Passive sampling device and method for odor substances in water body based on molecularly imprinted polymer

Abstract

The invention discloses a water body odor substance passive sampling device and method based on a molecularly imprinted polymer, and relates to the technical field of water body odor substance passive sampling devices.The water body odor substance passive sampling device comprises an upper shell, an upper mounting cover is mounted on the upper shell, and threads are formed in the inner side face of the upper mounting cover; the water storage tank is composed of a modified polyvinyl alcohol hydrophilic inner container and a hydrophobic photosensitive resin shell, and has the advantages that external water enters the water storage tank in a one-way mode through the 80-100-micrometer micropore array on the side wall of the water storage tank by means of the wetting gradient capillary force of the hydrophilic inner container and the hydrophobic shell, the miniature water pump is started, and water in the water storage tank enters the water storage tank in a one-way mode; a water sample in the water storage tank is pumped to the micro flow meter through the water pumping pipe, so that the water sample enters the detection box and is in full contact with the molecular imprinting layer for specific adsorption, the enrichment of trace odor substances is realized, the structure realizes one-way water feeding through capillary force, the water feeding efficiency is improved by 32%, and the blocking rate lt is increased; 8%.

Description

Technical Field

[0001] This invention relates to the field of passive sampling devices for odorous substances in water, specifically a passive sampling device and method for odorous substances in water based on molecularly imprinted polymers. Background Technology

[0002] Current water odor monitoring primarily relies on a combination of active sampling and laboratory GC-MS. This system has fundamental limitations: instantaneous sampling (<24 hours) cannot capture dynamic fluctuations in the concentrations of substances such as 2-methylisoborneol (2-MIB) / GSM, leading to repeated complaints about odors in water sources due to missed peak concentrations, rendering dynamic monitoring ineffective. Furthermore, deployment costs are high, requiring at least three people for each sampling operation. This results in monitoring blind spots in remote reservoirs (accounting for over 40% of water sources) due to excessive transportation costs, with an average annual manpower investment exceeding 120,000 yuan per 100 square kilometers. Even after sampling, while conventional GC-MS methods have detection limits as low as 5 ng / L for 2-MIB / GSM (below the national standard limit of 10 ng / L), the high detection requirements make it difficult to achieve early warning of trace pollution.

[0003] While traditional passive samplers can extend the monitoring cycle, the single-material shell has a particulate matter blockage rate of up to 35% when the flow rate is >0.5m / s. The sudden drop in diffusion channel stability leads to a significant weakening of the monitoring efficiency of existing technologies during high-temperature algal blooms. This forces water authorities to make a difficult trade-off between risk control and cost control. To address this, we propose a passive sampling device for water odor substances based on molecularly imprinted polymers. Summary of the Invention

[0004] The purpose of this invention is to provide a passive sampling device and method for odor substances in water based on molecularly imprinted polymers.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a passive sampling device for odor substances in water based on molecularly imprinted polymers, comprising an upper housing 2, an upper mounting cover 3 installed on the upper housing 2, the inner side of the upper mounting cover 3 having threads, a water storage tank 1 installed below the upper housing 2, the inner side of the lower end of the upper housing 2 having threads, a micro flow meter 11, a water suction pipe 15 and a micro water pump 14 installed on the upper inner surface of the upper housing 2, a test box 12 connected to the micro flow meter 11, a water outlet pipe 9 connected to the side of the test box 12, a test module 13 installed inside the test box 12, the liquid outlet end of the micro flow meter 11 connected to the test box 12 through a pipe, the liquid inlet end of the micro flow meter 11 connected to the drain end of the micro water pump 14 through a pipe, the water suction end of the micro water pump 14 connected to the water suction pipe 15, and the water suction pipe 15 extending through the upper housing 2 into the water storage tank 1;

[0006] The water storage tank 1 is composed of a modified polyvinyl alcohol hydrophilic inner liner 5 and a hydrophobic photosensitive resin outer shell 8, and the side wall of the water storage tank 1 is provided with a micropore array with a pore size of 80-100μm.

[0007] As a further embodiment of the present invention: an upper threaded tube 16 is fixedly connected to the upper surface of the upper housing 2, an upper rubber pad 17 is fixedly connected to the upper surface of the upper threaded tube 16, and the upper threaded tube 16 is threadedly connected to the upper mounting cover 3.

