Sampling device

Abstract

A sampling device for adsorptive sampling, comprising a sample container, a sorbent sample probe, and an actuator, such as a robotic arm (6). The sample container (2) is arranged for containing a liquid to be sampled. The sample probe (10) has a probe section comprising a sorbent material, the probe section being configured to be inserted into the sample container. The probe section comprises sorbent material arranged to acquire an analyte from the sample container. The actuator is configured to be independently connected to and to independently manipulate both the sample container and the sample probe. The sample probe (10) is detachably connectable to the actuator, such that the actuator can be connected to and detached from the sample probe in use, to selectively interchange the sample probe connected to the actuator with a further sample probe.

Description

[0001] This invention relates to sampling apparatus, and more particularly to apparatus for the automated sampling and analysis of liquid and gas samples.

[0002] Sampling and analytical techniques are commonly used to analyze liquids to identify their components. Examples include identifying contaminants in drinking water, fragrance allergens in cosmetics, or aroma profiling in beverages. Analysis of low levels of organic compounds in aqueous matrices presents significant challenges for performing rapid, sensitive, and automated analyses. Such analyses are often performed after extraction and concentration steps, frequently involving liquid-liquid extraction (LLE) or solid-phase extraction (SPE).

[0003] Solid-phase extraction can be achieved, for example, using polydimethylsiloxane (PDMS). PDMS extraction is based on adsorption, and the equilibrium technique is based on the partitioning of the analyte between the silica resin and the aqueous phase. The adsorbent material is placed in the liquid sample, and the adsorbent material absorbs the compound of interest contained in the liquid sample. Equilibrium is reached when the amount of extracted analyte is proportional to its concentration in the sample. The amount of extracted analyte also depends on the size of the analyte material and therefore on its maximum absorption volume. Extraction in PDMS can be estimated based on the octanol-water partition coefficient (KO / W) of the analyte. The ratio of PDMS to sample, known as the ratio, becomes an important factor in analyte recovery. Extraction efficiency depends on the quality of the solid phase.

[0004] PDMS can be used in solid-phase microextraction (SPME), a known solid-phase extraction sampling technique for extracting organic compounds from samples. SPME involves using fibers coated with a thin layer of an adsorbent material such as PDMS, which forms the extraction phase. The adsorbent material can be a solid adsorbent chosen to extract various types of analytes from many sample media, including both liquid and gas phases. SPME has been found to be widely used because it can be easily automated.

[0005] The size of the adsorbent-coated fiber allows it to be housed within the body of a needle used to pierce a sample vial. Once the needle is inserted into the vial, the fiber extends beyond the needle and is introduced into the sample matrix. The needle is then removed, and the sample retained on the fiber is subsequently desorbed for analysis in a gas chromatography system.

[0006] However, SPME must be confined within a very thin PDMS layer (~7-100 cm) inside the needle. Therefore, the total volume of the recovered compound is limited, typically around 0.5 CL, with a KO / W value below 1000 (log KO / W 3). Thus, a disadvantage of SPME is that it limits the amount of adsorbent that can be loaded onto the fiber.

[0007] Solid-phase extraction (SPE) is generally used to sample mixtures of compounds that may have undergone compositional changes due to the loss of one or more components. These mixtures require sealing before analysis to ensure that measurements of composition accurately reflect the original material. Typically, this involves capping and sealing the sample container with a septum or seal, including a polymer membrane. A seal is defined as one that can be penetrated by a sample probe but is flexible enough to reseal any holes created when the probe is removed.

[0008] To address the low-capacity limitations of SPME sampling, higher-capacity adsorption-extraction samplers have been developed. One such high-capacity sampler comprises a metal probe with a PDMS material sheath surrounding it. However, although SPME typically uses relatively fine needles, it has been found that the size of the metal probe required to support the necessary amount of PDMS for high-capacity sampling presents significant problems with penetration and resealing of container seals, which has so far limited the potential level of automation in high-capacity sampling.

[0009] Therefore, high-volume sampling is limited to non-automated methods, in which a probe in the form of a rod or bar coated with extraction medium is added directly to the sample. The vial is then manually sealed. After extraction, the seal is manually removed and the probe is manually reinserted for further analysis. This method is not only slow and laborious, but also carries the risk of contaminating the atmosphere, the sample, and / or neighboring samples during the processes of removing the seal, removing the probe, and resealing the container.

[0010] Therefore, it is desirable to provide an improved sampling device and / or sampling method that substantially solves the above-mentioned problems and / or proposes improvements.

[0011] According to the present invention, a sampling apparatus and a sampling method as described in the appended claims are provided.

[0012] In an embodiment of the invention, a sampling device for adsorption sampling is provided, comprising a sample container, a sample probe, and an actuator. The sample container is arranged to contain a liquid to be sampled. The sample probe has a probe section configured to be inserted into the sample container, the probe section including an adsorbent material arranged to extract an analyte from the sample container. The actuator is configured to be independently connected to and manipulate both the sample container and the sample probe independently. The sample probe is detachably connected to the actuator, such that the actuator can be connected to and detached from the sample probe in use to selectively interchange the sample probe connected to the actuator with another sample probe. The actuator is any device suitable for moving the sample probe in multiple axes, such as a robotic arm capable of moving in x, y, z axes and potentially including one or more linear actuators disposed thereon. In an alternative embodiment, the sample probe may be a non-adsorption sampling probe configured to extract samples from the container in an alternative manner.

[0013] In standard arrangements of existing technologies, actuators for automated sampling typically include dedicated headspace tools for headspace analysis or dedicated sample probe tools. In the case of sample probes, the probe is connected to the sample probe tool before the automated sampling process, and this sample probe tool is then connected to the robotic arm. The sampling process then proceeds. If additional sampling is required using a different sample probe, the operator must disconnect the sample probe from the sample probe tool and reconnect a replacement to the sample probe tool and subsequently to the actuator. Similarly, if an alternative sampling process is required, such as headspace sampling, the headspace tool must be exchanged with the sample probe tool. This requirement for manual disconnection of the sample probe limits the sampling process because the robotic arm must remain with the same sample probe throughout the entire sampling operation. If multiple containers are to be sampled, the actuator must remain with the sample probe for the entire required sampling period for each container.

[0014] A sample probe that can be detachably connected to the actuator allows the actuator to collect the sample probe, transport it to a sample container, and then, once the sample probe is stored in the container, detach it and collect additional probes for sampling other containers. The detachability of the probe frees up operator time, enabling multiple simultaneous samplings and significantly reducing the total sampling run time. Furthermore, the ability to simultaneously connect to the sample container and the probe allows both the sample container and the sample probe to be lifted through the sample container rather than directly through the sample probe when the sample probe is inserted into it. This advantageously eliminates the need for a robust and complex sealing arrangement on the container to hold the probe and seal the container, as would be required if the container and the probe were lifted directly through the probe.

[0015] The actuator may include a robotic arm. The actuator is preferably a three-axis robotic arm, providing maximum flexibility for transporting sample probes.

[0016] The actuator may include a releasable connector, and the sample probe may include a corresponding connector portion formed to be detachably held by the releasable connector. The releasable connector may be a releasable clamp, such as, but not limited to, a spring-loaded locking hook like a ball-loaded hook, and the sample probe includes a connector portion formed to be detachably engaged by the clamp. The term 'releasable connector' may refer to a standard spring-loaded clamping mechanism of a 3-axis actuator, but may mean any connector element capable of automatically releasably clamping, gripping, or otherwise mechanically connecting to another element.

[0017] The releasable connector can be a connector directly mounted on the robotic arm, or it can be a connector that is actuated and separated by the robotic arm. The releasable connector can also be a gripping tool with a movable gripping element that opens and closes to selectively release or grip the sample probe, the gripping element being actuated by the robotic arm. In the case of a gripping tool, the term "actuator" refers to both the combined robotic arm and the gripping tool connected to the robotic arm, wherein the robotic arm is connected to the sample probe via the gripping tool.

[0018] The sampling device may further include a sample probe adapter having a first connector and a second connector. The first connector is configured to be releasably connected to the actuator when the sample probe adapter is connected to the actuator, and the second connector is configured to be releasably connected to the sample container when the sample probe adapter is connected to the actuator, so that the actuator can connect to and manipulate both the sample probe and the sample container. Therefore, the adapter is an intermediate component for mating a standard actuator, and the adapter is configured to allow the actuator to be independently connected to and manipulate both the sample container and the sample probe. The adapter allows the sample probe to be inserted into the sample container and allows the container and the probe to be moved together. Furthermore, the sample probe and the container can be moved independently.

[0019] The sample probe adapter may include a connector for connecting the actuator to the sample probe.

[0020] The sample container preferably includes a metal cap, and the second connector of the sample probe adapter includes a magnetic element configured to magnetically secure itself to the metal cap of the sample container to move the container. This eliminates the need for any complex mechanical connection mechanisms.

