• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates both to a cartridge (1), a sampling device (2, 3) and an extraction device (4) which allow a safe measurement without contamination of the absorbent neither before nor after sampling. . Thus the cartridge (1) for sampling according to the invention comprises a cylindrical envelope (10) of inert material in which is disposed an absorbent material (13) and sealed by two caps (11, 12) at both ends ( 100, 101) of the cylindrical envelope (10), it is characterized in that each cap (11, 12) has an opening (111, 121) which is closed by a seal (110, 120) made of a film silicone and an aluminum barrier layer. The use of a specific silicone and aluminum or aluminum / silicone / aluminum film makes it possible to withstand the high temperatures required for the thermal desorption technique, ie between 250 ° C and 350 ° C.
    公开号:FR3036489A1
    申请号:FR1559891
    申请日:2015-10-16
    公开日:2016-11-25
    发明作者:Olivier Hoffarth；Serge Junca
    申请人:Action Europe Sarl；Ncx Sarl；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to the sampling of pollutants in air or in water, which is carried out according to specific standards described in the literature. Measurement of indoor air quality is generally applied to monitoring: -of dwellings -of public premises -of offices The measurement of the quality of running water concerns the water distributed in dwellings and all public places.
    [0002] State of the art The sampling of pollutants in the air is today carried out actively or passively. In the case of an active sampling the collection of the sample will be done using pumps connected to sampling tubes containing selective adsorbents depending on the pollutants to be collected. These absorbents are in powder form. After pumping a known quantity of air or water through the tube containing the adsorbent used to trap the pollutants, the tube is either extracted with a very toxic solvent of the CS2 type (sulfide of carbon) is desorbed thermally using a thermal desorber. Passive sampling methods exist. In this case it is necessary to work with a badge carried by a person and containing capsules filled with an adsorbent to perform a passive collection of pollutants by diffusion through a membrane. The collection can last 8 hours at 3036489 2 4.5 days depending on the exposure of people and the type of pollutants to be collected. The sampling is generally carried out using a constant-flow pump which is connected to a two-segment tube packed with a specific adsorbent of the activated carbon type, TenaxTM, chromosorb etc. to trap the pollutants in function. their nature and expected concentrations. The sampler connects the tube (trap) to the pump and adjusts the recommended flow rate according to the pollutant of the exposure concentration tolerated by the legislator. The recommended sampling time is 24 hours (Experimental Standard XPX43-402). After the sampling phase, the tube is opened at one end to remove the adsorbent on which pollutants have been collected. Both segments are extracted with CS2 or benzyl alcohol before being analyzed separately to verify that the adsorbent has not been saturated on the first segment. These systems have many drawbacks: the loss of information during the extraction by the solvent by the dilution of the sample, the reproducibility is difficult because of the sampling mode: air flow, flow control air, homogeneity of the adsorbent, etc. - The preservation of the sample and its integrity is not guaranteed, indeed, there is a risk of contamination of the absorbent to be analyzed, because the absorbent is brought into contact with the outside between the collection and the analysis. Some compounds remain adsorbed on the adsorbent. - The extraction requires the use of polluting solvents. - The time used for the extraction is very important. - The price remains high. The thermal desorption extraction technique is more efficient and sensitive. It is generally used in the context of active sampling by pumping on stainless steel or glass cartridges containing an adsorbent 3036489 3 maintained by quartz wool. A double sampling or the division of the gas flow during the desorption and the recollection of 50% on an empty tube is generally necessary to preserve a control. This technique requires the conditioning and the systematic control of the 5 tubes before use. The preservation after sampling requires the use of closure caps tubes whose sealing is often debatable. The tubes have a large dispersion with respect to the pressure drop of each tube before and during the sampling. The tubes can not be used for sampling liquids. The internal dead volume is very important and reduces the sensitivity. DESCRIPTION OF THE INVENTION The object of the invention is to provide a cartridge, a sampling device and an extraction device which allow a safe measurement without contamination of the absorbent either before or after sampling. In particular the cartridge may be inert, traced and recyclable to perform both active or passive sampling. The sampling cartridge according to the invention comprises a cylindrical casing of inert material in which is disposed an absorbent material and sealingly closed by two caps located at both ends of the cylindrical casing, it being characterized in that each cap has an opening which is closed by a seal made of a silicone film and at least one barrier layer of aluminum. The use of a specific silicone and aluminum or aluminum / silicone / aluminum film makes it possible to withstand the high temperatures required for