the discharge process is successful from the set of signals; (e) starting one or more operations selected from the group consisting of repair and warning in response to the detection step The gas chromatography system configured to perform. Claim 9: Further comprising a flow sensor in fluid communication with the sample probe, and a part of the set of signals is received from the flow sensor, the gas chromatography system according to claim 8. Claim 10: In step (d), the processor further determines a change in value within the set of signals, and determines from the change in value that the sample vial has been removed from the sample probe, The gas chromatography system according to claim 8, configured as such. Claim 11: In step (d), the processor further determines a rate of change within the set of signals, determines that the rate of change is less than a predetermined threshold, and determines that the discharge process has been successful. The gas chromatography system according to claim 8, configured as such. Claim 12: In step (d), the processor further determines a rate of change within the set of signals, determines whether the rate of change exceeds a predetermined threshold or is within a range of the predetermined threshold, and determines from the set of signals that the removal of the sample vial from the sample probe has failed. The gas chromatography system according to claim 8, configured as such. Claim 13: In step (d), the processor further determines a rate of change within the set of signals, determines that the rate of change exceeds a predetermined threshold, and determines from the set of signals that the sample probe is caught within the septum of the sample vial or that the sample probe is clogged. The gas chromatography system according to claim 8, configured as such. Claim 14: In step (e), the processor further controls the vial actuator to bias the sample vial towards the sample probe in response to a determination that the discharge process has failed, or is configured to control the vial rack to bias, the biasing occurring in response to a determination that the discharge process has failed. The gas chromatography system according to claim 8. Claim 15: including a heater that conducts heat with the sample vial, the heater being configured to generate a state in which the sample vial is heated, and the processor further receives a first set of signals from the pressure sensor, determines an initial pressure of the sample vial in the heated state from the first set of signals, performs an extraction process on the contents of the sample vial, receives a second set of signals from the pressure sensor after the extraction process, and determines a second pressure of the sample vial. Controlling a fluid source or outlet in fluid communication with the sample vial to return the second pressure of the sample vial to the initial pressure, The gas chromatography system according to claim 8, configured as such. Claim 16: A sample probe, A fluid source in fluid communication with the sample probe, A flow sensor in fluid communication with the sample probe, A processor A gas chromatography system including, wherein the processor (a) Performing a discharge process to remove the sample vial from the sample probe, Receiving a set of signals from the flow sensor, (c) Detecting from the set of signals whether the discharge process is successful, (d) Initiating one or more operations selected from the group consisting of repair and warning in response to the detection step A gas chromatography system configured to perform. Claim 17: In step (c), the processor further Determining a change in value within the set of signals, Determining from the change in value that the sample vial has been removed from the sample probe, The gas chromatography system according to claim 16, configured as such. Claim 18: In the gas chromatography system according to claim 16, the system attempts to maintain a constant pressure level within the sample probe between step (a) and step (b). The gas chromatography system. Claim 19: The repair further includes ending the chromatography function when the processor detects that the discharge process has failed. The chromatography system according to claim 16. Claim 20: In step (c), the processor further determines that no change in value has occurred within the set of signals, Determining from the set of signals whether the removal of the sample vial from the sample probe has failed, whether the sample probe has become immovable within the septum of the sample vial, or whether the sample probe is clogged, The gas chromatography system according to claim 16, configured as such. Claim 21: In step (e), the processor further Control the vial actuator to urge the sample vial towards the sample probe in response to a determination that the discharge process has failed, or configured to control the vial rack to urge, the urging occurring in response to a determination that the discharge process has failed, the gas chromatography system according to claim 16. Claim 22: A sample probe, A fluid source in fluid communication with the sample probe, A flow sensor in fluid communication with the sample probe, A processor A gas chromatography system comprising, wherein the processor is (a) Executing a discharge process to remove the sample vial from the sample probe; (b) Flowing fluid through the sample probe via the fluid source; (c) Receiving a set of signals from the flow sensor during step (b); (d) Detecting whether the discharge process has been successful from the set of signals; (e) Initiating one or more operations selected from the group consisting of repair and warning in response to the detecting step A gas chromatography system configured to perform. Claim 23: Further comprising a pressure sensor in fluid communication with the sample probe, wherein a portion of the set of signals is received from the pressure sensor, the gas chromatography system according to claim 22. Claim 24: In step (e), the processor further Controls the vial actuator to urge the sample vial towards the sample probe in response to a determination that the discharge process has failed, or Is configured to control the vial rack to urge, the urging occurring in response to a determination that the discharge process has failed, the gas chromatography system according to claim 24.