[0021] The actuator preferably includes first and second vertical actuators, a first connector of the sample probe adapter is arranged to be connected to the first vertical actuator, and the sample probe includes a connecting element configured to be connected to the second vertical actuator.

[0022] The sample probe adapter is configured to allow vertical movement of a second vertical actuator relative to the sample probe adapter when the sample probe adapter is connected to a first vertical actuator. The second vertical actuator includes a release mechanism arranged to release the sample probe from the second vertical actuator. The sample probe adapter includes a stop element configured to be geometrically aligned with the release mechanism as the second vertical actuator moves relative to the sample probe adapter, to operate the release mechanism and cause the release mechanism to release the sample probe.

[0023] The sample container preferably includes a sample probe along a sampling axis into which it is inserted, and a sample probe adapter includes a sampling axis aligned with the sampling axis of the sample container when the sample container is connected to a second connector of the sample probe adapter. A first connector of the sample probe adapter is spaced apart from the sampling axis such that a second vertical actuator is axially aligned with the sampling axis when the first connector is connected to a first vertical actuator. The second vertical actuator is used to connect to and operate the sample probe, and thus the alignment of the second actuator with the sampling axis ensures that the sample probe is axially aligned with the sampling axis of the container into which it is inserted.

[0024] The body of the sample probe adapter can be configured such that when the first connector of the sample probe adapter is connected to the first vertical actuator, the body of the sample probe adapter is spaced apart from the sampling axis, allowing the sample probe to be actuated vertically along the sampling axis without interfering with the body of the sample probe adapter. When the probe adapter is connected to the container, the body is configured to provide free access to the top of the container. This can take the form of a profile, recess, hole, or any other construction that ensures the sampling axis is not obstructed above the sample container when the sample container is connected to the sample probe adapter.

[0025] The sample probe connector and actuator can be arranged such that when the first connector is connected to the first vertical actuator and the second connector is secured to the sample container, the second vertical actuator can vertically actuate the sample probe independently of the sample container. In this way, while the second vertical actuator inserts or removes the sample probe from the sample container, the sample container can be held stationary by the probe connector.

[0026] Preferably, the sample probe connector includes a hole extending through the sample probe connector along the sampling axis, and a stop element is arranged at least partially around the periphery of the hole on the upper surface of the connector to engage the release mechanism when the second vertical actuator moves downward through the hole to reach a release position. Preferably, when the sample probe connector is connected to the first actuator, at least a portion of the release mechanism is radially spaced outward relative to the hole, and the second actuator operates across a first vertical movement range and is capable of moving to the release position below the lower limit of the first movement range, in which the release mechanism remains vertically spaced from and above the stop element, in which the at least radially spaced outward relative to the hole engages the stop element.

[0027] The second actuator may include a lower portion that extends through a hole in the connector during use. At least a portion of the release mechanism is radially spaced outward relative to the lower portion. The lower portion operates across a first vertical movement range during sampling, across which the release mechanism remains vertically spaced from and above a stop element. The lower portion also moves below the first movement range to a release position, and the release mechanism is arranged to engage a stop element surrounding the hole, with the lower portion extending through the hole to reach the release position.

[0028] The stop member may include an upright wall extending around at least a portion of the hole, the wall having an upper surface arranged to engage a release mechanism. The release mechanism may be a vertically sliding mechanism that causes the lateral release of the hook upon upward actuation relative to the hook, such as a sliding collar, and the hook may be a ball-bearing hook or a similar arrangement.

[0029] The sampling device preferably also includes an alignment element that, when received in the sample container, engages the sample probe to vertically align the probe so that it can be connected to a second vertical actuator. The sample probe is supported within the container by a flexible diaphragm. In use, although the sample probe is inserted into the container with a fully vertical orientation, it can begin to deviate from the vertical axis over time, especially during agitation. If the sample probe is not aligned with the vertical axis, it becomes difficult for the actuator operating on the vertical axis to retrieve the sample probe from the top.

[0030] The alignment element may include first and second alignment elements that are movable in opposite horizontal directions to engage with the opposite side of the sample probe. The alignment element is movable between an alignment position, in which it engages the sample probe to hold it in a substantially vertical orientation, and in the release position, in which the sample probe and sample container can be vertically lifted.

[0031] Preferably, each alignment element includes a guide section arranged to receive a portion of the sample probe, the guide section being aligned in the alignment position to maintain the sample probe vertical. The alignment element may include horizontally arranged alignment plates, each having a main aperture formed therein, the main aperture having a diameter larger than the diameter of the sample container, and a guide channel extending from the periphery of the main aperture into the plate. The main aperture is aligned in the release position to define a channel through which the sample container can move vertically without obstruction. In the alignment position, the guide channel is aligned and cooperates to define a substantially circular aperture corresponding to the diameter of the sample probe's axis, the circular aperture being concentrically aligned with the vertical axis of the probe.

[0032] The sampling device may also include a latching mechanism to hold the sample probe and vertically restrict it to a fixed vertical position, for example, when the sample probe is inserted into an oven. The latching mechanism preferably includes a single or a pair of latching plates, each latching plate including a guide section arranged to receive a portion of the sample probe. The guide section is aligned in the latched position to vertically lock the sample probe in place. The guide section is preferably arranged to engage a connector channel to which an actuator is attached. The latching plates are preferably horizontally arranged alignment plates, each latching plate having a main aperture formed therein, the main aperture having a diameter larger than the diameter of the sample container, and a guide channel extending from the periphery of the main aperture into the plate. The main aperture is aligned in the released position to define a channel through which the sample container can move vertically without obstruction. In the locked position, the guide channel is aligned and cooperates to define a substantially circular hole corresponding to the diameter of the connector channel of the sample probe head, with the plate vertically aligned to the hole.

[0033] The sample probe adapter may include a clamping mechanism configured to clamp the sample probe. The clamp provides a releasable connection between the actuator and the sample probe. The clamping mechanism includes a connecting element configured to connect to a second vertical actuator so that the clamping mechanism can be operated by the second vertical actuator. Specifically, operation of the second vertical actuator connected to the clamping mechanism causes the clamping mechanism to close and open to clamp and release the sample probe. The clamping mechanism serves as a connector for the actuator to connect the actuator to the sample probe. The actuator is preferably a robotic arm, and the clamping mechanism advantageously allows the robotic arm to be releasably connected to the sample without requiring the sample probe to be directly connected to the connector of the robotic arm. Therefore, wear on the connector of the robotic arm is avoided during the continuous connection and release of the sample probe.

[0034] At least one magnet of the sample probe connector may be disposed on the clamping mechanism. Preferably, the clamping mechanism comprises at least two movable clamping elements in the form of opposing fingers. The at least one magnet is disposed on the distal end face of at least one clamped element, the distal end being the end facing the sample container in use. Preferably, at least one magnet is disposed on the distal end of each clamping element.

[0035] In another aspect of the invention, a cleaning device is provided for use in a sampling system such as those described above. The cleaning device is a cleaning station comprising: a chamber configured to receive at least a portion of an elongated adsorbent sample probe; one or more liquid inlets configured to direct a stream of cleaning liquid into the chamber to clean the sample probe; and one or more air inlets arranged to direct a stream of air into the chamber to dry the sample probe. The cleaning station allows for automated cleaning of the sample probe to remove debris or other contaminants prior to desorption, eliminating the need for manual cleaning by removing the sample probe from the actuator, thereby preventing interruption of the automated sampling process.

[0036] The chamber preferably includes an opening into which a sample probe is inserted, and at least one liquid inlet is located near the opening for guiding cleaning fluid into the probe.

[0037] The at least one liquid inlet can be arranged to guide the cleaning liquid flow toward the inner end of the chamber in a longitudinally inward direction. This ensures that the cleaning liquid is contained within the chamber during use.

[0038] The chamber preferably includes a longitudinal axis along which the sample probe extends when it is received within the chamber, and the device includes a plurality of liquid inlets arranged in a ring array coaxial with the longitudinal axis of the chamber, such that liquid flow from each liquid inlet is guided radially inward. This generates a cleaning liquid curtain providing 360-degree cleanliness around the probe.

[0039] The chamber may also include multiple air inlets arranged in a ring array coaxial with the longitudinal axis of the chamber, such that airflow from each air inlet is guided radially inward. These air inlets enable drying of the probe after the cleaning stage, ensuring that no liquid remains on the probe when it is transferred to the probe drying oven.

[0040] The multiple air inlets can be longitudinally aligned with the multiple liquid inlets and arranged in a common annular array. This provides a compact arrangement in which all air and water connections are co-located, with the location near the openings allowing for cleaning upon entry and drying upon withdrawal.

[0041] The liquid inlet and / or air inlet may include a nozzle located at its inner end to generate a jet of liquid and / or air directed into the chamber.

[0042] The air inlet is preferably arranged to create a radially guided air curtain.

[0043] The cleaning equipment may also include a controller arranged to initiate a cleaning cycle by supplying cleaning liquid to a liquid inlet, and to initiate a drying cycle following the cleaning cycle by supplying pressurized air to an air inlet.