the thermal desorption technique, ie between 250 ° C and 350 ° C. The silicone has a capacity of recess that allows to close a hole that would be practiced there. Aluminum has a barrier effect which makes it possible to obtain a perfect seal to the most volatile molecules. The polymer is thus totally isolated from the outside environment thanks to a controlled and efficient seal. The film also makes it possible to limit the uncontrolled introduction of air at the end of an active sampling. On the other hand, the aluminum is neutral vis-à-vis the traces to be analyzed. The tubes are preferably packaged under an inert gas (eg argon heavier than air) to avoid cross-contamination with the external environment. To date, no adsorption tube for the environmental field is conditioned under an inert gas. Providing the cartridge sampling system makes it possible to add a solvent such as dichloromethane for extraction preferably by stirring the cartridge. The extract will not be in contact with the laboratory air and cross-contamination will be impossible unlike the systems on the market today. After the extraction phase, the injection can be done on an LCMS system (liquid chromatography coupled to mass spectrometry) for example to assay the drugs or endocrine disruptors in water. The solvent extraction technique directly into the cartridge may also be suitable for other applications such as the determination of allergens, narcotics, drugs or explosives. The device can be adapted to its geometry to be transferred directly to the sample racks of the various automatic analyzers. Advantageously, the cylindrical envelope is made of glass. The glass is amber or transparent. The use of amber glass avoids the degradation of photosensitive molecules collected. The glass surface treatment (passivation or deactivation) also makes it possible to lower the detection limits of certain molecules such as those of pesticides. The envelope may have the film-coated glass walls (deposition of a silicone or PDMS selective phase (polydimethylsiloxane) with a suitable selectivity and film thickness.After the phase deposition, the cartridge is sealed under inert gas.
    [0003] Advantageously, the absorbent material is a polymer. The cartridge contains a solid polymer or in the form of powder or glass beads coated with a polymer, an adsorbent of activated carbon or graphite type, a porous polymer of TenaxTM type, a diatomite or a clay, any microporous adsorbent support. miniaturized sensors, paper media impregnated with a reagent or calorimetric indicators, agar plates. The use of a solid single-use, ready-to-use polymer is positioned with one or two axial centerers in the tube. The centralizer is a metal grid with a known and regular porosity of 200 μm provided with a central hole equal to the diameter of the polymer (cylinder) for axially positioning the polymer in the center of the tube 10 and at an equal distance from the walls of the glass tube. . This technique will allow a homogeneous exchange of the gaseous or liquid phase with the polymer during the adsorption phase. Advantageously, one of the caps is crimped on the cylindrical envelope. The cartridge then has a crimping neck with a diameter of 11 mm, for example, on one side and a neck with a double ring of 11 mm, for example, on the other side allowing the use of the capsule to be clipped, but also crimp capsules. This configuration allows the opening of the cartridge without using specific tools to remove the polymer if necessary. Advantageously, one of the caps is clipped onto the cylindrical casing. Advantageously, the cylindrical envelope is made of reusable material. For example if the tube is glass. We have a partly recyclable and ecological device. The glass cartridge is recyclable by the manufacturer. The product is ecological and reusable after the extraction of the closures and the cleaning and decontamination of the glass. The invention also relates to a sampling device comprising a housing for a sampling cartridge with pierceable ends, characterized in that it comprises a fixed cannula and a translational cannula disposed on each side of the housing, a means for actuating the movable cannula between a retracted position and a piercing position of the cartridge. The cartridge may be open on one side without the use of particular tools since the sample will be made by the cannulas. The use is easy. Advantageously, a cannula is mounted on a removable connector. This allows disassembly and easy cleaning of the cannula.
    [0004] Advantageously, the cannula has a conical tip with a lateral piercing. This avoids clogging by the cartridge seal. Advantageously, the actuating means comprises a return spring. The spring allows the cannula to resume a retracted position when released from the piercing position.
    [0005] Advantageously, the actuating means comprises a baffle locking system. The cannula is locked in the piercing position by the actuating means itself. In a particular arrangement, the device includes a charge level indicator of the cartridge. This indicator will be for example a 15 LED. According to another arrangement, the device comprises a power interruption indicator. It will be possible to identify the distorted measures. This indicator may consist of an LED. Advantageously, it comprises an indicator of the time of the incrementation chosen. In a first variant, one of the cannulas is open to the outside air and the other to a suction pump. This variant makes it possible to measure the pollution of the air in a room, or in a given environment.
