Method and system for sensing presence of headspace vial

Abstract

This document describes methods and systems for sensing the presence of headspace vials. In one embodiment, a system may include a sample probe, a fluid source in fluid communication with the sample probe, one or more of a pressure sensor and a flow sensor in fluid communication with the sample probe, and a processor configured to: (a) receive a first set of signals from one or more of the pressure sensor and the flow sensor, execute an ejection procedure to remove the sample vial from the sample probe, receive a second set of signals from one or more of the pressure sensor and the flow sensor during step (b), (d) detect whether the ejection procedure was successful based on the first set of signals and the second set of signals, and (e) in response to the detection, initiate one or more actions selected from remediation and alarm.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 021,822, filed May 8, 2020, which is incorporated herein by reference in its entirety. Background Technology

[0003] In headspace gas chromatography, the contents of the vial are typically heated first, then pressurized, and subsequently sampled for volatile components. After sampling, the vial is ejected or removed from the sample probe. However, in some cases, the vial may not be successfully removed from the sample probe, potentially causing damage to the gas chromatography system, the vial, etc.

[0004] In addition, after sampling, allow the vial to cool to room temperature. The contents of the vial may still be under pressure or there may be a partial vacuum. Vial breakage can be hazardous, depending on the contents. Summary of the Invention

[0005] This document describes systems and methods for sensing the presence of headspace vials. In one aspect, a gas chromatography system may 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 configured to: (a) execute an ejection procedure to remove the sample vial from the sample probe; (b) receive a set of signals from the pressure sensor; (c) detect whether the ejection procedure was successful based on the set of signals; and (d) in response to said detection, initiate one or more actions selected from remediation and alarm.

[0006] This aspect can include various implementation schemes. In one implementation scheme, the processor in step (c) is further configured to: determine the change in value within the set of signals; and determine, based on the change in value, whether the sample vial has been removed from the sample probe.

[0007] In another implementation, the remedy may further include terminating the chromatography function if the processor detects a failed pop-up procedure.

[0008] In another embodiment, during step (a), the pressure readings of the set of signals can be measured to be below or within a predetermined threshold, or to atmospheric pressure when the ejection procedure is successful, and the predetermined threshold is determined by the processor based on vial volume, solvent composition, headspace composition, pressurized gas composition, flow path limitation, flow rate or pressure measurement of the test vial, or a combination thereof.

[0009] In another embodiment, the processor in step (c) is further configured to: determine that no change in value has occurred within the set of signals; and determine, based on the set of signals, that the sample vial failed to be removed from the sample probe, or that the sample probe is stuck in the septum of the sample vial, or that the sample probe is blocked.

[0010] In another embodiment, the processor in step (e) is further configured to: control the vial actuator to actuate the sample vial toward the sample probe in response to determining that the ejection procedure has failed; or control the vial holder to actuate, wherein the actuation occurs in response to determining that the ejection procedure has failed.

[0011] On the other hand, a gas chromatography system may 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 configured to: (a) execute an ejection procedure to remove a sample vial from the sample probe; (b) during step (a), allow fluid to flow through the fluid source to the sample probe; (c) during step (b), receive a set of signals from the pressure sensor; (d) detect whether the ejection procedure was successful based on the set of signals; and (e) in response to the detection, initiate one or more actions selected from a group consisting of remedies and alarms.

[0012] This aspect can include various implementation schemes. In one implementation, the gas chromatography system may further include a flow sensor in fluid communication with a sample probe, wherein a subset of the set of signals is received from the flow sensor.

[0013] In another implementation, the processor in step (d) is further configured to: determine the change in value within the set of signals; and determine whether the sample vial has been removed from the sample probe based on the change in value.

[0014] In another implementation, the processor in step (d) is further configured to: determine the rate of change within the set of signals; determine that the rate of change is below a predetermined threshold; and determine that the ejection procedure was successful.

[0015] In another embodiment, the processor in step (d) is further configured to: determine the rate of change within the set of signals; determine that the rate of change exceeds or is within a predetermined threshold; and determine, based on the set of signals, that the sample vial failed to be removed from the sample probe.

[0016] In another embodiment, the processor in step (d) is further configured to: determine the rate of change within the set of signals; determine that the rate of change exceeds a predetermined threshold; and determine, based on the set of signals, that the sample probe is trapped in the septum of the sample vial or that the sample probe is blocked. In some cases, the processor may be further configured to determine the predetermined threshold based on the composition of the fluid source, the composition of the sample in the sample vial, the volume of the sample vial, the flow rate or pressure measurement of the test vial, or a combination thereof.

[0017] In another embodiment, the processor in step (e) is further configured to: control the vial actuator to actuate the sample vial toward the sample probe in response to determining that the ejection procedure has failed; or control the vial holder to actuate, wherein the actuation occurs in response to determining that the ejection procedure has failed.

[0018] In another embodiment, the gas chromatography system may further include a heater in thermal communication with the sample vial, wherein the heater is configured to generate heating conditions for the sample vial, and wherein the processor is further configured to: receive a first set of signals from a pressure sensor; determine an initial pressure of the sample vial under the heating conditions based on the first set of signals; perform an extraction process of the contents of the sample vial; after the extraction process, receive a second set of signals from the pressure sensor; determine a second pressure of the sample vial; and control a fluid source or vent in fluid communication with the sample vial to restore the second pressure of the sample vial to the initial pressure.

[0019] In another aspect, the gas chromatography system may 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 configured to: (a) execute an ejection procedure to remove a sample vial from the sample probe; (b) receive a set of signals from the flow sensor; (c) detect whether the ejection procedure was successful based on the set of signals; and (d) in response to the detection, initiate one or more actions selected from remedies and alarms.

[0020] This aspect can include various implementation schemes. In one implementation scheme, the processor in step (c) is further configured to: determine the change in value within the set of signals; and determine, based on the change in value, whether the sample vial has been removed from the sample probe.

[0021] In another implementation, the system attempts to maintain a constant pressure level in the sample probe during steps (a) and (b).

[0022] In another implementation, the remedy may further include terminating the chromatography function if the processor detects a failed pop-up procedure.

[0023] In another embodiment, the processor in step (c) is further configured to: determine that no change in value has occurred within the set of signals; and determine, based on the set of signals, that the sample vial failed to be removed from the sample probe, or that the sample probe is stuck in the septum of the sample vial, or that the sample probe is blocked.

[0024] In another embodiment, the processor in step (e) is further configured to: control the vial actuator to actuate the sample vial toward the sample probe in response to determining that the ejection procedure has failed; or control the vial holder to actuate, wherein the actuation occurs in response to determining that the ejection procedure has failed.

[0025] In another aspect, the gas chromatography system may 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 configured to: (a) execute an ejection procedure to remove a sample vial from the sample probe; (b) allow fluid to flow through the fluid source to the sample probe; (c) receive a set of signals from the flow sensor during step (b); (d) detect whether the ejection procedure was successful based on the set of signals; and (e) initiate one or more actions selected from remedies and alarms in response to the detection.

[0026] This aspect can include various implementations. In one implementation, the gas chromatography system may further include a pressure sensor in fluid communication with a sample probe, wherein a subset of the set of signals is received from the pressure sensor.

[0027] In another embodiment, the processor in step (e) is further configured to: control the vial actuator to actuate the sample vial toward the sample probe in response to determining that the ejection procedure has failed; or control the vial holder to actuate, wherein the actuation occurs in response to determining that the ejection procedure has failed. Attached Figure Description

[0028] To gain a more complete understanding of the nature and intended purpose of the invention, reference is made to the following detailed description in conjunction with the accompanying drawings, wherein the same reference numerals denote corresponding parts in several views.