[0044] The chamber may also include a discharge device disposed at the inner end of the chamber for removing cleaning fluid that will be directed downward from the liquid inlet from the chamber.

[0045] In another aspect of the invention, a sample container is provided, comprising: a liquid container having an opening at one end and a sealing member covering and at least partially closing said opening; and a plug element configured to extend through a hole formed in the sealing member, the plug element including a tip having a first-diameter locking section and a sealing section positioned along the plug element toward a distal end having a diameter smaller than that of the locking tip, the locking tip sealing the hole formed in the sealing element during use, while the larger-diameter locking tip inhibits plug retraction. The plug element preferably includes a cap section comprising a metal portion capable of being secured by a magnetic connector of a probe mating device to allow the plug element and the sealed container to be transported by an actuator. The sealing element is a diaphragm and may include pre-formed holes for receiving a sample probe and / or sealing the plug element. Alternatively, the diaphragm may be configured to be punctured by the sample probe upon entry, while the plug element seals the hole created by the probe.

[0046] In another aspect of the invention, an elongated sample probe and an oven for heating a sample collected by the sample probe are provided. The oven includes a heated chamber and an opening to the heated chamber, the opening having a diameter configured to receive the elongated sample probe and a sealing element positioned adjacent to the opening for sealing around a sealing portion of the sample probe to create a seal between the oven chamber and the outside atmosphere. An oven adapter is also provided, comprising a body having a sealing portion having the same shape and size as the sealing portion of the sample probe, such that the sealing portion can seal within the oven opening in the same manner as the probe. The adapter includes an internal channel for connection to the oven chamber. A sealing element is provided that closes the channel and is formed of a material capable of being punctured by a syringe in a sealed manner. The sealing element is preferably a diaphragm formed of an elastic, flexible material such as silicone. Without such an adapter, the inlet would have to be manually constructed depending on the sampling method.

[0047] The sampling assembly may include one or more locking elements arranged to hold a sample probe in place within the sample oven and / or sample container when the container is positioned within the agitator. The locking elements are arranged to engage the sample probe to prevent vertical movement when it is inserted into the sample oven and / or sample container. This allows the sample probe to be released by the robotic arm and remain inside the sample oven or sample container. In the case of an oven, this allows the sample probe to remain in place without the risk of bursting due to chamber pressure. In the case of an agitator, this prevents the sample probe from collapsing while the container is agitated. The locking element is preferably a latching device arranged to engage the sample probe in the horizontal direction to prevent vertical movement. By vertically locking the sample probe, the latching device allows the robotic arm to disengage from the sample probe and perform other functions. In another aspect of the invention, an automated sampling system is provided, comprising a sample container for containing a liquid to be sampled; a sample probe having a probe section configured to be inserted into the sample container, the probe section including an adsorbent material arranged to acquire an analyte from the sample container; and an actuator configured to be independently connected to and manipulate the sample container and the sample probe. The system also includes an oven for heating a sample collected on the probe, a focusing cold trap for receiving a sample from the oven, and means for releasing a sample from the cold trap and guiding at least a portion of the sample to an analyzer. An automated sampler is provided, arranged to receive at least a portion of the released sample. The automated sampler includes a plurality of collection tubes for receiving and storing at least a portion of the released sample.

[0048] Preferably, the automated sampler further includes a release oven for desorbing and recollecting the sample for further analysis. The rereleased sample is guided backward in the opposite direction to a cold trap, a similar collection element on the same automated sampler, a different tube on the same automated sampler, and / or a tube on another automated sampler. The rereleased sample can be transferred from the cold trap to one or more analyzers. Fluid connectors are provided to link the automated sampler to the cold trap, the cold trap to the analyzer, and the cold trap to the original sampling oven.

[0049] The raw sampling oven can be used to release samples from sample probes, headspace injectors, and / or liquid samplers such as liquid syringes. Each of these samples can be recollected for archiving or reanalysis on a separate collection tube in an automated sampler and / or can be overlapped on the same collection tube for simultaneous analysis.

[0050] The sample probe can be detachably connected to the actuator, allowing the actuator to be connected to and disconnected from the sample probe in use, selectively interchangeable with another sample probe connected to the actuator.

[0051] In another embodiment of the invention, the sample probe includes a first diameter portion located at its distal end and a second, larger diameter segment positioned toward the distal end, the first diameter portion being at least partially received within a liquid sample during use. The sample container includes a sealing member for closing and sealing the container, the sealing member having an orifice formed therein having a diameter larger than the first diameter of the sample probe and smaller than the larger diameter of the sample probe, such that while the second segment engages and seals the orifice, the first probe segment is freely received through the orifice. The sealing member may include a first elastic membrane and a second membrane formed of PTFE that initially closes the orifice. The PTFE membrane layer may be separate from or bonded to the sealing member.

[0052] In another aspect of the invention, an adsorption sampling device is provided, comprising a sample container with an opening for receiving a sample and a sealing assembly for covering and sealing the opening, the sealing assembly comprising a first sealing membrane and a second flexible sealing element. A sample probe having an elongated body comprising an adsorbent material for insertion into the sample container is also provided, the elongated body having a lower section comprising the adsorbent material and an upper section having a diameter greater than the lower section. The flexible sealing element includes a pre-formed orifice for receiving the sample probe, the pre-formed orifice having a diameter smaller than the diameter of the upper section of the sample probe, the first sealing membrane being arranged to close and seal the container before sampling and to be punctured by the sample probe when inserted into the container, and the second flexible membrane being arranged to close and seal the container when the sample probe is inserted into the container, such that the upper section with the larger diameter is received in the orifice. The pre-formed orifice allows the lower section of the probe, containing the adsorbent material, to be easily inserted into the container via the sealing assembly without excessive frictional contact, and prevents damage to the adsorbent material that could occur if the probe punctures the flexible sealing element (diaphragm) without such a pre-formed orifice. Once of interest, the interference fit between the upper section of the probe and the orifice seals the container. However, before the probe is inserted, the flexible diaphragm cannot seal the container due to the orifice. Therefore, a sealing membrane is arranged to seal the container before probe insertion, and this membrane is arranged to be punctured upon insertion.

[0053] Preferably, the first sealing membrane is a thin film such as a PTFE membrane. The first sealing membrane is preferably a disc-shaped membrane corresponding to the size of the opening. The second sealing element is preferably formed of a flexible material such as silicone resin. The second sealing element is preferably substantially annular.

[0054] The first membrane seal is positioned between the container and the second flexible sealing element, above the container opening. The PTFE seal is thus sandwiched between the container and the diaphragm. When the PTFE membrane is punctured, it bends away from the diaphragm into the container without interfering with the seal between the probe and the diaphragm.

[0055] Alternatively, a cap may be provided, arranged to secure a sealing assembly to the container, the sealing assembly being secured between the cap and the container, and the cap including an opening having a diameter larger than that of the second flexible sealing element. In this way, the cap does not impede the insertion of a probe through the opening in the cap. Moreover, when the opening is radially spaced outward relative to the orifice of the diaphragm, the orifice exposes an area of ​​the diaphragm that can be used by the syringe for sampling based on methods such as headspace sampling or liquid sampling.

[0056] The diameter of the hole in the second sealing element is preferably larger than the diameter of the lower section of the sample probe, which ensures that the lower section smoothly passes through the hole while the upper section engages and seals the lower section.

[0057] The sample probe may include a radially tapered transition section arranged axially between a lower section and an upper section, the tapering section tapering from the diameter of the lower section to an increased diameter of the upper section. This tapered transition section has a wedging function, providing a smooth transition between the lower and upper sections when the probe is inserted through a hole causing hole expansion.

[0058] The invention will now be described with reference only to the following exemplary drawings, in which: Figure 1 It is an automated sampling system according to an embodiment of the present invention; Figure 2 A sampling probe according to an embodiment of the present invention is shown; Figure 3 An exploded view of a sample container and a probe according to an embodiment of the present invention is shown; Figure 4 This illustrates the case where a probe is inserted. Figure 3 Assembly and layout; Figure 5 An arrangement of container sealing plugs according to an embodiment of the present invention is shown; Figure 6 A container sealing arrangement according to another embodiment of the present invention is shown; Figure 7 This is a top view of a sample probe cleaning device according to an embodiment of the present invention; Figure 8 It is along Figure 7 A cross-sectional view of line AA; Figure 9 It is a probe connector according to an embodiment of the present invention; Figure 10 It comes from Figure 9 A view below the probe connector; Figure 11 An oven connector according to an embodiment of the present invention is shown; Figure 12 The oven in use is shown. Figure 11 Oven connectors; Figure 13 It is an automated sampler component according to an embodiment of the present invention; Figure 14 This is a cross-sectional view of the latch arrangement according to an embodiment of the present invention; Figure 15 It comes from Figure 14 The view above the arrangement; Figure 16 A sample probe connector including a clamping mechanism according to an embodiment of the present invention is shown; Figure 17 It shows Figure 16 Another view of the sample probe adapter; and Figure 18 The connection to the sample container is shown. Figure 16 Sample detector connector.