[0008] The upper surface of the upper rubber pad 17 is in contact with the lower inner surface of the upper mounting cover 3.

[0009] As a further aspect of the present invention: the inspection module 13 is threadedly connected to the inspection box 12. The inspection module 13 is composed of a ternary functional monomer system consisting of methacrylic acid, acrylamide and 2-hydroxyethyl methacrylate. Using 2-MIB and GSM as template molecules, a molecular imprinted layer is constructed on an FTO conductive glass substrate by electrochemical cyclic voltammetric polymerization.

[0010] As a further embodiment of the present invention: an airbag 10 is fixedly connected inside the upper housing 2.

[0011] As a further embodiment of the present invention: a lower threaded pipe 6 is fixedly connected to the upper surface of the water storage tank 1, a lower rubber pad 7 is fixedly connected to the upper surface of the lower threaded pipe 6, and the lower threaded pipe 6 is threadedly connected to the lower end of the upper shell 2.

[0012] The lower rubber pad 7 is in contact with the lower inner surface of the upper housing 2.

[0013] As a further embodiment of the present invention: the water outlet pipe 9 extends through the side wall of the upper housing 2 to the outside, and a one-way valve 4 is provided on the side of the upper housing 2, and the one-way valve 4 is connected to the water outlet pipe 9;

[0014] The one-way valve 4 allows liquid in the outlet pipe 9 to flow out through the one-way valve 4.

[0015] As a further aspect of the present invention: a sampling method for a passive sampling device for odor substances in water based on molecularly imprinted polymers, characterized by comprising the following steps:

[0016] S1. Device Assembly: Install the inspection module inside the inspection box via threaded connection, ensuring that the inspection module fits snugly against the inner wall of the inspection box; screw the lower threaded tube of the water storage tank into the thread on the inner side of the lower end of the upper shell, so that the lower rubber pad is in close contact with the lower inner surface of the upper shell; thread the upper mounting cover into the upper threaded tube of the upper shell, so that the upper rubber pad is in contact with the lower inner surface of the upper mounting cover.

[0017] S2. On-site deployment: Select monitoring points in the water source area that avoid the surface algae accumulation area, and fix the assembled device at a depth of 1.5m underwater;

[0018] S3. Passive Sampling: External water enters the water tank unidirectionally through the micropore array with a diameter of 80-100μm on the side wall of the water tank, aided by the capillary force of the wetting gradient formed by the modified polyvinyl alcohol hydrophilic inner liner and the hydrophobic photosensitive resin outer shell. The micro water pump is activated, and the water sample in the water tank is pumped to the micro flow meter through the pumping pipe. After the flow rate of the water sample is stabilized by the micro flow meter, it enters the test box, where it fully contacts the molecular imprinted layer on the surface of the test module and is specifically adsorbed. The adsorbed water sample is discharged unidirectionally from the outside of the device through the outlet pipe and the one-way valve.

[0019] S4. Module Recovery and Testing: After the sampling cycle is completed, remove the upper mounting cover, unscrew the testing module on the testing box, perform elution treatment on the testing module, and then test the concentration of odor substances in the eluent.

[0020] As a further aspect of the present invention: In step S1, the molecularly imprinted layer of the testing module is constructed by electrochemical cyclic voltammetric polymerization. Specifically, the process is as follows: using methacrylic acid, acrylamide, and 2-hydroxyethyl methacrylate as a ternary functional monomer system (molar ratio of the three is 1:1:1), and using 2-MIB and GSM as template molecules, the system is cyclically scanned 20 times in a potential range of -0.5V to 1.2V at a scan rate of 10mV / s in 0.1M KCl electrolyte to form a molecularly imprinted layer with a thickness of 10-15μm on an FTO conductive glass substrate; In step S4, the elution treatment uses a mixed solvent of methanol and acetic acid in a volume ratio of 9:1 to ultrasonically treat the testing module, and the residual rate of odor substances on the molecularly imprinted layer after treatment is <3%.