[0029] Figure 1 depicts a gas chromatography system according to an embodiment of the claimed invention.

[0030] Figure 2 illustrates the flow path of a headspace sampler according to an embodiment of the claimed invention.

[0031] Figure 3 illustrates a vial pressurized flow path configuration for a headspace sampler according to an embodiment of the claimed invention.

[0032] Figure 4 illustrates a sample ring filling flow path configuration for a headspace sampler according to an embodiment of the claimed invention.

[0033] Figure 5 illustrates the injection flow path configuration of a headspace sampler according to an embodiment of the claimed invention.

[0034] Figures 6 and 7 depict a sample vial sampling mechanism for a sample vial according to an embodiment of the claimed invention.

[0035] Figure 8 depicts the control system of a gas chromatography system according to an embodiment of the claimed invention.

[0036] Figures 9-14 depict pressure and flow rate measurements of a headspace sampler according to an embodiment of the claimed invention.

[0037] definition

[0038] The invention can be most clearly understood by referring to the following definitions.

[0039] Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” used herein include plural indicators.

[0040] Unless specifically stated or obvious from the context, as used herein, the term “about” is understood to mean within the normal tolerance range in the field, such as within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the specified value. Unless the context otherwise requires, all numerical values ​​provided herein are modified by the term “about”.

[0041] As used in the specification and claims, the terms “comprising,” “including,” “having,” etc., may have the meanings given to them by U.S. patent law and may mean “including,” etc.

[0042] Unless specifically stated or obvious from the context, the term "or" as used herein should be understood as inclusive. The term "set" as used in the specification and claims can include one or more objects contained therein.

[0043] The ranges provided in this document should be understood as abbreviations of all values ​​within that range. For example, the range 1 to 50 should be understood as including any number, combination of numbers, or subrange (and fractions thereof) selected from 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. Detailed Implementation

[0044] Gas chromatography system

[0045] The methods described herein can be implemented by a gas chromatography system, and the system described herein can be part of a gas chromatography system. Figure 1 illustrates an exemplary gas chromatography system. A gas chromatography system can inject, evaporate, separate, and detect components of a sample. Fluid flow through the system is depicted as a single-line arrow, such as arrow 175. However, those skilled in the art will understand that the invention described herein is not limited to the specific embodiment of the gas chromatography system depicted in Figure 1, nor to the specific component embodiments described in Figures 2-8, and that the invention described herein can be implemented by various gas chromatography systems and various system designs. For example, a gas chromatography system may include one or more samplers, inlets, columns, detectors, valves, gas control devices, heaters, etc.

[0046] Sample source

[0047] The headspace sample source 105 can contain any sample consisting of volatile components that partially evaporate and establish equilibrium with their low-volatility environment. A wide range of analytes can be used as the sample source 105 based on the typical temperatures associated with headspace sample analysis. In some cases, the sample source 105 can be stored prior to source extraction, for example, in vials or containers. The vials or containers can be sealed (substantially hermetically tight) by using a cap or other method to press a septum against the container, creating a substantially hermetically tight seal. The headspace sampler 120 receives the sample source 105 and establishes equilibrium between the volatile portion of the sample contained within the sample source 105 and the low-volatility components within the sample source 105. The seal of the equilibrated sample source 105 can be punctured by a syringe, needle, or other sample probe providing a conduit through which an aliquot of the volatile portion of the headspace sample within the sample source 105 is transferred to a gas chromatograph 180, where the aliquot is separated into its components for identification and / or quantification.

[0048] In some cases, the headspace sampler 120 may include devices for retrieving stored samples and positioning samples to be extracted from the container. For example, Figure 6 depicts a vial sampling mechanism for samples, which includes a holder 605 for positioning a sample vial 610 near a sample probe 615. In this example, the holder 605 is a circular turntable that is rotatably actuated perpendicular to the length of the probe 615. However, those skilled in the art will understand that other forms of retrieving and / or positioning sample vials for sample extraction can be implemented within the scope of this system, such as linear holders, any other vial manipulation robotic systems, etc. Furthermore, the holder 605 may include a set of boxes, each capable of holding a sample vial.

[0049] The headspace sampler 120 may further include a heating element (e.g., a resistance (ohmic or joule) heater) for controlling the temperature of the sample before and / or during extraction. For example, the entire holder 605 may be housed within the heating region. In headspace gas chromatography analysis, a sample probe can extract a sample through the headspace of a vial containing the sample. In some cases, the temperature of the liquid or solid sample in the vial can be increased to generate the headspace to be sampled. This can be achieved by increasing the temperature of the sample source 105. In other cases, the sample may be present in the gas phase at room temperature, thus eliminating the need to heat the vial. Typical temperature ranges from ambient temperature to 300°C.

[0050] To extract a sample from the vial for analysis, and as part of the extraction procedure, turntable 605 can be rotated until the vial 610 is positioned aligned with sample probe 615. Actuator 620 can then be actuated toward sample probe 615. In some cases, actuator 620 may include a lifting rod of a predetermined length, parallel to the length of sample probe 615. However, those skilled in the art will understand that other types of actuators can be implemented to actuate toward and / or away from the sample probe. When actuator 620 is actuated toward sample probe 615, actuator 620 may pass through a cavity holding the bottom of the vial 610 and force the vial 610 toward sample probe 615. Sample probe 615 may pierce the top of vial 610 (e.g., through the septum of vial 610), allowing sample probe 615 access to the contents stored in vial 610. Note that this is merely one embodiment of the mechanism for bringing the sample probe close to the contents stored in the vial. Additional mechanisms, including motors, motion conversion devices, and other combinations, can perform this task. Furthermore, besides moving the sample vial and keeping the sample probe stationary, the relative motion between the sample probe and the sample vial can be the result of the sample probe moving while the sample vial also moves or remains stationary.

[0051] The headspace sampler 120 may include a series of flow paths connected to the gas source 110 and the gas chromatograph 180. The flow paths provide fluid communication to extract a quantity of sample from the sample source and transfer it to the gas chromatograph for analysis. Furthermore, one or more proportional valves, one or more on / off valves, and / or a six-way valve can control which flow path(s) are connected at any given time. Figure 2 depicts an exemplary headspace sampler flow path.

[0052] The headspace sampler flow path implementation shown in Figure 2 may include various input / output channels. For example, the headspace sampler may include a flow path connected to vent 205, a flow path connected to vial pressurized gas source 210, a flow path connected to carrier gas source 215, a flow path connected to transfer line 220, and a flow path connected to sample probe 225. Vial pressurized gas source 210 and carrier gas source 215 may be part of gas source 110 of Figure 1. One or more of these flow paths may include a sample loop, such as sample loop 230. Alternatively, a sample trap may be used in place of the sample loop or as a supplement to the sample loop.

[0053] Various sensors and valves can be integrated into the headspace sampler flow path. These integrated sensors and valves help control and manage flow rates within the headspace sampler. For example, one or more sensors and one or more valves (not shown) can control the flow of carrier gas into carrier gas source 215. Flow sensor 240, pressure sensor 245, and proportional valve (PV1) 250 can be coupled to the flow path connected to the bottle pressurized gas source 210. Various types of flow sensors 240 can be used, including thermomass flow sensors.

[0054] Additionally, the on / off valve 255 can connect the flow path to the vial pressurization source 210 to the six-way valve 265. The proportional valve (PV2) 260 can connect the flow path to the vent 205 to the six-way valve 265 and / or the vial pressurization source 210. These valves, together with the aforementioned valves and the six-way valve, can control the introduction and extraction of various gases into and out of the headspace sampler.

