A method for the removal of diazepam from an aquaculture water body

Abstract

The application discloses a method for removing diazepam in fishery breeding water bodies, and comprises the following steps: placing an obtained adsorption device into a fishery breeding water body, adsorbing diazepam, and obtaining a fishery breeding water body with removed diazepam. The method can efficiently adsorb and remove diazepam without changing the original environmental conditions of the water body, and improves the success rate of water treatment. Compared with traditional methods, the success rate of the application is significantly improved, and the content of diazepam in aquatic products can be clearly reduced, thereby providing a reliable water purification scheme for breeders.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of water body drug residue remediation, and particularly relates to a method for removing diazepam in fishery aquaculture water bodies. BACKGROUND

[0002] The pollution problem of diazepam has been widely detected in surface water, groundwater and aquaculture water bodies. Although wastewater recycling technology is commonly used in aquaculture, the diazepam residues in the recycled water bodies are difficult to be effectively removed by traditional adsorption methods. In this process, diazepam is not only easily wasted, but also difficult to separate, and even may cause secondary pollution. Therefore, it is particularly urgent to develop a method for efficiently removing diazepam in water, which is of great significance to ensure the quality and safety of aquatic products and promote the sustainable development of aquaculture.

[0003] Physical remediation technology plays an important role in ecological governance due to its economic efficiency and environmental friendliness. By using physical means such as adsorption, sedimentation and filtration, this technology can effectively remove pollutants in water bodies, while avoiding the side effects that may be caused by chemical treatment. In addition, physical remediation technology does not produce new chemical substances during the treatment process, thereby reducing the potential threat to the environment, which has significant significance for maintaining water quality and ecological balance.

[0004] Adsorption resin is a high-efficiency, highly selective and recyclable adsorption material, which exhibits excellent performance in water treatment and environmental remediation due to its high specific surface area, suitable particle size and good physical and chemical stability. In particular, in the removal of pollutants such as diazepam in aquaculture water bodies, through its unique porous structure and high adsorption capacity, it provides an economical and environmentally friendly solution for water purification and resource recycling. SUMMARY

[0005] The purpose of the present application is to provide a method for removing diazepam in fishery aquaculture water bodies.

[0006] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0007] In the first aspect of the present application, a method for removing diazepam in fishery aquaculture water bodies is provided, comprising the following steps:

[0008] Firstly, melamine resin, urea-formaldehyde resin and polyurethane resin with a mass ratio of 1:1:1 are mixed to obtain adsorption resin;

[0009] 25-40g (preferably 30g) of adsorption resin is loaded into a porous disc, shaken and packaged (using non-woven fabric) to obtain a resin-filled adsorption disc;

[0010] Secondly, connect a plurality of (more than two, preferably 3 or 4) resin-filled adsorption discs together, with a distance of 20-50 cm (preferably 30 cm or 40 cm) between each two resin-filled adsorption discs, and connect the two resin-filled adsorption discs with a nylon rope, and sequentially connect a float, a double-loop tension spring, and a float on the nylon rope; connect a conical traction device with a nylon rope sequentially connecting a float, a double-loop tension spring, and a float below the lowermost resin-filled adsorption disc, and connect a buoyant plastic sealed round cake with a nylon rope sequentially connecting a float, a double-loop tension spring, and a float on the uppermost resin-filled adsorption disc, to form an adsorption device.

[0011] Thirdly, place the obtained adsorption device in the aquaculture water body to adsorb diazepam, and obtain an aquaculture water body with diazepam removed.

[0012] The adsorption resin has a milky white translucent spherical appearance, 95% of the particles in the adsorption resin have a particle size of 0.3-1.25 mm, a mesh number of 60-16, a water content of 60-70%, a specific surface area of 480-520 m 2 / g, a wet true density (wet state) of the resin-filled particles of 1.05-1.07 g / ml, and a wet apparent density (wet state) of the resin-filled particles of 0.67-0.73 g / ml.

[0013] The porous disc is made of plastic (preferably polypropylene plastic).

[0014] The porous disc has a size of a circular bottom with a diameter of 15-25 cm (preferably 20 cm) and a height of 0.5-2 cm (a disc height of 0.8 cm).

[0015] The buoyant plastic sealed round cake has a size of a circular bottom with a diameter of 15-25 cm (preferably 20 cm) and a height of 5-15 cm (a cake height of 10 cm), and is made of hard PVC foam.

[0016] The conical traction device is made of iron.

[0017] The aquaculture water body is selected from shrimp breeding water, fish breeding water, and crab breeding water.