[0059] Reference Figure 1 Apparatus 1 is provided for sampling and analyzing collected liquid samples. The collected liquid samples are contained in sample containers 2. Multiple sample containers 2 are held in sample trays 4. Each sample container 2 holds a volume of liquid, referred to as "bulk liquid," and a volume of gas, referred to as "headspace," above the bulk liquid. Figure 1 In this embodiment, the device 1 is capable of adsorption sampling and liquid sampling of bulk liquid samples, as well as adsorption sampling of headspace.

[0060] The apparatus includes a standard triaxial x, y, z linear actuator with a robotic arm capable of moving along track 8 in the X and Y directions. Multiple adsorption sample probes 10 are held within a probe carrier 12. The apparatus 1 also includes a cleaning and drying station 14 and an oven 16 connected to a cold trap and a gas chromatograph. A probe connector 18 is provided connected to the robotic arm, enabling the robotic arm to acquire the adsorption sample probes 10, as will be further described below. The probe connector 18 is used to configure a standard robotic arm, typically used for injection analysis, to acquire the adsorption sample probes 10. The probe connector 18 is also configured to enable the robotic arm to acquire the sample container 2. Thus, the probe connector 18 can transport the sample container 2 and the adsorption sample probes 10 simultaneously or independently.

[0061] During automated adsorption sampling of liquid samples held in sample container 2, an initial pre-sampling phase is first implemented by device 1, in which sample container 2 and adsorbent-carrying adsorption sample probe 10 are prepared. The following pre-sampling steps are non-exhaustive and not limited to being performed in the described order. First, sample container 2 is selected from a plurality of sample containers 2 stored in sample tray 4, the selection being determined by the controller under the operation of control software to be analyzed on sample container 2. Then, robotic arm 6 is operated to retrieve the selected sample container 2 from sample tray 4. Robotic arm 6, having already retrieved probe connector 18, lifts sample container 2 from sample tray 4 and moves the sample container to an incubator agitator, which is arranged to heat and / or agitate the sample container 2, as determined by the specific requirements of the sample contained in sample container 2. This incubation / agitation phase is implemented to achieve pre-sampling equilibration of the sample.

[0062] Before sampling, the adsorbent sample probe 10 is heat-pretreated by heating to ensure its cleanliness. This heat pretreatment can be performed using an oven 16 or a dedicated probe processing unit (not shown). Once pretreated, the adsorbent sample probe 10 is either used immediately or stored in a probe carrier 12. The probe carrier 12 includes a channel configured to receive a probe tip containing adsorbent material, wherein the channel is sealed to maintain probe integrity while the adsorbent sample probe 10 is stored in the channel.

[0063] The pre-processed adsorption sample probe 10 is selected from a plurality of adsorption sample probes 10 stored in the probe carrier 12, and the selected adsorption sample probe 10 is acquired by the robotic arm 6 using the acquired probe adapter 18. Once the adsorption sample probe 10 is held by the robotic arm 6, the sample probe is ready to begin sampling.

[0064] During the sampling phase, the sampling process and parameters depend on the sample to be obtained. Adsorbent sampling may include sampling of the bulk liquid contained in sample container 2 or sampling of the headspace above the bulk liquid present in sample container 2. Variables in the sampling process include the positioning of the adsorbent sample probe 10 within sample container 2, the required sampling time period, and the agitation rate. Each variable can be defined by the user in the system, wherein each element is controlled by a common controller and user interface.

[0065] The adsorption-type sample probe 10, selected during the pre-sampling stage and engaged by the robotic arm 6, is moved by the robotic arm 6 to the x, y position of the selected sample container 2. After being transferred to this position in the pre-sampling stage, the sample container 2 can be positioned in the incubation agitator. The probe robotic arm 6 then extends the adsorption-type sample probe 10 downward along the z-axis to introduce the probe into the sample container 2, as will be described in further detail below.

[0066] For liquid sampling, the adsorption sample probe 10 is inserted into the sample container 2, so that the adsorbent material at the tip of the adsorption sample probe 10 is introduced into the liquid sample. Once the adsorption sample probe 10 is fully inserted and the tip is sealed inside the sample container 2, the adsorption sample probe 10 is released and the sample retained in the sample container 2 is released by the robotic arm 6 for the required sampling time period. The robotic arm 6 is then free to perform other operations, such as manipulating other sample containers 2 and adsorption sample probes 10. The ability to release the adsorption sample probe 10 allows for the preparation and execution of multiple, simultaneous, overlapping samples by a single robotic arm 6. This also allows the sampling time for each sample container 2 to be set independently, and each sample container 2 can have a different sampling time period than the others, as required. The number of insertions and extractions of the adsorption sample probe 10 and the time period can be controlled to optimize the use of the robotic arm 6.

[0067] The adsorption sample probe 10 is allowed to remain within the sample container 2 for a period of time, which is predetermined by the user and / or processor of the control device based on sample demand. Depending on the contents of the sample container 2 and information regarding sample demand, the sampling period can be specifically defined for each sample container 2 and can vary as the sample changes if necessary. During the sampling period, the compounds contained within the sample are acquired by the adsorbent material present on the adsorption sample probe 10. During sampling, the sample container 2 can be agitated and / or incubated.

[0068] Once the sampling period is over, the robotic arm 6 is operated to remove the adsorption sample probe 10 from the sample container 2. Before removing the adsorption sample probe 10 from the sample container 2, the adsorption sample probe 10 and the sample container 2 are removed from the agitator by the engagement of the robotic arm 6 with the sample container 2. Preferably, the probe adapter 18 is configured to magnetically connect to the lid of the sample container 2 to allow the sample container 2 and the adsorption sample probe 10 to be lifted by the robotic arm 6. The sample container 2 and the adsorption sample probe 10 are transferred from the agitator to the sample tray 4. The adsorption sample probe 10 is then removed from the sample container 2 by the robotic arm 6. The sample container 2 is released by the robotic arm 6 and remains in the sample tray 4. The sample container 2 can then be sealed by a plug element or a sealing cap. This can be done while the adsorption sample probe 10 is held by the robotic arm 6 or once the adsorption sample probe 10 has been stored in an oven.

[0069] During the pre-desorption stage, between sample collection and desorption in the sample oven 16, the adsorbent sample probe 10, already removed from the sample container 2, is transferred by the robotic arm 6 to the cleaning and drying station 14 to remove any residual liquid or debris that may be present on the adsorbent sample probe 10. Where the adsorbent sample probe 10 has been inserted into the liquid sample, liquid droplets and / or surface films may remain on the adsorbent sample probe 10 when it is removed from the sample container 2. For continuous and accurate sample analysis, it is important to remove excess liquid from the adsorbent sample probe 10 to ensure that only compounds absorbed into the adsorbent material are desorbed and analyzed. It has also been found that some liquids present on the surface of the adsorbent sample probe 10, particularly those containing substances such as sugars, can burn or produce fumes at the high temperatures of the oven 16.

[0070] The cleaning and drying station 14 provides a cleaning liquid jet, which can be filtered water, a detergent solution, or an optional solvent directed onto the adsorption sample probe 10 at a user-defined flow rate, dilution rate, and duration. The cleaning and drying station 14 also includes multiple air nozzles. After the cleaning phase, the air nozzles are activated to direct air jets onto the adsorption sample probe 10 to dry it. The nozzles are arranged to create an air curtain, and the adsorption sample probe 10 is slowly withdrawn from the cleaning and drying station 14 during the drying phase, with the end of the adsorption sample probe 10 being drawn through the air curtain to optimize drying efficiency. The cleaning and drying station 14 is described in further detail below.

[0071] The cleaned and dried adsorption sample probe 10 is transferred by robotic arm 6 to oven 16. The adsorption sample probe 10 is lowered along the z-axis into a sealed inlet port of oven 16. Oven 16 includes a sliding latch mechanism arranged to slide into a locked position once the adsorption sample probe 10 is inserted into the inlet port of oven 16. This latch engages with the adsorption sample probe 10 and locks it in place within the oven by vertically restraining the probe along the z-axis to prevent release from oven 16. With the adsorption sample probe 10 restrained and locked in place, robotic arm 6 can release the adsorption sample probe 10 without the risk of it being ejected from oven 16 due to pressure generated within the oven. Furthermore, once robotic arm 6 releases the adsorption sample probe 10, it is free to perform further operations.