[0055] One or more components of the flow path (e.g., sample probe 225, six-way valve 265, sample ring 230, and / or transfer line 220) can be heated. Typical temperature ranges are from ambient temperature to 300°C.

[0056] In some cases, the headspace sampler can pressurize the vial before sample extraction. Typical pressure ranges from ambient pressure to 75 psig (517 kPa). Figure 3 illustrates the vial pressurization flow path. During the pressurization phase, the six-way valve and multiple valves depicted in Figure 2 can be oriented to connect the sample probe to the vial pressurization gas source 210. The pressurized gas can flow into the flow path (e.g., through the sample ring 310 and the six-way valve 315), through the sample probe 320, and into the vial. The gas flow can increase the pressure in the vial and the connected flow path. Typical gases used for pressurizing the vial can include helium and nitrogen. Additionally, a carrier gas can flow through a flow path connected to the transfer line 305 and into the gas chromatograph.

[0057] The headspace sampler 120 can then implement a sample loop filling flow path, an example of which is shown in Figure 4. A six-way valve 415 can be oriented to connect the sample probe 420 to a vent, the pressure of which can be lower than the vial pressure (e.g., atmospheric pressure). Venting the sample probe can draw sample from the vial and into the sample loop flow path 410. Alternatively, the sample probe can draw sample from the vial into a trap. As headspace gas is vented from the vial into the sample loop, the pressure in the vial decreases. Furthermore, a transfer line 405 can be connected to a carrier gas input via the six-way valve 415.

[0058] The headspace sampler 120 can then implement an injection flow path, an example of which is shown in Figure 5. A six-way valve 515 can be oriented to connect a carrier gas source to a transfer line 505 via a sample ring 510. Typical carrier gases may include hydrogen, helium, nitrogen, and argon-methane. The carrier gas can flow into the flow path, forcing the sample in the sample ring 510 into the transfer line 505. The sample can then flow from the transfer line 505 to a gas chromatograph (GC), such as the GC 180 of Figure 1, for analysis. In some cases, the six-way valve orientation can also connect the sample probe 520 to a vent (e.g., vent 205 of Figure 2). In these cases, the vent can vent the sample vial connected to the sample probe (e.g., modifying the headspace pressure of the sample vial to ambient pressure or to a pressure lower than that reached during headspace sampling of the sample vial).

[0059] column

[0060] The separation of sample components can occur in column 135 of gas chromatograph 180. Column 135 may have a coating (e.g., a stationary phase) on its inner surface that interacts differently with different sample components. The interaction can be physical in nature (e.g., adsorption, “solvation,” sieving, etc.) rather than chemical. An exemplary column may be a capillary (e.g., 5 to 100 meters long and 0.1 to 0.5 millimeters in diameter) with a suitable polymer film coating on its walls. The column may further contain particles that can interact with the sample directly or due to the coating on the particles. In both cases, as sample components pass through the column, some components interact more strongly with the stationary phase and have longer retention times than others. Therefore, based on the differences in interaction with the stationary phase, sample components are carried by the carrier gas to the detector end of column 135 at different exit times.

[0061] Column temperature control

[0062] The interaction between sample components and the column can be regulated by controlling the temperature of column 135 (e.g., via column temperature control device 140 of gas chromatograph 180). In some samples, at a given temperature, some components may interact with column 135 minimally, while others may remain at the same temperature indefinitely. Therefore, column temperature control device 140 controls the column temperature precisely (and repeatably) as sample components migrate through column 135. This temperature control may involve increasing the temperature of column 135 during sample elution. When the last component elutes from the column, the temperature can be restored to the initial temperature before introducing the next sample. For some samples, the desired initial temperature may be below room temperature; for some samples, the desired initial temperature may be room temperature or close to room temperature; for others, the desired initial column temperature may be above room temperature.

[0063] detector

[0064] The separated components of the sample can be received or identified by detector 145 of gas chromatograph 180. Detector 145 can provide changes in electrical signals as some or all of the sample components elute from column 135.

[0065] Signal processors and data analyzers

[0066] Signal processor 150 can receive and process the electrical signal generated by detector 145. Signal processor 150 can be an analog-to-digital converter that converts the analog output of detector 145 into a digital signal that can be used by data analyzer 155. Data analyzer 155 can convert the gas chromatographic signal received from signal processor 150 into compound identification and calibration quantities. In some cases, signal processor 150 and / or data analyzer can be external to gas chromatograph 180.

[0067] Input / output devices

[0068] Input / output device 165 can receive input from the gas chromatography system and / or display output from the gas chromatography system. Input / output device 165 can be an analog switch, keyboard, and display. Alternatively, setpoint input and system monitoring can be performed via an external computer with appropriate software. In some cases, input / output device 165 can be housed on the headspace sampler, on various parts of the gas chromatograph, or external to the chromatograph.

[0069] control system

[0070] The control system 160 can be an electronic device programmed to control the operation of the gas chromatography system to achieve desired results. The control system 160 can be programmed to automatically execute gas chromatography protocols without input (from feedback devices or a user), or it can incorporate such input. For example, in Karl Johan Astrom and Richard M. Murray's… Feedback Systems:An Introduction for Scientists&Engineers The principle of how to use feedback (e.g., from a temperature sensor) to regulate component operation is described in (2008).

[0071] Control system 160 can be a computing device, such as a microcontroller (e.g., a device that can be accessed from...). or IOIO TM Trademark acquisition), general-purpose computers (e.g., personal computers or PCs), workstations, mainframe computer systems, etc. An exemplary control system is illustrated in Figure 8. The control system 800 may include a processor device (e.g., 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.

[0072] The processor 802 can be any type of processing device used to execute instructions, process data, etc.

[0073] 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.

[0074] Storage device 806 can be any data storage device for reading from / writing to / from any removable and / or integrated optical, magnetic, and / or opto-magnetic storage media, such as hard disks, optical disc read-only memories (CD-ROMs), CD rewritable ROMs (CDRWs), digital versatile optical disc ROMs (DVD-ROMs), DVD-RWs, etc. Storage device 806 may further include a controller / interface for connection to system bus 810. Therefore, memory devices 804 and 806 are suitable for storing data and instructions for programmed processes executed on processor 802.

[0075] User interface 808 may include a touch screen, control panel, keyboard, keypad, display, or any other type of interface, which can be connected to system bus 810 through corresponding input / output device interfaces / adapters.

[0076] Communication interface 812 can be adapted and configured to communicate with any type of external device or other components of the gas chromatography system. For example, double-lined arrows (such as arrow 170 in Figure 1) illustrate electronic communication between control system 160 and other components of the gas chromatography system. Communication interface 812 can be further adapted and configured to communicate with any system or network, such as one or more computing devices on a local area network (“LAN”), wide area network (“WAN”), the Internet, etc. Communication interface 812 can be directly connected to system bus 810, or it can be connected via a suitable interface.

[0077] Therefore, the control system 800 can provide execution processes, which may include algorithms for controlling components of the gas chromatography system according to the claimed invention, by itself and / or in cooperation with one or more additional devices. The control system 800 can be programmed or instructed to execute these processes according to any communication protocol and / or programming language on any platform. Therefore, these processes can be embodied in data and instructions stored in memory device 804 and / or memory device 806 or received at user interface 808 and / or communication interface 812 for execution on processor 802.