[0018] The adsorption time of diazepam is 1-30 days (preferably 1, 2, 3, 4, 5, 6, or 7 days).

[0019] The diazepam removal rate is greater than 95%.

[0020] The concentration analysis method of the diazepam is as follows: after the water sample is collected and pretreated, the concentration of diazepam is detected by liquid chromatography tandem mass spectrometry.

[0021] The liquid chromatography conditions are as follows: mobile phase: A: water (5mmol / L ammonium acetate and 0.2% formic acid), B: acetonitrile, chromatographic column: ZORBAX Eclipus Plus C18 RRHD (3.0*150mm 1.8um), column temperature: 35 DEG C; injection volume: 4ul; flow rate: 0.5ml / min, gradient elution program: 0-1.5min:1% B; 1.5-4min:90% B; 4-6min:95% B; 6-6.15min:99% B; 6.15-8.5min:99% B; 8.5-8.65min:1% B; 8.65-10min:1% B.

[0022] The mass spectrometry conditions are as follows: HESI ion source: sheath gas flow rate is 50L / min, aux gas flow rate is 15L / min, spray voltage (kV) is 3.50kV, capillary temp is 320 DEG C, S-lens RF level is 50%, aux gas heater temp is 350 DEG C.

[0023] The pretreatment method is as follows: 100ml of water sample is accurately taken and placed in a separatory funnel, 20ml of dichloromethane and 10ml of 10% Na2CO3 solution are added, 5ng of internal standard solution is added, extraction is shaken for 5min, and the lower clear liquid is collected in a center bottle after layering. 20ml of dichloromethane is added, and the extraction is repeated once. The extraction liquid is combined and rotary evaporated at 45 DEG C until nearly dry, 1ml of 80% acetonitrile solution is added for dissolution, the solution is transferred to a 2ml centrifuge tube, 100mg of N-propyl ethylenediamine is added, vortex mixing is carried out for 1min, centrifugation is carried out at 4 DEG C and 10000r / min for 10min, the supernatant is passed through a 0.22um organic phase microporous filter membrane, and the liquid phase chromatography tandem mass spectrometer is determined.

[0024] Due to the above technical scheme, the application has the following advantages and beneficial effects:

[0025] The method for removing diazepam from aquaculture water bodies provided by the present application not only improves the removal efficiency but also avoids the secondary pollution problem that may be caused by traditional treatment methods. Under the premise of not interfering with the ecological balance of the water body, the present application can significantly reduce the impact of diazepam on the quality of aquatic products, and at the same time reduce the economic losses of aquaculture farmers due to unqualified aquatic products. In addition, the method is simple to operate, low in cost, and sustainable, providing an environmentally friendly and economical solution for the aquaculture industry. Through this method, the diazepam residue in the aquaculture water body is effectively controlled, ensuring the safety of aquatic products, and also providing strong technical support for the green development of the aquaculture industry.

[0026] The present application uses adsorption resin as the key material for removing diazepam residues in aquaculture water bodies, not only simplifying the traditional water treatment process, but also avoiding the use of potentially toxic chemicals, thereby reducing the impact on the environment and organisms. This method effectively reduces the residual level of diazepam without interfering with the ecological balance of the water body, ensuring the safety of aquatic products.

[0027] The method for removing diazepam from aquaculture water bodies provided by the present application can effectively remove diazepam residues from aquaculture water bodies, improve water quality, and at the same time simplify the recovery process of adsorption materials, providing a green and efficient solution for the aquaculture industry.

[0028] The method for removing diazepam from aquaculture water bodies provided by the present application aims to solve the problems of low treatment efficiency, difficulty in completely removing diazepam, easy loss, and potential secondary pollution caused by traditional adsorption methods. By using adsorption resin, the present application aims to achieve efficient, environmentally friendly, and economical water purification, ensuring the quality and safety of aquatic products, reducing the economic losses of aquaculture farmers, and promoting the sustainable development of the aquaculture industry. In addition, this method aims to simplify the operation process, improve the recycling rate of adsorption materials, and provide an innovative and practical solution for the management of drug residues in aquaculture water bodies.

[0029] The method of the present application can efficiently adsorb and remove diazepam without changing the original environmental conditions of the water body, improving the success rate of water treatment. Compared with traditional methods, the success rate of the present application is significantly improved, which can clearly reduce the content of diazepam in aquatic products, providing a reliable water quality purification scheme for aquaculture farmers.

[0030] The removal method of the present application has wide applicability, not only suitable for various freshwater aquaculture water bodies, but also adaptable to different types of aquatic organisms such as fish and crustaceans. The universality of this method provides a standardized treatment process for the aquaculture industry, which helps to improve the water quality management level of the entire industry.