    [0006] According to a second variant, one of the cannulas is connected to a water inlet and the other to a gravity flow outlet. This variant makes it possible, for example, to analyze and measure the pollution of tap water distributed daily to millions of households. A specific housing to be screwed on the outlet of the water taps is then provided. Once screwed in, it will be sufficient to engage or arm the double-needle device to let the tap water through the cartridge and concentrate the pollutants present on the polymer. The system may also be equipped with a device for measuring or checking the flow of water that has passed through the sampling cartridge. Advantageously, a solenoid valve is disposed upstream of the cannula connected to the water inlet. This solenoid valve may include a timer to define a quantity of water to be analyzed. According to a third variant, the cannulas open into the same bottle of water and a pump is disposed between one of the cannulas and the bottle. The water circuit is thus closed circuit, so it is possible to work on an unlimited time. According to a fourth variant, one of the cannulas comprises a mouthpiece. We can thus analyze the exhaled air. A disposable tip (such as an alcoholometer tip) will be screwed onto the device containing the sample cartridge. This device will allow the air exhaled by the human to be concentrated in order to concentrate any marker or metabolites which make it possible to identify certain forms of cancer. The exhaled air passes through the sample tube containing the polymer or a specific adsorbent to be concentrated before being discharged through a large-diameter cannula located at the outlet of the cartridge. The patient will have to repeat the blowing several times according to various criteria. The system may be equipped with a device for measuring or checking the air flow that has passed through the sampling cartridge. After the sampling phase, the cartridge will be analyzed by thermal desorption or extraction followed by identification by GC-MS or LC-MS (gas chromatography or liquid chromatography coupled to mass spectrometry). The invention also relates to a passive sampling device, said device comprises a cylindrical housing for a sampling cartridge with pierceable ends, it is characterized in that the housing comprises a sealed side and a side with a removable cap interchangeably, a first interchangeable plug 3036489 8 sealed and a second interchangeable plug comprising a diffusion grid. With this device, the cartridge is introduced into the cylindrical housing which is specific and can be carried by an operator with a staple, fixed to a metal base by means of the magnet or be suspended using the one ring attached to the clip. The device is provided with all these accessories because the sampling height is very important. Before use, remove the watertight cap from the cartridge, then interchange the waterproof cap with the cap with the diffusion grid. During sampling the air will pass through the diffusion grid which may be stainless steel which allows to obtain a controlled passage through a standardized orifice. After the sampling the waterproof cap is reassembled on the cartridge and the cap incorporating the seal is screwed onto the cylinder. The system has the advantage of dual sealing and dual functionality. Advantageously, the sealed side of the cylinder comprises a recess closed by an interchangeable removable plugs. The device thus serves not only for the collection of the sample but also to keep the sealing cap in the stopper pending the end of sampling, the seal ensures the sealing of the device for shipment of the whole laboratory. This is a device for taking and keeping the sample taken. The invention also relates to a passive sampling device comprising a cartridge according to the invention, characterized in that the cartridge is equipped with a diffusion grid disposed near one end of the cylindrical envelope and a sealed cap. clip. It is therefore possible to use the cartridge itself as a sampling device by removing the clip cap to take the sample and put it back once the sampling is complete.
    [0007] The invention also relates to an extraction device disposed between an inlet of a carrier gas and an analyzer, and comprising a housing for a sampling cartridge with pierceable ends, a heating system of the cartridge, it is characterized in that it comprises a fixed cannula and a translating cannula disposed on each side of the housing, between a retracted position and a drilling position of the cartridge. Advantageously, the movable cannula is actuated by screwing. The cannula can therefore be easily inserted into the cartridge to be analyzed. Advantageously, one of the cannulas is intended to be connected to the vector gas inlet. The carrier gas is injected on one side to extract the elements to be analyzed and emerged through the other cannula. Advantageously, the other cannula is intended to be connected to the injector of an analyzer. The carrier gas with the elements to be analyzed thus arrives without contamination outside the analyzer. The invention also relates to a sampling and extraction device, it is characterized in that it comprises the extraction device above connected a body comprising a suction pump and an inert gas tank. In this way, the cartridge can be put in the device, which in sampling mode, will be able to suck the outside air, for example, thanks to the pump; once the sample is finished, the cartridge is heated and the gas contained in the cartridge is reinjected to send it to an analyzer. Other advantages may still appear to those skilled in the art on reading the examples below, illustrated by the appended figures, given for illustrative purposes.