[0078] In some cases, the control systems used for the headspace sampler and the gas chromatograph can be the same or different control systems, and the control system can be housed on the headspace sampler, the gas chromatograph, or both, or housed on an external device.

[0079] Removal of sample vials

[0080] After a sample is extracted from the vial vial using the extraction procedure, the gas chromatography system may attempt to remove the vial from the sample probe. As previously described, Figure 6 depicts an actuator 620 that moves the vial 610 upward, thereby allowing the sample probe 615 to approach the contents of the vial 610. Figure 7 depicts successful removal of the vial 610 from the sample probe 615. The actuator 620 can be actuated distally away from the sample probe 615. In some cases, the actuator 620 can be actuated at one or more predetermined rates to perform a controlled descent away from the sample probe 615. Furthermore, the sample probe 615 may include a compression spring (as shown in Figure 7). When the sample probe 615 is in a position close to the contents of the vial 610 (e.g., as shown in Figure 6), the compression spring can be compressed. When the actuator 620 retracts away from the sample probe 615, the compression spring can be decompressed. This decompression can initiate a distal force away from the sample probe 615, thereby forcing the vial 610 away from the sample probe 615. Figure 7 shows the compression spring 625 in decompression mode. Furthermore, those skilled in the art will understand that the compression springs depicted in Figures 6 and 7 are merely examples of devices for removing sample vials from the vial holder, and that the gas chromatography system discussed herein may use other forms of force (e.g., gravity, elastomers, pistons, fluid bladders, Belleville washer, etc.) to provide distal force away from the sample probe.

[0081] However, in some cases, the sample vial may fail to be removed from the sample probe. For example, the sample probe may become stuck when its opening is within the headspace of the sample vial or within the septum of the sample vial. This could be due to friction between the sample probe and the septum, low force in the ejector spring, friction between the sample vial and nearby components, misalignment of the sample vial holder or other alignment problems, or other reasons. In some cases, the sample vial may be partially removed from the sample probe (e.g., the vial is partially repositioned back into the turntable's cassette). In the example mechanism of Figure 7, if the sample vial 610 is stuck on the sample probe, the actuator 620 is still able to retract fully to its rest position. Therefore, simply detecting the position of the lifting rod using an encoder or other position sensors known in the art is insufficient to determine whether the sample vial has been removed from the sample probe. These failed removal attempts can cause significant problems for gas chromatography systems, as conventional systems may fail to recognize the failure of the vial to be successfully removed from the probe and continue normal system processes (e.g., preparing the system for another chromatographic run, attempting to actuate another sample vial to the sample probe, etc.). Unidentified removal failures can ultimately lead to damage to the gas chromatography system, vial breakage, additional maintenance, etc.

[0082] Detecting the presence of headspace vials

[0083] A gas chromatography system can be configured to sense the presence of a sample vial on a sample probe. After sample extraction from the vial, the gas chromatography system can utilize fluid parameter sensors in the flow path to detect parameter values ​​within the corresponding flow path. Subsequently, the gas chromatography system can identify from the sensed parameter values ​​whether the vial remains on the sample probe, whether the vial has been successfully removed from the probe, and so on. In some cases, the gas chromatography system can be further configured with a headspace sampler (e.g., a six-way 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 Figure 3. The examples below rely on the physical components and flow paths depicted in Figures 1 and 2. However, those skilled in the art will understand that the invention described herein can be implemented in various gas chromatography systems, particularly those with different flow path configurations and the location or presence of fluid parameter sensors. For example, systems including pressure sensors and / or flow sensors in fluid communication with the sample probe can implement the techniques described herein.

[0084] Flow path configuration

[0085] Sensors in a gas chromatography system can monitor pressure and / or flow rate within one or more flow paths of a headspace sampler. The headspace sampler can be configured to provide access to a flow path connected to a sample probe via at least one of the pressure or flow rate sensors in the gas chromatography system. For example, in Figure 2, the headspace sampler can be configured to open a switching valve 255 to provide access for flow sensor 240 and / or pressure sensor 245 to measure pressure and / or flow rate in the flow path fluidly connected to the sample probe.

[0086] Based on the above example, the headspace sampler can be configured to use proportional valves 250 and / or 260 of Figure 2 to modify the pressure or flow rate of the gas connected to the sample probe. Feedback from sensors such as flow sensor 240 and pressure sensor 245 can be used to control the valves.

[0087] Passive pneumatic monitoring of the small bottle

[0088] The gas chromatography system can detect whether the vial has been successfully removed from probe 225 by taking measurements during the vial ejection procedure.

[0089] After retrieving the sample from the vial or aborting sample retrieval, the gas chromatography system may attempt to eject the vial from the sample probe. For example, as described above with reference to Figures 6 and 7, the ejector lever can be actuated distally away from the sample probe.

[0090] After the sample is retrieved from the vial, the gas chromatography system can increase, decrease, or maintain the vial pressure at approximately the same level as at the end of ring filling, so that the vial is pressurized at a non-ambient pressure at the start of the ejection procedure. During the ejection procedure, sensors coupled to the sample probe flow path can measure parameters such as pressure and / or flow rate through the flow path. In some cases, the gas chromatography system can then compare measurements taken during the ejection procedure when the vial is still expected to be on the sample probe (e.g., near the start of the ejection procedure) with measurements taken during the ejection procedure when the vial is expected to have been removed from the sample probe (e.g., near the end of the ejection procedure). The expected time when the vial has been removed from the sample probe can be based on the time elapsed since the start of the ejection attempt, the lifter position monitored by an encoder or other position sensor, etc. In other cases, the gas chromatography system can compare measurements taken during the ejection procedure when the vial is expected to have been removed from the sample probe (e.g., near the end of the ejection procedure) with a predetermined value or threshold (e.g., approximate ambient pressure, etc.). In other cases, a gas chromatography system can look for changes in the measured value during the ejection procedure (e.g., step changes, changes above a threshold, etc.). The measured value sensed by the sensor may depend on whether the vial successfully ejects from the sample probe. If the vial successfully ejects from the sample probe, the fluid path connected to the sample probe will be open to atmospheric pressure, rather than being confined within the pressurized vial.

[0091] For example, the sample probe can be fluidly connected to a pressure sensor, with virtually no gas flowing through the sample probe, and the vial is pressurized to a pressure above ambient pressure at the start of the ejection procedure. In the exemplary flow path shown in Figure 2, this can be achieved by closing proportional valves 250 and 260, opening switching valve 255, and directional six-way valve 265 to fluidly connect the sample probe to pressure sensor 245. If the sample vial is successfully removed from the sample probe, the pressure sensor (e.g., pressure sensor 245) can sense the pressure change (e.g., a decrease) as the flow path fluidly connected to the sample probe becomes open to atmospheric pressure, where the initial value of the sensed parameter appears during sensing when the sample vial is expected to still be on the sample probe. This pressure change occurs because the pressure sensor transitions from a pressurized environment (headspace) fluidly connected to the inside of the sample vial to being open to the atmosphere as the sample vial is removed from the sample probe.