[0021] As a further aspect of the present invention: In step S3, the range of the micro flow meter is 0-100 mL / min, and the flow rate of the water sample entering the test box is monitored in real time; the micro water pump drives the water sample to a constant flow rate of 0.28 mL / min; the contact angle of the hydrophobic photosensitive resin shell of the water storage tank is >110°, and the contact angle of the modified polyvinyl alcohol hydrophilic inner liner is <40°; the bottom of the water storage tank is a fully sealed structure, which can resist a hydrostatic pressure of not less than 10 cm, and prevent the water sample from leaking from the bottom.

[0022] As a further aspect of the present invention, it also includes a concentration inversion step S5: establishing a concentration inversion equation based on Fick's diffusion law, the formula being... ;in, To verify the mass (unit: μg) of odor substances adsorbed by the module. The cross-sectional area of ​​the diffusion path (unit: cm², the value is taken as the effective contact area of ​​the molecular imprinted layer of the test module). Sampling time (unit: seconds). The diffusion rate of odor substances (unit: cm² / s). The concentration of odorous substances in water (unit: μg / cm³). To verify the concentration of odor substances (unit: μg / cm³, value is 0) on the module interface. The length of the diffusion path (unit: cm, taken as the flow path length from the micropores of the water storage tank to the inspection module); diffusion rate. Based on water temperature correction, the correction formula is as follows: , Water temperature diffusion rate at time, The diffusion rate at 25℃; the adsorption rate ,and The calibration rate was 0.28 mL / min.

[0023] Compared with the prior art, the beneficial effects of the present invention by adopting the above technical solution are as follows:

[0024] 1. This invention selects monitoring points in the water source area that avoid surface algae accumulation zones (to prevent algae from clogging the micropores of the water storage tank or interfering with MIPs adsorption), fixes the assembled device at a depth of 1.5m underwater, adds a counterweight to the bottom of the device (to prevent the device from floating), and connects a GPS buoy to the top (for real-time positioning, facilitating inspection and retrieval after a 7-day monitoring cycle), ensuring the device's stable position without deviation. External water enters the water storage tank unidirectionally through the 80-100μm micropore array on the side wall of the tank, utilizing the wetting gradient capillary force of the "hydrophilic inner liner-hydrophobic outer shell." A micro water pump is activated, and the water sample in the tank is pumped to a micro flow meter through a pumping pipe, ensuring a stable flow rate of water entering the testing chamber. After the water sample with a stable flow rate enters the testing chamber, it makes full contact with the testing module—the molecularly imprinted layer performs specific adsorption, achieving the enrichment of trace odor substances. This structure achieves unidirectional water intake through capillary force, improving water intake efficiency by 32% and reducing the clogging rate to <8%.

[0025] 2. By removing the upper mounting cover, the test module on the test box can be unscrewed, and the test module 1 can be placed in a methanol / acetic acid (9:1) mixed solvent for ultrasonic treatment, elution, and testing.

[0026] Other advantages, objectives and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination or study, or may be learned from the practice of the invention. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the overall structure of the device in an embodiment of the present invention;

[0028] Figure 2 This is a schematic cross-sectional view of a partial structure of the device in an embodiment of the present invention;

[0029] Figure 3 This is a schematic diagram of a partial structure of the device in an embodiment of the present invention;

[0030] Figure 4 for Figure 2 Enlarged structural diagram at point A in the middle;

[0031] Figure 5 for Figure 2 Enlarged structural diagram at point B.

[0032] In the diagram: 1. Water storage tank; 2. Upper shell; 3. Upper mounting cover; 4. One-way valve; 5. Modified polyvinyl alcohol hydrophilic inner liner; 6. Lower threaded pipe; 7. Lower rubber gasket; 8. Hydrophobic photosensitive resin shell; 9. Water outlet pipe; 10. Airbag; 11. Miniature flow meter; 12. Inspection box; 13. Inspection module; 14. Miniature water pump; 15. Pumping pipe; 16. Upper threaded pipe; 17. Upper rubber gasket. Detailed Implementation

[0033] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings. It should be noted that the description of these embodiments is for the purpose of helping to understand the present invention, but does not constitute a limitation of the present invention.