[0072] With the adsorbent sample probe 10 inserted and locked in the oven 16, an automated leak test is performed to ensure sample integrity. The adsorbent material on the adsorbent sample probe 10 is then heated by the oven 16, and the compounds collected from the sample container 2 on the adsorbent material are transferred in an inert carrier gas stream to a focusing trap, commonly referred to as a cold trap. The sample is then rapidly released from the focusing trap, and at least a portion of the released sample is transferred to a gas chromatograph (GC) for analysis. A portion of the released sample may also be transferred to an adsorbent tube. In this example, the cold trap acts as a buffer, holding the sample in place while the adsorbent tube is positioned for sample collection. Collection of the sample on the adsorbent tube allows for archiving of the sample for future reanalysis. If the sampling procedure requires one or more reanalysis steps, the sample on the adsorbent tube can also be reanalyzed shortly after the initial analysis. The system utilizes an 'automated sampler' of adsorbent tubes, comprising a cartridge or conveyor belt and an oven. The cartridge of the automated sampler houses multiple adsorbent tubes. After release from the focusing trap, the sample can be separated, and a portion of the released sample can be delivered to an adsorbent tube selected from the cartridge by the automated sampler. The adsorbent tube may be empty of sample or may retain a sample previously obtained during the sampling procedure. For example, the adsorbent tube may retain a headspace sample, which is subsequently supplemented with an adsorbent sample to provide a more complete analysis of the sample compounds. The adsorbent tube holding the sample can then be replaced by another tube from the cartridge, or the automated sampler's adsorbent tube oven can be used to re-release the stored sample to the GC for secondary analysis.

[0073] The combination of automated samplers and automated probe samplers enables rapid sample analysis with options for repeatable analysis, the possibility of concentrating multiple samples onto a single adsorbent tube, and / or the possibility of archiving samples. These facilities are currently unavailable for automated probe sampling systems.

[0074] After the sample is released into the cold trap, the oven 16 is isolated from the carrier gas. The oven 16 is then cooled, and once cooled, the robotic arm 6 is reattached to the adsorption sample probe 10 and the latching mechanism is released. The adsorption sample probe 10 is then removed from the oven 16 and placed back into the probe carrier 12 for reuse. After the adsorption sample probe 10 is removed, the lid is closed on the oven 16 to prevent debris from entering.

[0075] During the analysis of a single sample, when the robotic arm 6 detaches from the adsorption sample probe 10, it can be operated to perform one or more additional pre-sampling, sampling, pre-desorption, and desorption operations for multiple other sample container probes. The controller can be programmed to operate these multiple simultaneous operations in the most efficient manner to optimize productivity by maximizing output.

[0076] Reference Figure 2 The adsorption sample probe 10 includes a handle section 20 and a tip section 22. The handle section 20 comprises the body of the adsorption sample probe 10. The columnar handle section 20 includes a connector portion 26 at its upper end 24, which has a diameter larger than the main shaft of the handle section 20. The connector portion 26 includes a circumferentially extending beveled engagement channel 28 with a reduced diameter, which is configured to receive a corresponding latching element of the z-axis actuator of the robotic arm 6. The latching element may be a spring-loaded ball lock hook or any other suitable element configured to extend into and engage with the beveled engagement channel 28 to vertically retain the adsorption sample probe 10. The z-axis actuator also includes a release mechanism that slides vertically to release the spring-loaded ball lock hook.

[0077] Handle section 20 includes a locking section. The locking section includes a radially extending upper shoulder section and a lower shoulder section, the upper and lower shoulder sections having a diameter larger than the diameter of the body of handle section 20, wherein a channel 38 is formed between the upper and lower shoulder sections. Channel 38 is arranged to receive a latch plate or similar locking element. The latch plate is arranged such that, in a given position, when the adsorption sample probe 10 is received in a position requiring vertical locking of the adsorption sample probe 10 in place, the latch plate is vertically aligned with channel 38, and preferably such that the lower surface of the latch plate is vertically aligned with the upper surface of the lower shoulder section. The adsorption sample probe 10 can be received through a hole in the latch plate. The latch plate is capable of sliding horizontally to a locked position, in which at least a portion of the plate is received within at least a portion of channel 38. When the latch plate is received in the channel 38, the engagement of the lower shoulder section with the latch plate prevents the vertical removal of the adsorption sample probe 10.

[0078] The handle has a recessed section 30 with concentric rings, which are printed, laser-marked, or otherwise provide a barcode or other identifier for the probe. The recessed section 30 minimizes wear on the barcode or other identifier. The barcode or other identifier is positioned within the probe adapter 18 as a barcode reader 122 or as a separate module (not shown).

[0079] The upper handle section includes an inner channel with internal threads at its base end. The lower handle section includes a corresponding threaded portion that engages with a threaded portion of the upper handle section to connect the lower handle section to the upper handle section. The upper end of the lower handle section has the same diameter as the upper handle section. The diameter of the lower handle section decreases along its length at a tapered transition section 46 to a lower end section 48 with a decreasing diameter. At the distal end of the lower handle section, the lower handle section includes a protruding piercing tip 50 to assist insertion of the probe through a hole in the diaphragm of the sample container.

[0080] The lower stalk section includes the adsorbent material. Figure 2In the arrangement, the adsorbent material is provided with a pair of longitudinally aligned and diametrically opposed grooved adsorbent channels 52. The adsorbent channels 52 extend longitudinally and are radially recessed into the body of the lower handle section. The adsorbent channels 52 have equal lengths and a first lower end portion longitudinally spaced inward from a tapered protruding tip 50. The upper end portion of each channel is longitudinally spaced downward from a tapered section 46. The adsorbent channels 52 contain adsorbent material 54 suitable for performing adsorption sampling. Preferably, the adsorbent material 54 is polydimethylsiloxane (PDMS); however, other materials detailed in the claims may be used. The dimensions of each adsorbent channel 52, including length, depth, and width, are selected to define the volume of the adsorbent material 54 contained therein.

[0081] As in Figure 3 As shown, the sample container 2 includes: a cylindrical hollow glass body 58 defining the storage container, and a neck 60 having an edge 62 at its opening. The edge 62 includes an outwardly extending rib 64 having a lower edge 66 spaced apart from an upper shoulder 68 of the cylindrical hollow glass body 58. A silicone disc 70 having a diameter corresponding to the diameter of the edge 62 is disposed on the upper surface of the edge 62 and provides a diaphragm for the container. The silicone diaphragm 70 includes a central aperture 72 having a diameter configured to allow passage of the lower segment 48 of the adsorption sample probe 10. The diameter of the central aperture 72 is equal to or greater than the diameter of the lower segment of the tip segment 22, but smaller than the diameter of the upper segment. A PTFE membrane 71 is positioned below the silicone diaphragm 70, disposed on the edge 62, between the edge 62 and the silicone diaphragm 70. The PTFE membrane 71, formed as a disc, is bonded to the silicone diaphragm to optimize the seal between the two components. The PTFE membrane does not contain pores and seals the sample container 2 to prevent gas release through the central pore 72 of the membrane. When the adsorption sample probe 10 is inserted through the central pore 72, the probe punctures the PTFE seal. (As in...) Figure 4 As illustrated, when the PTFE membrane 71 is punctured by the lower end of the tip section 22 of the adsorption sample probe 10, the PTFE seal bends inward.

[0082] The sample container 2 also includes a metal cap 74 having an annular upper surface 76. This metal cap has an opening larger than the maximum diameter of the adsorption sample probe 10, allowing the adsorption sample probe 10 to be inserted through this opening without engaging with the edge of the opening in the upper surface 76. The cap 74 also includes a sidewall 78 open at its lower edge. The diameter of the cap 74 is substantially equal to the diameter of the rib 64, allowing the cap 74 to be inserted into the rib 64. The lower end of the sidewall 78 then curls over the lower edge 66 of the rib 64 to secure the cap 74 in place on the edge 62. A silicone diaphragm 70 and a PTFE membrane 71 are held in place between the cap 74 and the edge 62. The opening of the cap 74 is larger than the central hole 72 of the diaphragm seal. The central hole 72 is therefore radially spaced inward relative to the opening of the cap 74, exposing the section of the diaphragm seal between the inner periphery of the opening and the central hole 72. The exposed annular section of the diaphragm allows the diaphragm to be punctured by a syringe to obtain a sample, such as a headspace sample, from the sample container 2 prior to adsorption sampling. The silicone diaphragm 70 can reseal when the syringe needle is withdrawn and maintains the container's seal while the exposed PTFE membrane 71 within the orifice remains intact.

[0083] The reduced diameter of the lower section 48 of the tip section facilitates the initial and easy insertion of the adsorption sample probe 10 through the central hole 72 of the silicone diaphragm 70. The diameter of the lower section 48 is chosen such that it slides relatively easily and with limited friction through the opening of the diaphragm during use. The diameter of the central hole 72 can be chosen to provide a slight sealing fit with the lower section 48, or to space the periphery of the hole from the lower section 48 to prevent the lower section 48 from rubbing against the silicone diaphragm 70. As the adsorption sample probe 10 is further inserted, the tapered transition section 46 reaches the silicone diaphragm 70. The expanding diameter of the tapered transition section 46 transitions to the larger diameter of the upper section 44. The diameter of the central hole 72 is chosen such that it is smaller than the diameter of the upper section 44 to provide tight tolerances or preferably an interference fit. In this way, when the upper section is received in the central hole 72, a reliable (positive) seal is formed with the silicone diaphragm 70.