[0092] As another example, the sample probe can be fluidly connected to a flow sensor and a pressure sensor, allowing gas to flow through the sample probe and pressurizing the vial to a non-ambient pressure at the start of the ejection procedure. The gas flow rate can be substantially constant. In the exemplary flow path shown in Figure 2, this can be achieved by opening a switching valve 255 and optionally a proportional valve 260, and orienting a six-way valve 265 such that the sample probe is fluidly connected to a pressure sensor 245 and a flow sensor 240. The flow sensor 240 can be used to control the flow rate through the flow path by controlling the proportional valve 250. If the sample vial is successfully removed from the sample probe, the pressure sensor (e.g., pressure sensor 245) can sense a change in pressure (e.g., a decrease) when the flow path fluidly connected to the sample probe becomes open to atmospheric pressure, wherein the initial values ​​of the sensed parameters are present during sensing, while the sample vial is still expected to be on the sample probe (e.g., the sample probe is fluidly connected to the interior of the pressurized sample vial). As gas flows through the flow path, the pressure sensed by the pressure sensor 245 may be higher than atmospheric pressure due to any fluid restriction in the flow path between the pressure sensor 245 and the opening in the sample probe.

[0093] Alternatively, as another example, the sample probe can be fluidly connected to a flow sensor and a pressure sensor, with the pressure in the vial controlled to a setpoint during the ejection procedure. In the exemplary flow path shown in Figure 2, this can be achieved by closing proportional valve 260, opening switching valve 255 and directional six-way valve 265, such that the sample probe is fluidly connected to pressure sensor 245 and flow sensor 240. Proportional valve 250 can be used to control the pressure in the vial fluidly connected to the sample probe by adjusting the pressurized gas in the vial according to the setpoint of pressure sensor 245. If the vial is successfully removed from the sample probe, the flow rate will increase (e.g., an increase in variation) as the vial is removed, as measured by flow sensor 240, because the controller attempts to maintain the pressure in the flow path connected to the sample probe while the flow path is open to atmospheric pressure, where the initial values ​​of the sensed parameters occur during the sensing period, when the vial is still expected to be on the sample probe (e.g., the sample probe is fluidly connected to the headspace of the pressurized vial). Depending on the pressure setpoint, limitations of the connection path, and gas viscosity, a headspace sampler may fail to maintain the pressure setpoint. In some cases, this could also be an indication that the vial has successfully ejected.

[0094] If the vial fails to eject successfully from the sample probe, the sensor can sense the static value of the sensed parameter during the vial ejection procedure. Alternatively, for example, when the vial is introduced at a constant flow rate during ejection, the sensor can sense the pressure increase to the maximum value allowed by the system (e.g., 75 psi could be the maximum applied during vial pressurization, but the maximum allowed by the system could be 100 psi). In another case, if the sample probe is trapped in the septum of the vial, or if the sample probe is blocked, the sensor can sense the essentially static value of the sensed parameter during the vial ejection procedure. Figures 9-11 show graphs of flow rate and pressure measurements for an example gas chromatography system implementing the above methods. The flow rate and pressure measurements are for the flow path fluidly connected to the sample probe of the gas chromatography system. Figure 9 depicts a case where the sample vial is successfully ejected, Figure 10 depicts a case where the sample vial is not successfully ejected, and Figure 11 depicts a case where the sample probe is blocked (e.g., due to the septum or sample stuck in the sample probe) or the opening of the sample probe is stuck in the septum of the vial.

[0095] Successful pop-up example

[0096] Figure 9 is a timing diagram of an embodiment of the claimed invention, depicting pressure and flow rate measurements during a successful vial ejection. As described above, in events A and B, the gas chromatography system can connect the vial to the sample probe flow path and the pressurized gas in the vial, and pressurize the contents of the vial. The headspace sampler can then fill the sample ring with the sample, for example, by fluidly connecting the sample probe and the sample ring to the vent, as described by event C. At event D, the gas chromatography system can deliver the contents of the sample ring to the transfer line and the gas chromatograph by fluidly connecting the sample ring to the carrier gas source.

[0097] At event E, the gas chromatography system can execute the vial ejection procedure. The system can be configured to close proportional valves 250 and 260 of Figure 2 using the headspace sampler. Therefore, the headspace sampler does not experience gas input from the individual sensors fluidly connected to the sample probe, but a pressure higher than atmospheric pressure exists in the vial at the start of the ejection procedure. During event E, as the vial leaves the sample probe, the gas chromatography system can measure the pressure drop, for example using pressure sensor 245 of Figure 2. Based on the pressure drop, the gas chromatography system can determine that the vial has been successfully removed and continue operating according to the normal procedure. At event F, the system can purge the sample probe and vent. Then, at event G, the system can purge only the sample probe and initiate standby mode at event H to await another vial.

[0098] Example of sample vials stuck on probes

[0099] Figure 10 illustrates pressure and flow rate measurements during the ejection of a failed vial, according to an embodiment of the claimed invention. The measurements depicted in Figure 10 relate to the case where the vial remains on the sample probe after the ejection procedure performed by the headspace sampler.

[0100] Events A, B, C, and D are as described above in relation to Figure 9.

[0101] At event E, the gas chromatography system can execute a vial ejection procedure. The system can be configured to close proportional valves 250 and 260 of Figure 2. During the ejection procedure, the headspace sampler does not experience gas input from the various sensors fluidly connected to the sample probe, but a pressure higher than atmospheric pressure exists in the vial. Since the vial remains on the sample probe during the ejection procedure, the gas chromatography system experiences essentially static pressure in the flow path fluidly connected to the sample probe. Therefore, the gas chromatography system can, for example, use pressure sensor 245 of Figure 2 to identify the static pressure value in the probe connection flow path. Based on the static pressure measurement (e.g., pressure value remains within a predetermined threshold, pressure change rate remains within a predetermined threshold, etc.), the gas chromatography system can determine that the vial remains on the sample probe and that the vial ejection has failed. If the system continues the normal cleaning operation for events F, G, and H, the pressure reading will increase because the sample probe is fluidly connected to the vial (e.g., gas flows into the closed volume).

[0102] Examples of probe blockage or probe stuck in septum

[0103] Figure 11 illustrates pressure and flow rate measurements according to an embodiment of the claimed invention in the case of a blocked probe or probe opening stuck in a vial septum. The measurements depicted in Figure 11 relate to the situation where the sample probe is blocked or the sample probe opening is stuck in a vial septum during an ejection procedure performed by a gas chromatography system.

[0104] Events A, B, C, and D are as described above with reference to Figures 9 and 10.

[0105] At event E, the gas chromatography system may execute a vial ejection procedure. The system may be configured to close proportional valves 250 and 260 of Figure 2. During the ejection procedure, the headspace sampler does not experience gas input from the various sensors fluidly connected to the sample probe, but a pressure higher than atmospheric pressure exists in the vial. Because the sample probe is blocked or its opening is stuck in the vial septum during the ejection procedure, the gas chromatography system experiences essentially static pressure during the ejection procedure. Therefore, the gas chromatography system may, for example, use pressure sensor 245 of Figure 2 to measure the static pressure value in the probe connection flow path. Based on the static pressure measurement (e.g., the pressure value remains within a predetermined threshold, the rate of pressure change remains within a predetermined threshold, etc.), the gas chromatography system may determine that the vial remains on the sample probe and the vial ejection has failed, or this may mean that the probe is blocked. If the system continues normal operation for events F, G, and H, the pressure reading within the system will increase because the sample probe is not in communication with the atmosphere and therefore not with the confined volume within the system. In the event that the sample probe is blocked or the opening of the sample probe is stuck in the septum, the volume in the flow path connected to the sample probe is more limited than the volume of the sample probe opening in the internal volume (headspace) of the sample vial (e.g., the volume of the flow path connected to the sample probe will be the flow path between the pressure sensor 245 and the sample probe tip, and will not include the volume of the sample vial if the sample vial probe is blocked or the opening of the sample probe is stuck in the septum of the sample vial).