[0034] Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0035] Please see the appendix Figure 1 - Appendix Figure 5 This invention relates to a passive sampling device for odor substances in water based on molecularly imprinted polymers, comprising an upper shell 2, an upper mounting cover 3 mounted on the upper shell 2, the inner side of the upper mounting cover 3 having threads, a water storage tank 1 mounted below the upper shell 2, the inner side of the lower end of the upper shell 2 having threads, a micro flow meter 11, a water suction pipe 15 and a micro water pump 14 mounted on the upper inner surface of the upper shell 2, a test box 12 connected to the micro flow meter 11, a water outlet pipe 9 connected to the side of the test box 12, a test module 13 installed inside the test box 12, the liquid outlet end of the micro flow meter 11 connected to the test box 12 through a pipe, the liquid inlet end of the micro flow meter 11 connected to the drain end of the micro water pump 14 through a pipe, the water suction end of the micro water pump 14 connected to the water suction pipe 15, the water suction pipe 15 extending through the upper shell 2 into the water storage tank 1, the water storage tank 1 being composed of a modified polyvinyl alcohol hydrophilic inner liner 5 and a hydrophobic photosensitive resin outer shell 8, and a micropore array with a pore size of 80-100μm being provided on the side wall of the water storage tank 1;

[0036] In practical use, select monitoring points in the water source area that avoid surface algae accumulation areas (to prevent algae from clogging the micropores of the water tank or interfering with MIPs adsorption). Fix the assembled device at a depth of 1.5m underwater, add a counterweight to the bottom of the device (to prevent the device from floating), and connect a GPS buoy to the top (for real-time positioning, facilitating inspection and retrieval after a 7-day monitoring cycle). Ensure the device is stable and does not shift. External water enters the water tank 1 unidirectionally through the 80-100μm micropore array on the side wall of the water tank 1, aided by the capillary force of the wetting gradient of the "hydrophilic inner liner-hydrophobic outer shell". Start the micro water pump 14, and pump the water through the suction pipe 15. Water samples from tank 1 are pumped to micro flow meter 11 to ensure a stable flow rate of water entering test box 12. After the water sample with a stable flow rate enters test box 12, it comes into full contact with test module 13—the molecular imprinted layer performs specific adsorption to achieve the enrichment of trace odor substances. The adsorbed water sample is discharged through outlet pipe 9 and one-way valve 4. After the 7-day monitoring cycle, the device is located by GPS buoy positioning and retrieved to the laboratory. The upper mounting cover 3 is removed, and the test module 13 on test box 12 is unscrewed. The test module 13 is placed in a methanol / acetic acid (9:1) mixed solvent for ultrasonic treatment and elution, and then tested.

[0037] Furthermore, an upper threaded tube 16 is fixedly connected to the upper surface of the upper housing 2, and an upper rubber pad 17 is fixedly connected to the upper surface of the upper threaded tube 16. The upper threaded tube 16 is threadedly connected to the upper mounting cover 3.

[0038] Among them, the upper surface of the upper rubber pad 17 is in contact with the lower inner surface of the upper mounting cover 3;

[0039] Specifically, the combination structure of "upper threaded tube 16 + upper rubber gasket 17" achieves a tight seal between the upper mounting cover 3 and the upper shell 2, which can effectively prevent external water, impurities or microorganisms from entering the interior of the upper shell 2.

[0040] Furthermore, the inspection module 13 is threadedly connected to the inspection box 12. The inspection module 13 is composed of a ternary functional monomer system of methacrylic acid, acrylamide and 2-hydroxyethyl methacrylate. Using 2-MIB and GSM as template molecules, a molecular imprinted layer is constructed on the FTO conductive glass substrate by electrochemical cyclic voltammetric polymerization.

[0041] Specifically, the threaded connection design between the inspection module 13 and the inspection box 12 allows for quick disassembly and replacement of the module.

[0042] Furthermore, an airbag 10 is fixedly connected inside the upper shell 2;

[0043] Specifically, the airbag 10 ensures that the device remains suspended in the water.

[0044] Furthermore, a lower threaded pipe 6 is fixedly connected to the upper surface of the water storage tank 1, and a lower rubber pad 7 is fixedly connected to the upper surface of the lower threaded pipe 6. The lower threaded pipe 6 is threadedly connected to the lower end of the upper shell 2.

[0045] Among them, the lower rubber pad 7 is in contact with the lower inner surface of the upper housing 2;

[0046] Specifically, the threaded connection design facilitates quick disassembly of the water storage tank 1, and the structure of the lower threaded pipe 6 + lower rubber gasket 7 can achieve a tight seal between the water storage tank 1 and the upper shell 2.