[0084] This sealing joint between the upper section 44 and the silicone diaphragm 70 seals the sample container 2 in a very simple way, without the need for a more complex arrangement of additional seals on the sample container and / or the adsorption sample probe 10.

[0085] Before the insertion of the adsorption sample probe 10, the sample container 2 is sealed with a PTFE membrane 71. To obtain a sample from the sample container 2, the adsorption sample probe 10 is inserted through a pre-formed hole in the silicone diaphragm 70. The tip 50 pierces the PTFE membrane, and the adsorption sample probe 10 extends through the silicone diaphragm 70 and the PTFE membrane 71 into the sample container 2. Figure 4 An arrangement is shown in which the adsorption sample probe 10 is inserted into the sample container 2 such that the lower section 48 of the tip section 22 and the tapered transition section 46 are fully inserted through the central hole 72 in the silicone diaphragm 70. This opening has been expanded to the larger diameter of the upper section 44 of the tip section 22. In this configuration, the central hole 72 is expanded by the larger diameter of the upper section 44 of the tip section 22, and the engagement between the inner edge of the central hole 72 and the outer surface of the upper section 44 creates a tight seal between liquid and gas and provides a sufficiently tight interference fit so that the sample container 2 can be raised through the adsorption sample probe 10 if necessary. Furthermore, the engagement between the hole and the outer surface of the tip section 22 allows the silicone diaphragm 70 to act to wipe away a significant amount of liquid from the tip section 22 when the adsorption sample probe 10 is withdrawn from the sample container 2.

[0086] When the adsorption-type sample probe 10 is withdrawn from the sample container 2, the central hole 72 remains open. Therefore, as in Figure 5 As shown, a stop 80 is provided for closing and sealing the central hole 72. The stop 80 includes a disc-shaped cover portion 82 and a plug section 84 extending from the lower surface of the cover portion 82. The plug section 84 is substantially cylindrical and centrally positioned and configured to be inserted through the central hole 72 of the silicone diaphragm 70. The plug section 84 includes a lower section 86 with an increased diameter, wherein the upper portion 88 of the plug section 84 has a diameter decreasing relative to its distal end, the diameter of which is greater than the diameter of the unexpanded free state of the central hole 72. The plug section 84 is inserted through the central hole 72, and once fully inserted, the cover portion 82 rests on the upper surface 76 of the cover 74 of the sample container 2. Once the larger-diameter lower section 86 of the plug section 84 has completely passed through the central hole 72, the increased diameter acts as a barb and helps retain the plug section 84 within the hole and prevents retraction. Since the upper section 88 has a larger diameter than the central hole 72, the upper section seals the central hole 72 in the same way as the adsorption sample probe 10. The sealing cover portion 82 is made of metal, so that it can be magnetically lifted by the probe connector 18 of the robotic arm 6 in the same way as the cover 74 of the sealed sample container 2.

[0087] For stop 80, alternatively, Figure 6A sealing cap 118 is shown that can be applied to a sampling bottle to seal the bottle after sampling. The sealing cap 118 includes a handle 120 and a head section 126 corresponding in shape to the handle 120 and head section 126 of the adsorption sample probe 10. The sealing cap 118 is configured to fit onto the upper end of the sample container 2. An O-ring 128 or similar seal can be configured to surround the inner edge of the sealing cap 118, abutting against the outer surface of the cap and the upper end of the sample container 2 for sealing. A robotic arm presses the sealing cap 118 onto the sample container 2, creating a seal between the inner and outer diameters of the container's cap. The shape of the handle 120 and head section 126 allows the handle 120 to be engaged with and lifted by the robotic arm for transporting the sample container 2.

[0088] Figure 7 This is a view taken from above the cleaning and drying station 14. The cover section of the cleaning and drying station 14 includes multiple inlet ports. As described above, the first set of liquid inlet ports 90 are connected to a supply source of cleaning liquid via multiple liquid conduits. The second set of air inlet ports 92 are connected to a pressurized air source. The inlet opening 94 is centrally located within the cover to receive the adsorption-type sample probe 10.

[0089] exist Figure 8 A cross-sectional view of the through-line AA is shown. Liquid inlet holes 90 and air inlet holes 92 are arranged in an annular array formed in an annular beveled surface extending downward from the upper surface of the cover section. The liquid inlet holes 90 and air inlet holes 92 are angled downward, substantially perpendicular to the surface of the annular beveled surface of the body through the cover section. The wider outer ends of the liquid inlet holes 90 and air inlet holes 92 define connection ports for connection via connectors, for securing to liquid and gas conduits. The channel tapers inward at its inner end to a decreasing diameter outlet section 98, which extends into a chamber 100 defined within the first body 102 of the cleaning and drying station 14. A nozzle may be provided at the inner end of the inlet, configured to provide the desired flow rate and jet characteristics of the liquid or gas into the chamber 100.

[0090] In the first stage of the cleaning process, a cleaning fluid, which may be heated, cooled, or at room temperature, is provided to the liquid inlet orifice 90 and pumped under pressure through the inlet channel. A spray is generated by the liquid flow entering the chamber 100, which is directed onto the tip section 22 of the adsorption sample probe 10. The timing of the liquid spray can be selectively varied and is user-defined. For example, the spray can be activated once the adsorption sample probe 10 is fully inserted into the chamber 100. Alternatively, the spray can be activated during or before the initial introduction of the adsorption sample probe 10 into the chamber, so that the probe is sprayed directly along its length as it is inserted into the chamber 100. The downward angle of the liquid inlet orifice 90 means that the jet is directed downward onto the tip section 22. This limits any backward splashing or upward spraying through the inlet opening 94 without a seal, which in turn is limited by the tight fit between the adsorption sample probe 10 and the inlet opening 94. The avoidance of the seals prevents the cleaning probe 10 from being contaminated by contact with seals that may harbor contaminants when it is withdrawn from the chamber 100. The annular arrangement of multiple liquid inlet holes 90 around the cover means that the entire periphery of the tip section 22 is sprayed. Liquid flowing down from the tip section 22 flows downward to the outlet 108, through which it is discharged from the chamber 100.

[0091] The controller is configured to run the cleaning cycle for a predetermined period of time. Once the cleaning cycle is complete, the drying cycle begins. This drying cycle can begin immediately or after an interval set to allow bulk liquid to drip from the tip section 22. Pressurized air is pumped into the chamber through an air inlet port 92, where annularly arranged air nozzles create a circumferential air curtain around the periphery of the tip section 22. Like the liquid inlet port 90, the air inlet port 92 is angled downward toward the base of the chamber 100. The air curtain is confined to the area of ​​the air inlet port 92, but some drying does not occur below this area due to air circulation generated within the chamber 100. Once the air curtain has been created through the air inlet port 92, the adsorption sample probe 10 can be vertically withdrawn from the chamber 100. As the adsorption sample probe 10 is withdrawn upward, the tip section 22 is pulled along its entire length by the drying air curtain provided. To improve drying efficiency, the air supplied to the air inlet port 92 can be heated or cooled before entering the chamber 100. The cleaning and drying station 14 can also be used to remove the sample from the probe by passing the solvent through the adsorption sample probe 10. The liquid sample can be collected as it exits the substrate of the chamber 100.

[0092] To enable the robotic arm to manipulate the adsorption-type sample detector 10, a detector adapter 18 is provided, which adapts the robotic arm for use with the adsorption-type sample detector 10, such as... Figure 9 As shown in the diagram. The probe adapter 18 or transport assembly is also designed to transport the sample container 2 and / or simultaneously transport both the sample container 2 and the adsorption sample probe 10. The probe adapter 18 includes a second body 110 having a first pickup connector 112 extending upward from the second body 110. The pickup connector 112 has a head 114 having the same construction as the head of the handle segment 20 of the adsorption sample probe 10. The adapter pickup connector 112 is configured to be picked up and engaged by a fixed mechanical latch of the robotic arm 6.

[0093] The first and second z-axis actuators of the robotic arm 6 are laterally spaced apart by a distance D. An annular hole 116 is formed in the second body 110, having a central axis spaced apart by a distance D from the longitudinal axis of the connector pickup 112, such that the central axis is coaxial with the second z-axis actuator when the probe connector 18 is connected to the retaining latch mechanism of the first z-axis actuator. A hollow columnar wall extends around the periphery of the annular hole 116, standing upright from the upper surface of the probe connector 18. The wall is semi-annular with a gap formed therein and includes an upper surface 119. In use, when the second z-axis actuator moves downward through the annular hole 116 to reach the release depth, the sliding collar of the release mechanism engages the upper surface 119 to release the spring-loaded latch and allow the suction-type sample probe 10 to be disassembled. Without the stop surface provided by the element provided by the probe connector 18, it would be impossible for the standard z-axis actuator of the robotic arm to release the adsorption sample probe 10 as required for automated multi-sample sampling.