[0106] Furthermore, in some cases, the risk of probe clogging can be reduced by performing a limitation test before connecting the sample vial to the sample probe. For example, a gas chromatography system can flow gas through the sample probe and monitor the rate of pressure change at the sample probe. If the rate of pressure change exceeds a predetermined threshold, the gas chromatography system can determine that the sample probe is clogged (e.g., the rate of pressure change would be faster compared to an unclogged sample probe exposed to the environment). In other cases, the gas chromatography system can monitor the pressure value of the sample probe as gas flows through it. If the pressure value exceeds a predetermined threshold at a specified flow rate, the gas chromatography system can determine that the sample probe is clogged (e.g., the sample probe would reach a higher pressure value compared to an unclogged sample probe exposed to the environment). In still other cases, the gas chromatography system can monitor the continuous back pressure generated by a backup flow. If the back pressure exceeds a predetermined threshold, the gas chromatography system can determine that the sample probe is clogged.

[0107] If the gas chromatography system determines that the sample probe is not clogged (e.g., through a restriction procedure), the system can connect the sample vial to the sample probe. If the sample probe is not clogged before being connected to the sample vial, the likelihood of the sample probe becoming clogged during sampling is low.

[0108] Active pneumatic testing of the small bottle

[0109] Alternatively, a gas chromatography system can be configured with a headspace sampler to introduce pressurized gas into the flow path connected to the sample probe after it is expected that the vial has been ejected from the sample probe, to determine whether the vial has been successfully ejected. In some cases, this configuration allows the vial to be ventilated to ambient pressure before attempting to remove it from the sample probe, which can provide the additional benefit of ventilating the vial prior to post-ejection disposal or treatment.

[0110] Before ejecting the vial, the system can vent the vial to atmospheric pressure or a pressure lower than the final sampling pressure, giving the vial residual pressure from the sampling process, or otherwise increasing or decreasing the pressure in the vial, or keeping it constant relative to the end of the sampling process. The gas chromatography system can execute a vial ejection procedure and attempt to eject the sample vial from the sample probe. During the vial ejection procedure after the vial is expected to be removed from the sample probe (based on the time elapsed since the attempt to eject, the lifter position monitored by an encoder or other sensor, etc.), the gas chromatography system can configure the pressurized gas from the vial to flow into the connected flow path and through the sample probe. For example, the on / off valve 255 in the flow path shown in Figure 2 can be open, and the proportional valve 250 controls the gas flow rate through the sample probe or the pressure in the flow path connected to the sample probe. In some cases, the pressurized gas can flow through the flow path at a constant flow rate. One or more sensors coupled to the sample probe flow path (e.g., pressure sensor 245 and flow sensor 240 in Figure 2) can measure various parameters of the flow path, such as flow rate and / or pressure.

[0111] One or more connected sensors can sense the rate of change of pressure or flow rate in the connected flow path during the ejection procedure and as gas flows into the connected flow path. The rate of change of the measured parameter depends on whether the vial successfully ejects from the sample probe. For example, when the vial successfully ejects from the sample probe, one or more sensors can measure a slow increase (e.g., pressure value). Alternatively, when the vial fails to eject successfully from the sample probe, if the sample probe is trapped in the septum of the vial, or if the sample probe is blocked, one or more sensors can measure a rapid increase (e.g., pressure value). The possibility of probe blockage can be limited by performing a constraint test before sampling the vial. These differences in rate of change may depend on the volume of gas flowing in.

[0112] For example, after anticipating that the vial has been removed from the sample probe, the system can attempt to control the gas flow rate through the sample probe to a set point (e.g., by using flow sensor 240 and proportional valve 250), and can measure the pressure in the flow path coupled to the sample probe (e.g., by using pressure sensor 245 in Figure 2). If the vial is still on the sample probe, or if the sample probe is blocked or trapped in the vial septum, gas flows into a confined volume (e.g., the flow path, the sample probe, and in some cases, the vial). Therefore, the sensed pressure will increase rapidly. Alternatively, if the vial has been successfully removed, the gas will flow out of the sample probe and into the surrounding environment (i.e., a larger volume). Therefore, the sensed pressure will increase more slowly (if it can be measured). The pressure value within a given time after the measurement begins can also indicate whether the vial has been successfully ejected. For example, if the vial has been successfully ejected, given a constant gas flow rate through the sample probe, the pressure will increase to a value depending on the confinement between the pressure sensor and the sample probe outlet, the gas viscosity, and the flow rate. Alternatively, if the sample vial fails to eject successfully, the pressure will increase to a higher value as gas flows into the closed system.

[0113] In some cases, the pressure in the flow path connected to the sample probe can be controlled to attempt to reach a pressure setpoint after the sample vial is expected to be removed from the sample probe, and the gas flow rate required to reach that setpoint can be measured (e.g., by monitoring flow sensor 240 in Figure 2). In these cases, the gas chromatography system can increase the flow rate of the flowing gas until the pressure setpoint is reached (e.g., by monitoring the pressure value from a pressure sensor (e.g., pressure sensor 245 in Figure 2) connected to the flow path to the sample probe). If and when the pressure setpoint is reached, the gas chromatography system can identify the flow rate required to satisfy the pressure setpoint. Depending on the pressure setpoint, the limitations of the connected flow path, and the gas viscosity, the headspace sampler may not be able to reach the pressure setpoint. In some cases, this may also be an indication of successful vial ejection. If the sample vial does not eject successfully, and the sample probe remains in fluid communication with the sample vial, a lower flow rate is required to reach the pressure setpoint compared to if the sample vial successfully ejected from the sample probe. In some cases, the flow rate may be essentially zero if ejection is unsuccessful.

[0114] Additionally or alternatively, the system can identify the time taken to reach the pressure setpoint. If the ejection procedure is successful, it may take longer to reach the pressure setpoint compared to a failed ejection procedure using the same flow rate. Based on these monitoring values, the system can identify whether the vial was successfully ejected from the sample probe.

[0115] Figures 12-14 show graphs of flow rate and pressure measurements of the gas chromatography system used to perform the above measurement examples. The flow rate and pressure measurements are performed on the flow path fluidly connected to the sample probe of the gas chromatography system. Figure 12 depicts a case where the sample vial is successfully ejected, Figure 13 depicts a case where the sample vial is not successfully ejected, and Figure 14 depicts a case where the sample probe is blocked.

[0116] Example of successful ejection of the small bottle

[0117] Figure 12 illustrates pressure and flow rate measurements during successful vial ejection according to an embodiment of the claimed invention. As described above, in events A and B, the gas chromatography system can connect the vial to the sample probe flow path and the vial pressurizing gas, and pressurize the contents of the vial. The headspace sampler can then fill the sample loop with the sample, for example by fluidly connecting the sample probe to the vent, as described in event C. At event D, the gas chromatography system can deliver the contents of the sample loop to the transfer line and GC column by fluidly connecting the sample loop to the carrier gas source. Optionally, at event D, the system can also vent the vial to a pressure setpoint or pressurize the vial to a setpoint.

[0118] At event E, the gas chromatography system can execute the sample vial ejection procedure. The system can attempt to remove the sample vial from the sample probe. During the ejection procedure, after the expected removal of the vial from the sample probe, the gas chromatography system can allow gas to flow through the flow path connected to the sample probe. As the vial successfully ejects from the sample probe, the pressure will increase to a value based on the limit of the flow path between the pressure sensor and the sample probe outlet, gas viscosity, and flow rate. The pressure value may be lower than the pressure value when the sample probe is still in the sample vial. At event F, the system can purge the sample probe and vent. Then, the system can purge the sample probe at event G and initiate standby mode at event H to await another sample vial.