[0047] Furthermore, the water outlet pipe 9 extends through the side wall of the upper housing 2 to the outside, and a one-way valve 4 is provided on the side of the upper housing 2, which is connected to the water outlet pipe 9.

[0048] Among them, the one-way valve 4 allows the liquid in the outlet pipe 9 to flow out through the one-way valve 4;

[0049] Specifically, the one-way valve 4 only allows the "adsorbed water sample" flowing out of the test box 12 to be discharged from the device.

[0050] This invention also discloses a sampling method for the aforementioned passive sampling device for odor substances in water based on molecularly imprinted polymers, comprising the following steps:

[0051] S1. Device assembly: Install the inspection module 13 inside the inspection box 12 via a threaded connection, ensuring that the inspection module 13 fits snugly against the inner wall of the inspection box 12; screw the lower threaded tube 6 of the water storage tank 1 into the thread on the inner side of the lower end of the upper shell 2, so that the lower rubber pad 7 is in close contact with the lower inner surface of the upper shell 2; thread the upper mounting cover 3 into the upper threaded tube 16 of the upper shell 2, so that the upper rubber pad 17 is in contact with the lower inner surface of the upper mounting cover 3.

[0052] S2. On-site deployment: Select monitoring points in the water source area that avoid the surface algae accumulation area, and fix the assembled device at a depth of 1.5m underwater;

[0053] S3. Passive Sampling: External water enters the water storage tank 1 unidirectionally through the micropore array with a diameter of 80-100μm on the side wall of the water storage tank 1, aided by the capillary force of the wetting gradient formed by the modified polyvinyl alcohol hydrophilic inner liner 5 and the hydrophobic photosensitive resin outer shell 8. The micro water pump 14 is activated, and the water sample in the water storage tank 1 is pumped to the micro flow meter 11 through the water pumping pipe 15. After the water sample is stabilized by the micro flow meter 11, it enters the test box 12, where it comes into full contact with the molecular imprinted layer on the surface of the test module 13 and is specifically adsorbed. The adsorbed water sample is discharged to the outside of the device unidirectionally through the outlet pipe 9 and the one-way valve 4.

[0054] S4. Module recovery and testing: After the sampling cycle is completed, remove the upper mounting cover 3, unscrew the test module 13 on the test box 12, perform elution treatment on the test module 13, and then test the concentration of odor substances in the eluent.

[0055] In step S1 of this invention, the molecularly imprinted layer of the testing module 13 is constructed by electrochemical cyclic voltammetric polymerization. The specific process is as follows: using methacrylic acid, acrylamide, and 2-hydroxyethyl methacrylate as a ternary functional monomer system (molar ratio of the three is 1:1:1), and using 2-MIB and GSM as template molecules, the system is cyclically scanned 20 times in a potential range of -0.5V to 1.2V at a scanning rate of 10mV / s in 0.1M KCl electrolyte to form a molecularly imprinted layer with a thickness of 10-15μm on an FTO conductive glass substrate. In step S4, the elution treatment uses a mixed solvent of methanol and acetic acid in a volume ratio of 9:1 to ultrasonically treat the testing module 13. After treatment, the residual rate of odor substances on the molecularly imprinted layer is <3%.

[0056] In step S3 of this invention, the range of the micro flow meter 11 is 0-100 mL / min, which monitors the flow rate of the water sample entering the test box 12 in real time; the micro water pump 14 drives the water sample to a constant flow rate of 0.28 mL / min; the hydrophobic photosensitive resin shell 8 of the water storage tank 1 has a contact angle >110°, and the modified polyvinyl alcohol hydrophilic inner liner 5 has a contact angle <40°; the bottom of the water storage tank 1 is a fully sealed structure, which can resist a hydrostatic pressure of not less than 10 cm, and prevent the water sample from leaking from the bottom.

[0057] This invention also includes a concentration inversion step S5: establishing a concentration inversion equation based on Fick's diffusion law, the formula being... ;in, To verify the mass (unit: μg) of odorous substances adsorbed by module 13. The cross-sectional area of ​​the diffusion path (unit: cm², the value is the effective contact area of ​​the molecular imprint layer of the test module 13). Sampling time (unit: seconds). The diffusion rate of odor substances (unit: cm² / s). The concentration of odorous substances in water (unit: μg / cm³). To verify the concentration of odor substances (unit: μg / cm³, value is 0) on the interface of module 13. The length of the diffusion path (unit: cm, taken as the flow path length from the micropore of water tank 1 to inspection module 13); diffusion rate Based on water temperature correction, the correction formula is as follows: , Water temperature diffusion rate at time, The diffusion rate at 25℃; the adsorption rate ,and The calibration rate was 0.28 mL / min.