    [0008] BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a sectional view of a first example of a cylindrical envelope of the cartridge according to the invention; FIG. 2 is a section of a second example of a cylindrical envelope of the cartridge according to FIG. FIG. 3 is a perspective view of a cap of the cartridge according to the invention, FIG. 4 is a cross-section of a first embodiment of a sampling device according to the invention. FIG. FIG. 5 is a detail of the cannula of the device of FIG. 4; FIG. 6 is a detail of the tip of the cannula of FIG. 5; FIG. 7 is a perspective view of the device of FIG. FIG. 8 is a cross-section of a second embodiment of a sampling device according to the invention in the sampling position, FIG. 9 is a cross-section of the second extraction mode in position of FIG. FIG. 10 is a section of the extraction device according to the invention; Fig. 11 is a cross-section of a passive sampling cartridge; Fig. 12 is a sectional view of the sampling and extraction device according to the invention; Fig. 13 is a perspective view of Fig. 12. The sampling cartridge 1 according to the invention comprises a cylindrical envelope 10, two caps 11 and 12 disposed on each side 100, 101, of the envelope 10 and an absorbent material 13 placed inside the envelope 10. The envelope 10 may be amber or transparent glass. The absorbent material 13 will be, for example, a ready-to-use disposable polymer or specific adsorbents making it possible to universally trap all types of pollutants. The caps 11 and 12 are sealingly sealed to the cylindrical envelope 10, they can be aimed, clipped or crimped, the closure should preferably be able to withstand high temperatures, up to 350 ° C, and have properties special reconciliation and excellent neutrality. If a solid single-use, ready-to-use polymer is used, it is positioned with one or two axial centerers 14 in the casing 10. The centralizer 14 is a metal grid of known and regular porosity. for example 200 μm, provided with a central hole equal to the diameter of the polymer (cylinder) for axially positioning the polymer in the center of the casing 10 and at an equal distance from its walls. This technique allows a homogeneous exchange of the gaseous or liquid phase with the polymer during the adsorption phase. Cartridge 1 may also contain a solid polymer or in the form of powder or glass balls coated with a polymer, an adsorbent of activated carbon or graphite type, a porous polymer of TenaxTm type, a diatomite or clay, any microporous adsorbent support but also miniaturized sensors, paper media impregnated with a reagent or calorimetric indicators, agar plates. The cartridge 1 may also contain a combination of several portions of capillaries containing phases or adsorbents and arranged axially through the centraliser 14. The air will circulate through the multi-selective capillaries and the pollutants will be retained in this device specific. Cartridges 1 may also contain an agar for microbiological analyzes. The dosage of legionella may be possible.
    [0009] It is also possible to serially mount several cartridges containing the same trap or traps of a different nature to increase the selectivity when removing unknown substances. The packaging of the cartridges 1 is done under an inert gas, for example argon which is heavier than air, in order to avoid any cross-contamination with the external environment. The sealing of the cartridge 1 is done by using a cap 11, 12 with a specific seal 110, 120 made of silicone / aluminum or aluminum / silicone / aluminum which is resistant to the high temperatures necessary for the thermal desorption technique, ie between 250 ° C. and 350 ° C. The neutrality of aluminum with respect to the races to be analyzed is advantageous, and the barrier effect of aluminum makes it possible to obtain a perfect seal for the most volatile molecules. Each cap 11,12 comprises an outer metal part pierced with a hole 111, 121 closed by the seal 110, 120. The seal 110, 120 may be pierced by a cannula.
    [0010] The envelope 10 of FIG. 1 is mixed on the side 100, it has the form of a crimping neck and on the other side 101 it has a screw thread. The closure of the envelope of the cartridge illustrated in FIG. 2, is of mixed type: the envelope 10 has on one side 100 a crimping collar, its diameter may for example be 11 mm, and a double-ring collar of 10 11 mm on the other side 101 allowing the use of a cap to clip but also crimping caps. These configurations allow the opening of the cartridge 1 without the use of specific tools to remove the absorbent material 13 if necessary.