[0119] Example of sample vials stuck on probes

[0120] Figure 13 illustrates pressure and flow rate measurements during the ejection of a failed vial according to an embodiment of the claimed invention. The measurements described in Figure 13 pertain to a situation where, during and after the ejection procedure performed by a gas chromatography system, the vial remains on a sample probe, the opening of which is fluidly connected to the internal volume (headspace) of the vial.

[0121] Events A, B, C, and D are as described above with reference to Figure 12.

[0122] At event E, the gas chromatography system may execute the sample vial ejection procedure. During the ejection procedure, after the vial is expected to be removed from the sample probe, the gas chromatography system may allow gas to flow through the flow path connected to the probe. While the sample vial remains on the sample probe, the flow path is connected to a predetermined volume (e.g., the volume of the sample vial). As the gas flows through the flow path, the pressure within the flow path will increase at a greater rate than when the sample probe is open to the surrounding environment. Therefore, the gas chromatography system can identify the increased pressure value in the flow path connected to the probe. Based on the rate of pressure increase or the pressure reached by the flow rate, the gas chromatography system can determine that the sample vial remains on the sample probe and the ejection procedure has failed. If the system continues normal operation for events F, G, and H, the pressure reading will increase due to the predetermined volume of gas flowing within the system.

[0123] Examples of probe blockage or probe stuck in septum

[0124] Figure 14 illustrates pressure and flow rate measurements under conditions of probe blockage according to one embodiment of the invention. The measurements depicted in Figure 14 relate to a situation where the sample probe is blocked or the opening of the sample probe is stuck in the vial septum during an ejection procedure performed by the gas chromatography system.

[0125] Events A, B, C, and D are as described above with reference to Figures 12 and 13.

[0126] At event E, the gas chromatography system may execute a vial ejection procedure. The system may attempt to remove the vial from the sample probe. During the ejection procedure, after the expected removal of the vial from the sample probe, the gas chromatography system may allow pressurized gas to flow into the flow path connected to the probe. When the sample probe is blocked or its opening is stuck in the vial septum, the flow path is fluidly connected to a predetermined volume (even smaller than if the sample probe were stuck in the sample probe opening within the internal volume of the vial). As the gas flows through the flow path, the pressure within the flow path will increase at a greater rate than if the sample probe were open to the surrounding environment or stuck in the sample probe opening within the internal volume of the vial. Therefore, the gas chromatography system can identify the increased pressure value in the flow path connected to the probe. Based on the rate of pressure increase or the pressure reached for a specified flow rate, the gas chromatography system can determine that the sample probe is blocked or stuck in the vial septum, and the ejection procedure has failed. If the system continues normal operation for events F, G, and H, the pressure reading within the system will increase due to the limited volume within the system.

[0127] It should be noted that because the volume of the flow path is smaller than the probe opening remaining in the sample vial, the pressure will increase more rapidly if the probe is trapped by a clogged septum. Similarly, when reaching the pressure setpoint, the flow rate and / or time required for the system to meet the predetermined pressure setpoint will be lower when the probe is clogged or trapped by a septum, compared to when the sample probe opening remains in the volume of the sample vial.

[0128] Parameter threshold

[0129] Before executing the ejection procedure, parameter thresholds can be determined by the gas chromatography system. In some cases, parameter thresholds (e.g., step change threshold, rate of change threshold, etc.) can be determined by different characteristics of the sample, vial, and / or headspace sampler. For example, vial volume, solvent composition, headspace composition, pressurized gas composition, flow path limitations, etc., can be used to determine the thresholds used by the system to identify whether the vial has been successfully ejected from the sample probe. In some cases, some of these characteristics can be input by the user of the gas chromatography system. Additionally or alternatively, some of these characteristics can be determined by the gas chromatography system (e.g., sensed).

[0130] In some cases, it is not necessary to calculate parameter thresholds based on the measured parameter values. For example, if no gas flows through the flow path connected to the probe and the sample vial was previously pressurized, the pressure will drop to ambient pressure if the vial is successfully ejected, regardless of the vial's parameters.

[0131] In other cases, the threshold can be calculated based on the measured parameters, or the test vial can be placed on the probe before the sampling procedure. The test vial can then be ejected while measuring the flow rate and / or pressure. These flow rate and / or pressure values ​​can then be used to determine the threshold. It can be confirmed that the test vial has been ejected manually by the user or by another part of the system (e.g., by sensing that the vial eventually returns to its storage location).

[0132] System Remedies

[0133] Once the gas chromatography system detects that the sample vial has not successfully ejected from the sample probe, the system can implement various remedial procedures. For example, the system can terminate the chromatographic function, such as preparing another sample vial for sampling. In some cases, the system can generate and transmit (e.g., via the control system of Figure 1) a notification, which includes information corresponding to the unsuccessful ejection attempt. In some cases, the lifting lever of Figures 6 and 7 can be configured to actuate toward the sample probe, which can re-energize the compression spring 625 and may release the sample vial during a second ejection attempt and / or prevent the sample vial from falling from the sample probe. In some cases, the holder of Figures 6 and 7 can be actuated to rotate or swing, which can tap the sample vial 610 and may release the sample vial 610. Similar mechanisms for tapping or re-engaging the sample vial can be performed by the ejection mechanism, and those skilled in the art will understand that the examples provided above are not self-limiting.

[0134] Sample vial pressure recovery

[0135] A gas chromatography system can be configured to restore the pressure of the vial after sample extraction. When the sample is loaded into the vial and sealed, the vial is typically at or near ambient temperature and pressure. After being placed in the headspace sampler in preparation for sampling, the vial can be heated to a high temperature. This causes the pressure in the vial, which is a closed system, to increase. Before the sample is extracted from the vial, the headspace sampler can connect a sample probe to the flow path using at least one coupled sensor. For example, the system can connect the vial to sample probe 225 in the flow path of Figure 2, while simultaneously closing proportioning valves 250 and 260 to prevent gas from entering or leaving the vial, but opening switch valve 255 to fluidly connect pressure sensor 245 to sample probe 225. In some cases, when the vial is placed on the sample probe before pressurizing it with gas and / or extracting the sample, the coupled sensor can measure the pressure in the flow path and thus the pressure in the vial.

[0136] Furthermore, after extraction, the gas chromatography system can measure the pressure of the sample vial. For example, the same configuration used to measure vial parameters can be used to measure parameters after extraction. Alternatively, another configuration can be used for post-extraction measurements. The system can identify (e.g., via the control system of Figure 1) the pressure difference of the sample vial after extraction relative to before extraction. Furthermore, the system can allow pressurized gas or carrier gas to flow 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 vent gas from the sample vial to restore the pressure of the sample vial to the level before extraction. This can be implemented by monitoring the pressure value of the pressure sensor and identifying when the pressure value reaches the pressure setpoint.

[0137] Therefore, when the vial is removed from the heated position and returns to near its pre-analytical temperature (e.g., room temperature), the pressure inside the vial can return to levels close to ambient. When the pressure inside the vial is close to ambient pressure, the forces caused by the pressure difference are minimized. This reduces the risk of vial septum yielding or vial breakage due to structural weakening. Furthermore, the process can be independent of the contents, as it can depend on the pressure of the vial before and after extraction. This eliminates user errors, especially when the user enters incorrect parameters related to the sample (e.g., gas composition, solvent composition, etc.).

[0138] equivalent

[0139] Although preferred embodiments of the invention have been described using specific terminology, such description is for illustrative purposes only, and it should be understood that changes and variations may be made without departing from the spirit or scope of the appended claims.