[0058] Working principle:

[0059] First, select monitoring points in the water source area that avoid surface algae accumulation zones (to prevent algae from clogging the micropores of the water tank or interfering with MIPs adsorption). Fix the assembled device at a depth of 1.5m underwater. Add a counterweight to the bottom of the device (to prevent it from floating), and connect a GPS buoy to the top (for real-time positioning, facilitating inspection and retrieval after a 7-day monitoring cycle). Ensure the device's position is stable and without deviation. External water flows through the 80-100μm micropore array on the side wall of water tank 1, utilizing the "hydrophilic inner liner - hydrophobic outer shell" structure. The water sample enters the water storage tank 1 unidirectionally through the capillary force of the wetting gradient. The micro water pump 14 is started, and the water sample in the water storage tank 1 is pumped to the micro flow meter 11 through the water pumping pipe 15 to ensure that the water sample flow rate entering the test box 12 is stable. After the water sample with a stable flow rate enters the test box 12, it makes full contact with the test module 13—the molecular imprinted layer performs specific adsorption to achieve the enrichment of trace odor substances. This structure achieves unidirectional water intake through capillary force, which improves the water intake efficiency by 32% and the clogging rate is <8%. At this point, the entire workflow is completed.

[0060] The terms "front," "back," "left," "right," "top," and "bottom" all refer to the figures in the accompanying drawings. Figure 1 Based on.

[0061] In the description of this invention, it should be understood that the terms "center", "longitudinal", "lateral", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting the scope of protection of this invention.

[0062] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments.

[0063] For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A passive sampling device for odor substances in water based on molecularly imprinted polymers, comprising an upper housing (2), characterized in that: The upper housing (2) is equipped with an upper mounting cover (3), and the inner side of the upper mounting cover (3) is threaded. The upper housing (2) is equipped with a water storage tank (1), and the inner side of the lower end of the upper housing (2) is threaded. The upper surface of the upper housing (2) is equipped with a micro flow meter (11), a water pump (15), and a micro water pump (14). The micro flow meter (11) is connected to a test box (12), and the side of the test box (12) is connected to a water outlet pipe (9). The test box (12) is equipped with a test module (13). The liquid outlet of the micro flow meter (11) is connected to the test box (12) through a pipe. The liquid inlet of the micro flow meter (11) is connected to the drain end of the micro water pump (14) through a pipe. The water pump (14) is connected to the water pump pipe (15). The water pump pipe (15) extends through the upper housing (2) into the water storage tank (1). The water storage tank (1) is composed of a modified polyvinyl alcohol hydrophilic inner liner (5) and a hydrophobic photosensitive resin outer shell (8). The side wall of the water storage tank (1) is provided with a micropore array with a pore size of 80-100μm.

2. The passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 1, characterized in that: The upper shell (2) is fixedly connected to the upper threaded tube (16), and the upper threaded tube (16) is fixedly connected to the upper rubber pad (17). The upper threaded tube (16) is threadedly connected to the upper mounting cover (3). The upper surface of the upper rubber pad (17) is in contact with the lower inner surface of the upper mounting cover (3).

3. The passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 1, characterized in that: The inspection module (13) is threadedly connected to the inspection box (12). The inspection module (13) is composed of a ternary functional monomer system of methacrylic acid, acrylamide and 2-hydroxyethyl methacrylate. Using 2-MIB and GSM as template molecules, a molecular imprinted layer is constructed on the FTO conductive glass substrate by electrochemical cyclic voltammetric polymerization.

4. The passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 1, characterized in that: An airbag (10) is fixedly connected inside the upper shell (2).

5. The passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 1, characterized in that: The upper surface of the water storage tank (1) is fixedly connected to a lower threaded pipe (6), and the upper surface of the lower threaded pipe (6) is fixedly connected to a lower rubber pad (7). The lower threaded pipe (6) is threadedly connected to the lower end of the upper shell (2). The lower rubber pad (7) is in contact with the lower inner surface of the upper housing (2).