[0094] As in Figure 10 As shown, a columnar wall extends downward from the lower surface of the second body 110. A magnet, one of a plurality of magnets, is disposed on the lower edge of the wall. The diameter of the annular aperture 116 is selected to allow the adsorption sample probe 10 to extend upward unobstructed through the annular aperture 116, and the diameter of the aperture is larger than the diameter of the adsorption sample probe 10. The probe adapter 18 also includes a barcode reader 122, which is arranged to read a recessed barcode segment disposed on the handle section 20 of the adsorption sample probe 10. This allows each adsorption sample probe 10 to be tracked throughout the sample and analysis process.

[0095] In addition to the first probe attached to the robotic arm 6 via the annular hole 116, a second identical probe can be attached to the robotic arm along the second axis 124 using a second z-axis actuator. This allows the robotic arm 6 to transport up to two adsorption sample probes 10 and sample containers 2 at any given time.

[0096] In use, the robotic arm 6 selects and acquires the probe connector 18, wherein the first z-axis actuator of the robotic arm picks up the probe connector 18 via the pick-up connector 112. The diameter of the annular wall is preferably substantially equal to the diameter of the sample container's lid, but can be any suitable configuration that allows at least a portion of the magnetic segment to be disposed on and engaged with the lid of the sample container 2 when the annular hole 116 is co-centered with the sample container 2. The probe connector 18 can acquire the sample container 2 by placing the lower surface of the wall in contact with the lid 74 of the sample container 2, such that the magnetic portion is magnetically secured to the metal lid of the sample container 2. This can be achieved with or without the magnetic probe 10 positioned in the sample container 2. The probe connector 18 can also be moved to acquire the magnetic probe 10 by co-centeredly aligning the annular hole 116 with the axis of the magnetic probe 10. The handle section 20 of the adsorption sample probe 10 can extend upward through the annular hole 116, and then the Z-axis actuator of the robotic arm 6 can acquire the adsorption sample probe 10 by connecting to the head of the handle section 20. The adsorption sample probe 10 can be actuated along the Z-axis through the annular hole 116.

[0097] When the adsorption sample probe 10 is inserted into the sample container 2 for sampling, the probe connector 18 is also able to acquire both the adsorption sample probe 10 and the sample container 2. In this arrangement, the probe connector 18 can be lowered over the adsorption sample probe 10 until the magnetic segment engages the lid of the sample container 2 with the extended adsorption sample probe 10. The adsorption sample probe 10 then simultaneously engages with the Z-axis actuator, and the probe connector 18 is raised by the Z-axis actuator, wherein the sample container 2 is raised through its lid 74 rather than directly through the adsorption sample probe 10. However, it should be noted that the seal between the adsorption sample probe 10 and the sample container 2 is such that when the adsorption sample probe 10 is raised by the Z-axis actuator, the sample container 2 can be raised directly through the probe without jeopardizing the sealing lid.

[0098] The robotic arm 6 can be controlled and operated to select and acquire probe adapter 18 from the adapter change station. As will be described in further detail below, the adapter change station houses the probe adapter 18 and the headspace syringe tool. The probe adapter 18 serves as a adapter that enables the standard robotic arm 6, typically used for syringe analysis, to acquire the adsorption sample probe 10. The probe adapter 18 is also configured to enable the robotic arm to acquire the sample container 2.

[0099] The advantage of using a mechanism similar to that used for acquiring and manipulating the syringe adapter is evident: the series of operations using the syringe and the adsorption sample probe 10 can be performed automatically on a single sample or a series of samples, thereby increasing sample output and analytical flexibility. As an example, a syringe may be provided to enable headspace sampling. The needle of the headspace syringe is configured to be inserted through a septum of a sealed sample container to collect a sample of headspace gas. The headspace syringe is configured to be engaged and manipulated by the same robotic arm used to manipulate the adsorption sample probe 10.

[0100] In such Figure 16 In an alternative embodiment shown, the probe adapter 318 includes a gripping tool 320 configured to hold a sample probe 310. The gripping tool 320 includes opposing fingers 322 movable between a closed configuration and an open configuration to grip and release the sample probe 310. The gripping tool 320 includes gripping fingers 321 having a tip 323 configured to securely grip the head of the sample probe 310, such that the probe is linearly fixed relative to the gripping tool 320. The probe adapter 318 includes a pickup connector 312 extending from the body, which allows the probe adapter 318 to be acquired and engaged by a fixed mechanical latch of a robotic arm to pick up and move the probe adapter. The probe adapter 318 also includes a second connector 324 projecting upward from the body, operatively connected to the gripping tool 320. The second connector 324 includes a connection head 326 having the same construction as the connection head of the pickup connector 312 arranged for automatic mechanical connection.

[0101] The probe adapter 318 also includes a third connector 325, which includes a connector head 329 having the same construction as the connector head of the pickup connector 312 arranged for automatic mechanical connection.

[0102] When connected by an automated mechanism, the linear actuation of the third connector 325, performed by the automated mechanism, causes the clamping tool 320 to rotate about the vertical axis of the second connector 324. This rotation allows the sample probe 310 to rotate, which in turn allows the sample probe 310 to be positioned in any direction. One application of this mechanism is to automate the reading of barcodes mated to the body of the sample probe 310 or mated to the sample container 2.

[0103] When connected to the automated mechanism, linear actuation of the second connector 324 by the automated mechanism causes the gripper 320 to open and close. During the probe sampling cycle, the probe connector 318 of the gripper is acquired by the automated mechanism. The automated mechanism connects to the first connector and the second connector 324. The automated mechanism can then pick up and release the sample probes and containers as many times as required for actuating the gripper 320 during the sampling cycle without disconnecting from the probe connector 318. The advantage of this arrangement is that it protects the connector of the automated mechanism from wear, as connection to the probe connector is only required once during the sampling cycle. In contrast, in the aforementioned embodiment, the automated mechanism is directly connected to the adsorption sample probe 10, and thus must be connected and disconnected with each adsorption sample probe 10 during the sampling cycle. Replacing the tips of the gripping fingers due to wear is significantly simpler and cheaper than replacing the connector of the automated mechanism.

[0104] Each tip 323 of the clamping finger 321 includes a channel 327 configured to receive an enlarged diameter segment 328 of the head of the sample probe 310. (As in...) Figure 17 As shown, each of the opposing distal ends of the tip 323 includes a curved section 332 that corresponds to the outer surface of the diameter-reducing section 334 of the head of the sample probe 310. The axial end face 336 of the tip 323 facing the sample container in use includes an embedded magnet 338.

[0105] Magnet 338 is arranged to engage with the lid 74 of sample container 2. (As in...) Figure 18 As shown, the gripping tool 320 is moved to engage with the cover 74. A magnet 338, positioned in the axial end face 336 of the finger tip 323, engages with and is magnetically connected to the metal cover 74. Once magnetically secured, the gripping tool 320 is able to pick up the sample container 2. This allows the gripping tool to selectively pick up either the sample container or the sample probe, enabling both the sample container and the sample probe to be automatically and mechanically manipulated without altering the probe adapter.

[0106] To facilitate the analysis of the combined liquid and headspace samples, the oven must be able to accommodate both the adsorption sample probe 10 and the needle of the headspace sampling syringe. If configured for use with the adsorption sample probe 10, the oven's inlet orifice is not suitable for use with the syringe needle. A fine needle cannot create a seal within the relatively large inlet channel required by the adsorption sample probe 10.

[0107] Therefore, as Figure 11 As shown, an oven adapter 150 is provided. The oven adapter 150 is positioned and secured within the inlet opening of the oven 16. The oven adapter 150 has an external shape corresponding to the shape of the upper portion of the adsorption sample probe 10, and is secured and sealed within the opening of the oven 16 in the same manner as the adsorption sample probe 10. The oven adapter 150 has a central channel 152 that is in open communication with the heated chamber of the oven 16, and this central channel is configured to receive a needle 154 of a syringe. A sealing arrangement is provided to maintain a seal between the external atmosphere and the heated chamber of the oven when the needle is inserted into the channel. Figure 11 In the arrangement, the gas-tight arrangement between the syringe and the oven includes a diaphragm 156, which is held between the lower portion and the upper portion 160 of the connector body 158.

[0108] Oven connector 150 Figure 12 The syringe is shown fitting into the opening of the oven 16. The oven connector 150 fits into and is sealed in the inlet in the same manner as the adsorption sample probe 10. The oven connector 150 is held in place in the oven 16 by the same lid latch mechanism 161 described above for retaining the adsorption sample probe 10 within the oven 16. The needle 154 passes through the diaphragm 156 of the oven connector 150, which creates a seal between the syringe needle and the interior of the oven 16. The sample is injected from the syringe into the liner 162 of the oven 16 and then swept into the cold trap by the carrier gas, after which the sample is transferred to the GC, as described above.

[0109] The shape of the connector's head allows it to be manipulated by the robotic arm 6, enabling the oven 16 to be automatically reconfigured for both syringe-based sampling and solid-phase analysis in the same analytical run, without user intervention. It is envisioned that the same principle could be employed to configure the sample inlet for operation alongside other sample extraction devices.