Claims

1. A sample probe that can be fluidly connected to a sample vial, A fluid source in fluid communication with the sample probe, A pressure sensor in fluid communication with the sample probe, A processor A gas chromatography system comprising: wherein the processor (a) performing a discharge process to remove a fluidly connected sample vial from the sample probe; (b) receiving a set of signals from the pressure sensor; (c) detecting from the set of signals whether the discharge process was successful; (d) initiating a repair process or notification in response to detecting that the discharge process has failed in the detecting step A gas chromatography system configured to perform.

2. In step (c), the processor further Determines a change in the value within the set of signals, From the change in the value, determines that the sample vial has been removed from the sample probe, The gas chromatography system according to claim 1, configured as such.

3. The repair process further includes ending the chromatography function when the processor detects that the discharge process has failed, the gas chromatography system according to claim 1.

4. Reading of the pressure value among the set of signals is to measure whether, during step (b), when the discharge process is successful, it is less than a predetermined threshold value, within a range of the predetermined threshold value, or has reached atmospheric pressure, and the predetermined threshold value is determined by the processor from the volume of the vial, solvent composition, headspace composition, pressurized gas composition, flow path restriction, measured value of the flow rate or pressure of the test vial, or a combination thereof. The gas chromatography system according to claim 1.

5. The processor further, in step (c), determines that no change in value has occurred within the set of signals, and determines from the set of signals whether the removal of the sample vial from the sample probe has failed, whether the sample probe has become immovable within the septum of the sample vial, or whether the sample probe is clogged. The gas chromatography system according to claim 1, configured as such.

6. The processor further, in step (d), controls the vial actuator to bias the sample vial towards the sample probe in response to a determination that the discharge process has failed, or is configured to control the vial rack to bias, and the biasing occurs in response to a determination that the discharge process has failed. The gas chromatography system according to claim 1.

7. Further, it includes a heater that conducts heat with the sample vial, the heater is configured to generate a state in which the sample vial is heated, and the processor further receives a first set of signals from the pressure sensor, determines an initial pressure of the sample vial in the heated state from the first set of signals, and executes an extraction process of the contents of the sample vial. receive a second set of signals from the pressure sensor after the extraction process, determine a second pressure of the sample vial, control a fluid source or outlet in fluid communication with the sample vial to return the second pressure of the sample vial to the initial pressure, The gas chromatography system according to claim 1, which is configured as described above.

8. a sample probe fluidly connectable to a sample vial, a fluid source in fluid communication with the sample probe, a pressure sensor in fluid communication with the sample probe, a processor A gas chromatography system comprising: wherein the processor (a) performing a discharge process to remove a fluidly connected sample vial from the sample probe; (b) flowing fluid through the sample probe via the fluid source during step (a); (c) receiving a set of signals from the pressure sensor during step (b); (d) detecting whether the discharge process has been successful from the set of signals; (e) initiating a repair process or notification in response to detecting that the discharge process has failed in the detection step A gas chromatography system configured to perform the above.

9. Further comprising a flow sensor in fluid communication with the sample probe, wherein a portion of the set of signals is received from the flow sensor, the gas chromatography system according to claim 8.

10. In step (d), the processor further determines a change in the values within the set of signals, Determining from the change in the value that the sample vial has been removed from the sample probe The gas chromatography system according to claim 8, configured as described above.

11. In step (d), the processor further Determines the rate of change within the set of signals Determines that the rate of change is less than a predetermined threshold Determines that the discharge process has been successful The gas chromatography system according to claim 8, configured as described above.