[0140] By incorporating via reference

[0141] All patents, published patent applications and other references cited in this article are hereby explicitly incorporated in their entirety by reference.

Claims

1. A gas chromatography system, comprising: Sample probe; A fluid source in fluid communication with the sample probe; A pressure sensor in fluid communication with the sample probe; as well as Processor, the processor being configured to: (a) Execute the ejection procedure to remove the sample vial from the sample probe; (b) Receive a set of signals from the pressure sensor; (c) Detect whether the pop-up procedure was successful based on the group signal; and (d) In response to the detection, initiate one or more actions selected from remediation and alarms.

2. The gas chromatography system of claim 1, wherein, The processor in step (c) is further configured to: Determine the changes in values ​​within the group of signals; and The change in the value determines whether the sample vial has been removed from the sample probe.

3. The gas chromatography system of claim 1, wherein, The remedy further includes terminating the chromatography function if the processor detects a failed pop-up procedure.

4. The gas chromatography system according to claim 1, wherein, During step (a), the pressure readings of the group signals are measured to be below or within a predetermined threshold, or to atmospheric pressure when the ejection procedure is successful, and the predetermined threshold is determined by the processor based on vial volume, solvent composition, headspace composition, pressurized gas composition, flow path limitation, flow rate or pressure measurement of the test vial, or a combination thereof.

5. The gas chromatography system according to claim 1, wherein, The processor in step (c) is further configured to: It was determined that no value change occurred within the group of signals; and Based on the set of signals, it is determined that the sample vial failed to be removed from the sample probe, or the sample probe was stuck in the septum of the sample vial, or the sample probe was blocked.

6. The gas chromatography system according to claim 1, wherein, The processor in step (e) is further configured to: In response to determining that the ejection procedure has failed, control the vial actuator to actuate the sample vial toward the sample probe; or Actuation of the vial holder is controlled, wherein the actuation occurs in response to determining that the ejection procedure has failed.

7. The gas chromatography system according to claim 1, further comprising: A heater in thermal communication with the sample vial, wherein the heater is configured to generate heating conditions for the sample vial, wherein the processor is further configured to: Receive a first set of signals from the pressure sensor; The initial pressure of the sample vial under the heating condition is determined based on the first set of signals; Execute the procedure for extracting the contents of the sample vial; After the extraction procedure, a second set of signals is received from the pressure sensor; Determine the second pressure of the sample vial; and Control the fluid source or vent that is in fluid communication with the sample vial to restore the second pressure of the sample vial to the initial pressure.

8. A gas chromatography system comprising: Sample probe; A fluid source in fluid communication with the sample probe; A pressure sensor in fluid communication with the sample probe; as well as Processor, the processor being configured to: (a) Execute the ejection procedure to remove the sample vial from the sample probe; (b) During step (a), fluid is directed to the sample probe via the fluid source; (c) Receive a set of signals from the pressure sensor during step (b); (d) Detect whether the pop-up procedure was successful based on the group signal; and (e) In response to the detection, initiate one or more actions selected from remediation and alarms.

9. The gas chromatography system of claim 8, further comprising a flow sensor in fluid communication with the sample probe, wherein, A subset of the group of signals is received from the flow sensor.

10. The gas chromatography system according to claim 8, wherein, The processor in step (d) is further configured to: Determine the changes in values ​​within the group of signals; and The change in the value determines whether the sample vial has been removed from the sample probe.

11. The gas chromatography system according to claim 8, wherein, The processor in step (d) is further configured to: Determine the rate of change within the group of signals; Determining that the rate of change is below a predetermined threshold; and The pop-up program was confirmed to have succeeded.

12. The gas chromatography system according to claim 8, wherein, The processor in step (d) is further configured to: Determine the rate of change within the group of signals; Determine that the rate of change exceeds a predetermined threshold or is within a predetermined threshold; and Based on the set of signals, it was determined that the sample vial failed to be removed from the sample probe.

13. The gas chromatography system according to claim 8, wherein, The processor in step (d) is further configured to: Determine the rate of change within the group of signals; Determine that the rate of change exceeds a predetermined threshold; and Based on the set of signals, it is determined that the sample probe is trapped in the septum of the sample vial or that the sample probe is blocked.

14. The gas chromatography system according to claim 8, wherein, The processor in step (e) is further configured to: In response to determining that the ejection procedure has failed, control the vial actuator to actuate the sample vial toward the sample probe; or Actuation of the vial holder is controlled, wherein the actuation occurs in response to determining that the ejection procedure has failed.

15. The gas chromatography system according to claim 8, further comprising: A heater in thermal communication with the sample vial, wherein the heater is configured to generate heating conditions for the sample vial, wherein the processor is further configured to: Receive a first set of signals from the pressure sensor; The initial pressure of the sample vial under the heating condition is determined based on the first set of signals; Execute the procedure for extracting the contents of the sample vial; After the extraction procedure, a second set of signals is received from the pressure sensor; Determine the second pressure of the sample vial; and Control the fluid source or vent that is in fluid communication with the sample vial to restore the second pressure of the sample vial to the initial pressure.

16. A gas chromatography system comprising: Sample probe; A fluid source in fluid communication with the sample probe; A flow sensor in fluid communication with the sample probe; as well as Processor, the processor being configured to: (a) Execute the ejection procedure to remove the sample vial from the sample probe; (b) Receive a set of signals from the flow sensor; (c) Detect whether the pop-up procedure was successful based on the group signal; and (d) In response to the detection, initiate one or more actions selected from remediation and alarms.

17. The gas chromatography system according to claim 16, wherein, The processor in step (c) is further configured to: Determine the changes in values ​​within the group of signals; and The change in the value determines whether the sample vial has been removed from the sample probe.

18. The gas chromatography system according to claim 16, wherein, The system attempts to maintain a constant pressure level in the sample probe during steps (a) and (b).

19. The gas chromatography system according to claim 16, wherein, The remedy further includes terminating the chromatography function if the processor detects a failed pop-up procedure.

20. The gas chromatography system according to claim 16, wherein, The processor in step (c) is further configured to: It was determined that no value change occurred within the group of signals; and Based on the set of signals, it is determined that the sample vial failed to be removed from the sample probe, or the sample probe was stuck in the septum of the sample vial, or the sample probe was blocked.

21. The gas chromatography system according to claim 16, wherein, The processor in step (e) is further configured to: In response to determining that the ejection procedure has failed, control the vial actuator to actuate the sample vial toward the sample probe; or Actuation of the vial holder is controlled, wherein the actuation occurs in response to determining that the ejection procedure has failed.

22. A gas chromatography system comprising: Sample probe; A fluid source in fluid communication with the sample probe; A flow sensor in fluid communication with the sample probe; as well as Processor, the processor being configured to: (a) Execute the ejection procedure to remove the sample vial from the sample probe; (b) To direct fluid through the fluid source to the sample probe; (c) Receive a set of signals from the flow sensor during step (b); (d) Detect whether the pop-up procedure was successful based on the group signal; and (e) In response to the detection, initiate one or more actions selected from remediation and alarms.

23. The gas chromatography system of claim 22, further comprising a pressure sensor in fluid communication with the sample probe, wherein, A subset of the group of signals received from the pressure sensor.

24. The gas chromatography system according to claim 22 or 23, wherein, The processor in step (e) is further configured to: In response to determining that the ejection procedure has failed, control the vial actuator to actuate the sample vial toward the sample probe; or Actuation of the vial holder is controlled, wherein the actuation occurs in response to determining that the ejection procedure has failed.

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