[0110] As with probe sampling, additional headspace samples can be applied to the focusing / cold trap and / or the second adsorbent trap for archiving and repeat analysis. Once the required sample is present on the cold trap, oven 16 is isolated from the carrier gas and the focusing trap is heated in the carrier gas flow directed to the GC column for analysis and / or the second adsorbent trap for archiving and repeat analysis. Once the sample collected on the cold trap is delivered to the GC column or if additional headspace sampling is not required, oven 16 is cooled. Once cooled, robotic arm 6 engages oven adapter 150 and latching mechanism 161 is released, allowing oven adapter 150 to be removed so that the adsorbent sample probe 10 can be inserted as required.

[0111] Figure 13 A multi-tube sampling assembly 170 is shown, in which one or more samples desorbed from an adsorption sample probe 10 or acquired from headspace sampling can be collected on adsorbent-filled recollection tubes 172 for archiving purposes. The recollection tubes 172 are loaded into sample trays 174 configured to hold multiple recollection tubes 172. The sample trays 174 are inserted into tray chambers 176 that can hold multiple sample trays 174. The sample trays 174 are moved via actuators to present the recollection tubes 172 in a position where they are sealed to nozzles 178 via their caps. A valve arrangement guides the sample partially or entirely from the oven 16 directly or via a cooling trap toward the recollection tubes 172, thereby selectively adsorbing the analytes within the sample onto the adsorbent material contained therein.

[0112] The desorption oven 180 allows the recollection tube 172 to be heated, so that the recollected sample can be re-desorbed back to the same or alternative focusing device for reanalysis or further recollection. It can be seen that, in the same manner, samples collected on the tube can be analyzed and recollected independently of the implementation method.

[0113] The sampling device preferably also includes an alignment element that, when received within the sample probe for vertical alignment, engages the sample probe to allow it to be connected to a second vertical actuator. The sample probe is supported within the container by a flexible diaphragm. In use, although the sample probe is inserted into the container with a fully vertical orientation, it can begin to deviate away from the vertical axis over time, particularly during agitation. If the sample probe is not aligned with the vertical axis, it becomes difficult for the actuator operating on the vertical axis to retrieve the sample probe from the top.

[0114] The alignment element may include first and second alignment elements that are movable in opposite horizontal directions to engage with the opposite side of the sample probe. The alignment element is movable between an alignment position, in which it engages the sample probe to hold it in a substantially vertical orientation, and in the release position, in which the sample probe and sample container can be vertically lifted.

[0115] As in Figure 14 As shown, alignment mechanisms are provided to vertically align the adsorption sample probe 10 when it is received in the sample container 2, for example, during agitation. The alignment mechanisms include a horizontally arranged upper alignment plate 202 and a lower alignment plate 204 arranged parallel to the upper alignment plate 202. The upper alignment plate 202 includes a first aperture 206, and the lower alignment plate includes a second aperture 208, both having a diameter larger than the diameter of the sample container 2. The upper alignment plate 202 and the lower alignment plate 204 are actuated to be movable in opposite horizontal directions. Figure 15 As shown, the first holes 206 formed in the upper alignment plate are substantially circular. Each first hole 206 includes a first guide channel 210 extending therefrom. The upper alignment plate 202 is movable in the horizontal direction along the longitudinal axis C. The first guide channel 210 has a diameter substantially equal to the diameter of the handle of the adsorption sample probe 10, and this first guide channel extends from the hole in a common longitudinal direction corresponding to the longitudinal movement axis C. The third hole 212 of the lower alignment plate 204 is arranged in the same positioning array as the holes of the upper alignment plate 202 and is fully aligned with the holes in the first release position. The second guide channel 214 of the third hole 212 extends to the first guide channel 210 in the opposite longitudinal direction. Figure 15 In the alignment position, the first guide channel 210 and the second guide channel 214 are aligned to define a circular hole for receiving and engaging the adsorption sample probe 10. In the alignment position, the fourth hole 218 defined by the first guide channel 210 and the second guide channel 214 is aligned with the center of the sampling axis of the sample container 2. In this way, the adsorption sample probe 10 is held on the sampling axis at its lower end by the sample container 2 and at its upper end by the fourth hole 218 of the upper alignment plate 202 and the lower alignment plate 204. In the release position, the main hole is aligned to define a channel through which the sample container can move vertically without obstruction, allowing the actuator to lift the sample container 2 and the adsorption sample probe 10 vertically through the upper alignment plate 202 and the lower alignment plate 204.

Claims

1. A sampling device for adsorption sampling, comprising: A sample container for holding the liquid to be sampled; A sample probe having a probe section housed within the sample container, the probe section including an adsorbent material arranged to acquire an analyte from the sample container; as well as An actuator configured to be independently connected to and manipulate the sample container and the sample probe; Controller; A first connector releasably connects the actuator to the sample probe; A second connector releasably connects the actuator to the sample container; as well as A sample probe adapter having a first mating connector configured to be releasably connected to the actuator, and a second connector releasably connected to the sample container, the second connector being included on the sample probe adapter. In a first operating mode, the actuator is operated by the controller to selectively and automatically connect to and disconnect from the sample probe and the sample container, the sample probe and the sample container being independent of each other. In a second operating mode, the first connector and the second connector are arranged to connect simultaneously to the sample probe and the sample container, the probe section of the sample probe being housed within the sample container. The sample container includes a lid with a metal element, and the second connector of the sample probe adapter includes at least one magnet arranged to magnetically secure it to the metal element of the lid of the sample container; and The actuator includes a first vertical actuator and a second vertical actuator, and the first mating connector of the sample probe mating device is arranged to be connected to the first vertical actuator.

2. The sampling device according to claim 1, wherein, The actuator is a three-axis robotic arm.

3. The sampling device according to claim 1 or 2, wherein, The actuator includes a releasable connector, and the sample probe includes a connector portion that is shaped to be detachably held by the releasable connector.

4. The sampling device according to claim 1, wherein, The sample probe includes a connecting element configured to connect to the second vertical actuator.

5. The sampling device according to claim 4, wherein, When the sample probe adapter is connected to the first vertical actuator, the sample probe adapter allows the second vertical actuator to move vertically relative to the sample probe adapter.

6. The sampling device according to claim 5, wherein, The second vertical actuator includes a release mechanism arranged to release the sample probe from the second vertical actuator, and the sample probe connector includes a stop element configured to engage the release mechanism when the second vertical actuator moves downward relative to the sample probe connector to operate the release mechanism and cause the release mechanism to release the sample probe.

7. The sampling device according to claim 6, wherein, The sample probe adapter includes a hole extending through it along the sampling axis, and the stop element is arranged at least partially around the periphery of the hole on the upper surface of the sample probe adapter to engage the release mechanism when the second vertical actuator moves downward through the hole to reach the release position.

8. The sampling device according to claim 7, wherein, When the sample probe connector is connected to the first actuator, at least a portion of the release mechanism is radially spaced outward relative to the hole, and the second actuator operates across a first vertical movement range and is capable of moving below the lower limit of the first movement range to reach a release position. Within the first vertical movement range, the release mechanism remains vertically spaced from and above the stop element. In the release position, the at least a portion of the release mechanism that is radially spaced outward relative to the hole engages with the stop element.

9. The sampling device according to claim 7 or 8, wherein, The stop element includes an upright wall extending around at least a portion of the hole, the wall having an upper surface arranged to engage the release mechanism.

10. The sampling device according to claim 1, wherein, The sample probe adapter includes a clamping mechanism configured to clamp the sample probe to provide a releasable connection between the actuator and the sample probe. The clamping mechanism includes a connecting element configured to connect to the second vertical actuator so that the clamping mechanism can be operated by the second vertical actuator.

11. The sampling device according to claim 10, wherein, The at least one magnet of the sample probe connector is disposed on the clamping mechanism.

12. The sampling device according to claim 11, wherein, The clamping mechanism includes a movable clamping element, and the at least one magnet is disposed at the distal end of at least one clamping element in the clamping element.

13. The sampling device according to claim 4, wherein, The sample container includes the sample probe along a sampling axis inserted into the sample container, and the sample probe adapter includes a sampling axis aligned with the sampling axis of the sample container when the sample container is connected to the second connector of the sample probe adapter, the first mating connector of the sample probe adapter being spaced apart from the sampling axis such that when the first mating connector is connected to the first vertical actuator, the second vertical actuator is axially aligned with the sampling axis.

14. The sampling device according to claim 13, wherein, The body of the sample probe adapter is configured such that when the first mating connector of the sample probe adapter is connected to the first vertical actuator, the body of the sample probe adapter is spaced apart from the sampling axis, so that the sample probe can be actuated vertically along the sampling axis without interfering with the body of the sample probe adapter.

15. The sampling device according to claim 14, wherein, The sample probe connector and the actuator are arranged such that when the first connector is connected to the first vertical actuator and the second connector is secured to the sample container, the second vertical actuator can actuate the sample probe vertically independently of the sample container.

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