    [0011] The cartridge 1 may comprise an envelope whose walls are made of glass coated with a film (deposition of a selective phase of silicone or PDMS type) with a selectivity and a suitable film thickness. After the phase deposition the cartridge 1 is sealed under inert gas as indicated above. This envelope can be reused several times. Another variant of longer envelope may contain commercial sampling tubes used in thermo desorption. The identification, tracking and traceability of the cartridge will be possible because it may be marked by an engraving or laser QR code or barcode for monitoring the batch and its use during implementation. Cartridge 1 may contain a transponder (not shown) in order to be easily identified during the entire cycle of use, from collection to storage until analysis. Calibration and ready-to-use calibration is possible. In order to allow quantification of the pollutants taken, a kit of calibrated calibration cartridges may be proposed. The polymers will be labeled with isotopes to avoid possible cross-contamination errors. The series of 5Ong, 100, 200,500, 1000ng stallions will also contain a white and a tube containing quartz wool. A calibration by the user is also possible. Delivering the cartridge sampling system sealed on both sides with a silicone / aluminum or aluminum / silicone / aluminum seal allows the user to inject his own standard into the cartridge through the seal. and using a suitable syringe. The cartridge system containing the polymer is not subject to loss of charge and therefore to variations in flow rates due to the clogging of conventional polymers or adsorbents under the influence of the moisture content present during the sampling. where regularity and accuracy of sampling. The absorbent 13 may also be grafted or soaked with a DNPH drifting agent for formaldehyde analysis. The use of amber glass avoids the degradation of photosensitive molecules collected. The glass surface treatment (passivation or deactivation) also makes it possible to lower the detection limits of certain molecules such as pesticides. The use of an absorbent such as ready-to-use polymers makes it possible to retain a control. before the analysis. It is possible to use several polymers and to keep one as a control or to cut a polymer in two equal parts before analysis. The sampling is done on a device 2 according to the invention illustrated in FIGS. 4 to 7. The device 2 comprises a housing 20 for a cartridge 1 for sampling, a fixed cannula 21 and a mobile cannula 22 in translation arranged on each side of the housing 20, an actuating means 23 of the movable cannula 22 between a retracted position and a piercing position of the cartridge 1.
    [0012] Each cannula 21, 22, detailed in FIGS. 5 and 6, is mounted on a ring 220, 210 of the Luer type and ends with a conical tip with a lateral piercing 221, 211. The fixed cannula 21 is placed at one of the ends 200 of the recess 5 20 with a nut 205. A compression spring 202 is disposed around the fixed cannula 21 bearing on the end 200 on one side and on the cartridge 1 of the other. Two washers 203 and 204 may be placed on each side of the spring 202. The spring 203 will facilitate the extraction of the cartridge from the device. The fixed cannula 21 is connected to a suction pump. The movable cannula 22 is placed at the other end 201 of the recess 20; it is secured to the actuating means 23 which comprises a locking system 207 and a return spring 206. The locking system 207 here consists of a pin 207a sliding in a path 24. The return spring 206 is in support on the end 201 on one side and on a flange 230 of the actuating means 23 of the other. The device also includes a control 250 for adjusting the flow rate of the pump 25 and an outlet 251 for discharging the air or water to be analyzed. The pump 25 is powered by a battery 252 disposed in the body of the device 2. It may also have magnets 26 for attachment to a metal surface or clips for attachment to the belt. The device 2 operates in the following way: the cartridge 1 is placed in the recess 2, the mobile cannula 22 is pushed towards the cartridge 1 which will move until it reaches the fixed cannula 21, and then the spring 202 is compressed, this will have the effect of piercing the cartridge 1 at each of its ends, then the pump 25 is started to pass air or water to be analyzed in the cartridge 1. The sampling can also be done passively with the device 3 illustrated in FIGS. 8 and 9. The device 3 comprises a hollow body 30 with two threaded ends 300 and 301, a sealing cap 31 and an open cap 32 equipped with a clipped diffusion gate 320. One end 3036489 is closed while the other 301 is open. The end 300 comprises a recess 302. The two plugs 31 and 32 are interchangeable, that is to say that they can be arranged indifferently on each of the ends 300 and 301. The device 3 is equipped with a clip 5 33 to be attached to the belt. The sealing plug 31 has a magnet 310 on the opposite side to the threaded side, and a seal 311 inside the threaded portion. The magnet 310 makes it possible to fix the device 3 on a metal base. To carry out the sampling, the clipped cap 11 is removed from the cartridge 1, the cartridge 1 is placed in the hollow body, the open cap 32 is applied to the end 301, the cap 11 is placed in the recess 302 and the sealing cap 31 is tightened on the end 300. Once the sample has been taken, the plugs 31 and 32 are unscrewed, the cap 11 is replaced on the cartridge 1 and the sealing plug 31 is screwed onto the open end 301. and the cap 32 on the end 301. The cartridge is thus protected from the external elements and can be transported safely. The sample can also be made with a cartridge 1 like that of FIG. 11. In this cartridge 1 a diffusion grid 15 has been inserted at one of the ends 100, 101 of the tube 10. The cartridge 1 may comprise a clip of fixing to be able to door at the waist. To carry out the sampling, the clip-on cap 12 is removed to open the tube 10 and let the air in. Once the sample has been taken, the tube is closed with the cap 12.