12. In step (d), the processor further Determines the rate of change within the set of signals Determines whether the rate of change exceeds a predetermined threshold or is within a predetermined threshold range Determines from the set of signals that the removal of the sample vial from the sample probe has failed The gas chromatography system according to claim 8, configured as described above.

13. In step (d), the processor further Determines the rate of change within the set of signals Determines that the rate of change exceeds a predetermined threshold Determines from the set of signals that the sample probe is caught in the septum of the sample vial or that the sample probe is clogged The gas chromatography system according to claim 8, configured as described above.

14. In step (e), the processor further Controls the vial actuator to bias the sample vial towards the sample probe in response to a determination that the discharge process has failed, or A gas chromatography system according to claim 8, configured to control and bias a vial rack, wherein the biasing occurs in response to the discharge process failing.

15. Including a heater that conducts heat with the sample vial, the heater being configured to generate a state in which the sample vial is heated, and the processor further Receives a first set of signals from the pressure sensor, Determines an initial pressure of the sample vial in the heated state from the first set of signals, Performs an extraction process on the contents of the sample vial, Receives a second set of signals from the pressure sensor after the extraction process, Determines a second pressure of the sample vial, Controls a fluid source or outlet in fluid communication with the sample vial to return the second pressure of the sample vial to the initial pressure, A gas chromatography system according to claim 8, configured as described above.

16. A sample probe fluidly connectable to a sample vial, A fluid source in fluid communication with the sample probe, A flow sensor in fluid communication with the sample probe, A processor, and A gas chromatography system including the same, wherein the processor (a) Performing a discharge process to remove a fluidly connected sample vial from the sample probe; (b) Receiving a set of signals from the flow sensor; (c) Detecting whether the discharge process is successful from the set of signals; (d) Initiating a repair process or notification in response to detecting that the discharge process has failed in the detection step. A gas chromatography system configured to perform the above steps.

17. In step (c), the processor further determines a change in value within the set of signals, and determines from the change in value that the sample vial has been removed from the sample probe, The gas chromatography system according to claim 16, configured as such.

18. In the gas chromatography system according to claim 16, the system attempts to maintain a constant pressure level within the sample probe between step (a) and step (b). The gas chromatography system.

19. The repair process further includes ending the chromatography function when the processor detects that the discharge process has failed. The chromatography system according to claim 16.

20. In step (c), the processor further determines that no change in value has occurred within the set of signals, and determines from the set of signals whether the removal of the sample vial from the sample probe has failed, whether the sample probe has become immovable within the septum of the sample vial, or whether the sample probe is clogged. The gas chromatography system according to claim 16, configured as such.

21. In step (d), the processor further controls the vial actuator to urge the sample vial towards the sample probe in response to a determination that the discharge process has failed, or controls the vial rack to be configured to urge, the urging occurring in response to a determination that the discharge process has failed. The gas chromatography system according to claim 16.

22. A sample probe that can be fluidly connected to a sample vial, A fluid source in fluid communication with the sample probe, A flow rate sensor in fluid communication with the sample probe, A processor, A gas chromatography system comprising: the processor is configured to: (a) performing a discharge process to remove a fluidly connected sample vial from the sample probe; (b) flowing fluid through the sample probe via the fluid source; (c) receiving a set of signals from the flow rate sensor during step (b); (d) detecting whether the discharge process has been successful from the set of signals; (e) initiating a repair process or notification in response to detecting that the discharge process has failed in the detection step. A gas chromatography system configured to perform the above steps.

23. The gas chromatography system according to claim 22, further comprising a pressure sensor in fluid communication with the sample probe, wherein a part of the set of signals is received from the pressure sensor.

24. In step (e), the processor is further configured to: Control a vial actuator to bias the sample vial towards the sample probe in response to a determination that the discharge process has failed, or Control a vial rack to bias it, wherein the biasing occurs in response to a determination that the discharge process has failed. The gas chromatography system according to claim 22.

Images