6. The passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 1, characterized in that: The water outlet pipe (9) extends through the side wall of the upper housing (2) to the outside. A one-way valve (4) is provided on the side of the upper housing (2), and the one-way valve (4) is connected to the water outlet pipe (9). The one-way valve (4) allows the liquid in the outlet pipe (9) to flow out through the one-way valve (4).

7. A method for using a passive device for odor-causing substances in water based on molecularly imprinted polymers as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. Assembly of the device: Install the inspection module (13) inside the inspection box (12) by threaded connection, and the inspection module (13) fits against the inner wall of the inspection box (12); screw the lower threaded tube (6) of the water storage tank (1) into the thread on the inner side of the lower end of the upper shell (2) so that the lower rubber pad (7) is in close contact with the inner lower surface of the upper shell (2); thread the upper mounting cover (3) into the upper threaded tube (16) of the upper shell (2) so that the upper rubber pad (17) is in contact with the inner lower surface of the upper mounting cover (3); S2. On-site deployment: Select monitoring points in the water source area that avoid the surface algae accumulation area, and fix the assembled device at a depth of 1.5m underwater; S3. Passive sampling: External water enters the water storage tank (1) unidirectionally through the micropore array with a diameter of 80-100μm on the side wall of the water storage tank (1) by means of the capillary force of the wetting gradient formed by the modified polyvinyl alcohol hydrophilic inner liner (5) and the hydrophobic photosensitive resin outer shell (8); the micro water pump (14) is started, and the water sample in the water storage tank (1) is pumped to the micro flow meter (11) through the water pumping pipe (15). After the water sample enters the test box (12) after the flow rate of the micro flow meter (11) is stabilized, it fully contacts the molecular imprinted layer on the surface of the test module (13) and is specifically adsorbed; the adsorbed water sample is discharged to the outside of the device unidirectionally through the outlet pipe (9) and the one-way valve (4); S4. Module recovery and testing: After the sampling cycle is completed, remove the upper mounting cover (3), unscrew the test module (13) on the test box (12), perform elution treatment on the test module (13), and then test the concentration of odor substances in the eluent.

8. The method of using the passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 7, characterized in that, In step S1, the molecular imprinted layer of the test module (13) is constructed by electrochemical cyclic voltammetric polymerization. The specific process is as follows: using methacrylic acid, acrylamide and 2-hydroxyethyl methacrylate as a ternary functional monomer system, and using 2-MIB and GSM as template molecules, respectively, the molecular imprinted layer with a thickness of 10-15 μm is formed on the FTO conductive glass substrate by cyclic scanning 20 times in a potential range of -0.5V to 1.2V at a scanning rate of 10mV / s in 0.1M KCl electrolyte. In step S4, the elution treatment uses a mixed solvent of methanol and acetic acid in a volume ratio of 9:1 to perform ultrasonic treatment on the test module (13).

9. The method of using the passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 7, characterized in that, In step S3, the range of the micro flow meter (11) is 0-100 mL / min, and the flow rate of the water sample entering the test box (12) is monitored in real time; the micro water pump (14) drives the water sample to a constant flow rate of 0.28 mL / min; the hydrophobic photosensitive resin shell (8) of the water storage tank (1) has a contact angle >110°, and the modified polyvinyl alcohol hydrophilic inner liner (5) has a contact angle <40°; the bottom of the water storage tank (1) is a fully sealed structure.

10. The method of using the passive sampling device for odor substances in water based on molecularly imprinted polymers according to claim 7, characterized in that, It also includes concentration inversion step S5: establishing a concentration inversion equation based on Fick's diffusion law, the formula is as follows: Where m is the mass of the odor substance adsorbed by the test module (13), A is the cross-sectional area of ​​the diffusion path, t is the sampling time, and D is the diffusion rate of the odor substance. The concentration of odor-causing substances in the water. To verify the concentration of odor substances on the interface of module (13), L is the length of the diffusion path; the diffusion rate D is corrected according to the water temperature, and the correction formula is: , The diffusion rate at water temperature T. The diffusion rate at 25℃; the adsorption rate And the UR was calibrated to 0.28 mL / min.

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