    [0013] Once the sample has been taken, the results must be extracted and for this purpose an extraction device 4 as shown in FIG. 10 is used. The extraction device 4 comprises a hollow body 46, a fixed cannula 40, a cannula movable 41 secured to a plug 42, a heating element 43, an insulator 44 preferably ceramic and a connector 45. The fixed cannula 40 is placed in a needle holder 400 placed in the hollow body 46 and connected to a nozzle 47 through a septum 401. The movable cannula 41 is connected to the stopper 42 by an elastic ring 420 and to a pusher 421 placed inside the stopper 42. The stopper 42 is equipped with an adapter 422 so that to be able to connect the device 4 to a vector gas supply.
    [0014] The sampling and extraction device 5 of FIGS. 12 and 13 comprises an extraction device similar to that of FIG. 10 connected to a body 50 comprising a suction pump 51 and an inert gas tank 52. The inert gas may for example be helium. This device operates in the following way: a cartridge is placed in the device 5 in the same way as for the extraction device 4, a filter 53 is placed on the extraction device 4 on the opposite side to the body 50, the suction pump 51 will suck the outside air through the cartridge and the body 50, the air will emerge through a hole 54 and when the sampling is completed, the pump is cut, the filter 53 is removed to replace it by a needle 15 with a luer connector for connection to an analyzer (not shown). The gas tank 52 is opened and with the solenoid valve 55 the tank is put into communication with the cartridge 1.
    权利要求:
    Claims (5)
    [0001]
    REVENDICATIONS1. Extraction device (4) disposed between an inlet of a carrier gas and an analyzer, comprising a housing for a sampling cartridge (1) with pierceable ends, a heating system (43) of the cartridge (1), characterized in that it comprises a fixed cannula (40) and a movable cannula (41) in translation disposed on each side of the housing, between a retracted position and a drilling position of the cartridge.
    [0002]
    2. Extraction device (4) according to claim 1 characterized in that the movable cannula (41) is actuated by screwing.
    [0003]
    3. extraction device (4) according to one of claims 1 or 2 characterized in that one of the cannulas (41) is intended to be connected to the vector gas inlet.
    [0004]
    4. Extraction device according to the preceding claim, characterized in that the other cannula (40) is intended to be connected to the injector of an analyzer.
    [0005]
    5. Sampling and extraction device, characterized in that it comprises an extraction device according to one of claims 1 to 4 connected to a body (50) comprising a suction pump (51) and a tank of inert gas (52).
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP3298378A1|2018-03-28|
    FR3036490B1|2021-07-30|
    EP3298378B1|2020-02-26|
    FR3036488A1|2016-11-25|
    FR3036488B1|2017-10-06|
    WO2016188796A1|2016-12-01|
    CN107636441A|2018-01-26|
    FR3036489B1|2021-07-30|
    FR3036490A1|2016-11-25|
    JP2018519503A|2018-07-19|
    FR3036491B1|2020-11-27|
    US20180202902A1|2018-07-19|
    FR3036491A1|2016-11-25|
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    CN103398878B|2013-08-15|2015-08-19|深圳市建筑科学研究院股份有限公司|A kind of passive type air sampler|FR3095516A1|2019-04-25|2020-10-30|Universite De Pau Et Des Pays De L'adour|Device for taking a sample of elements of interest present in trace amounts in a pressurized gas|
    LU101569B1|2019-12-23|2021-06-28|Luxembourg Inst Science & Tech List|Passive sampler deployment housing|
    CN111323274B|2020-03-27|2021-07-02|北京市环境保护科学研究院|Low-rate quantitative passive monitoring system and method for air exposure concentration of polluted site|
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    2016-11-25| PLSC| Publication of the preliminary search report|Effective date: 20161125 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1554663A|FR3036488B1|2015-05-22|2015-05-22|DEVICE FOR SAMPLING AND ANALYSIS|
    FR1559891A|FR3036489B1|2015-05-22|2015-10-16|SAMPLING AND ANALYSIS DEVICE|FR1559891A| FR3036489B1|2015-05-22|2015-10-16|SAMPLING AND ANALYSIS DEVICE|
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