[0031] After the method of the present application is implemented, the residue of diazepam in the water body is effectively controlled, which not only helps to improve the market competitiveness of aquatic products, but also reduces the economic losses caused by unqualified aquatic products. In addition, the method of the present application has little disturbance to the water body during the treatment process, ensuring the health of aquatic organisms and the ecological balance of the water body, and has high environmental compatibility.

[0032] The method for removing diazepam in fishery culture water provided by the present application effectively removes the residue of diazepam in fishery culture water, and adopts macroporous adsorption resin as a key material. The method places melamine resin, urea-formaldehyde resin and polyurethane resin in a special plastic porous disc at a ratio of 1:1:1 (m / m), and the top of the disc is provided with a buoyant plastic sealing disc to keep the resin on the water surface, and the bottom is fixed by an iron cone. This design enables the adsorption resin to effectively adsorb diazepam in the water body, and facilitates movement and recovery in the water body. By controlling the distribution density and adsorption time of the disc, the culture water can be efficiently purified, the water quality can be improved, the safety of aquatic products can be ensured, and the resource utilization of diazepam can be realized. The method is simple to operate, low in cost, and has a wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is a schematic diagram of the resin used in the method for removing diazepam in fishery culture water of the present application.

[0034] Figure 2 is a result schematic diagram of the dynamic residual concentration of diazepam in the water body for raising shrimp by resin adsorption.

[0035] Figure 3 is a result schematic diagram of the dynamic residual concentration of diazepam in the water body for raising fish by resin adsorption.

[0036] Figure 4 is a result schematic diagram of the dynamic residual concentration of diazepam in the water body for raising crabs by resin adsorption. DETAILED DESCRIPTION

[0037] In order to more clearly illustrate the present application, the present application will be further described below in combination with preferred embodiments. Those skilled in the art should understand that the specific description below is illustrative rather than limiting, and should not limit the protection scope of the present application.

[0038] Example 1

[0039] A method for removing diazepam in fishery culture water, Figure 1 is a schematic diagram of the resin used in the method for removing diazepam in fishery culture water of the present application, comprising the following steps:

[0040] The first step, melamine resin, urea-formaldehyde resin and polyurethane resin (melamine resin CAS 3089-11-0, Jiangsu Guoli Chemical Technology Co., Ltd.; urea-formaldehyde resin CAS: 9011-05-6, Shanghai Maikelin Biochemical Technology Co., Ltd.; polyurethane resin CAS: 9009-54-5, East China University of Technology Huachang Polymer Co., Ltd.) with a mass ratio of 1:1:1 are mixed to obtain an adsorption resin, 30g of the adsorption resin is loaded into a porous disc to ensure that the adsorption resin can be fully contacted and adsorbed with diazepam in the water body, and then the non-woven fabric is used for packaging after shaking to obtain a resin-filled adsorption disc;

[0041] The adsorption resin has a milky white translucent spherical particle appearance, 95% of the particles in the adsorption resin have a particle size of 0.3-1.25mm, the mesh number is 60-16, the water content is 60-70%, the specific surface area is 480-520m 2 / g, the wet true density (wet state) of the resin-filled particles is 1.05-1.07g / ml; and the wet apparent density (wet state) of the resin-filled particles is 0.67-0.73g / ml.

[0042] The material of the porous disc is plastic (polypropylene plastic);

[0043] The size of the porous disc is that the bottom is a circle with a diameter of 15-25cm (preferably 20cm) and a height of 0.5-2cm (the height of the disc is 0.8cm).

[0044] The second step is to prepare a buoyancy plastic sealing disc at the top of the porous disc to maintain the stable floating state of the disc on the water surface, which is convenient for deployment in the aquaculture water body.

[0045] The size of the buoyancy plastic sealing disc is that the bottom is a circle with a diameter of 15-25cm (preferably 20cm) and a height of 5-15cm (the height of the disc is 10cm), and the material is hard PVC foam.

[0046] The third step is to connect multiple (more than two) resin-filled adsorption discs together, the distance between every two resin-filled adsorption discs is 20-50cm (preferably 20cm, 30cm, 40cm), the two resin-filled adsorption discs are connected by a nylon rope, and the nylon rope is sequentially connected with a float, a double-loop tension spring and a float; a conical traction device is connected to the nylon rope with a float, a double-loop tension spring and a float below the lowermost resin-filled adsorption disc, and a buoyancy plastic sealing disc is connected to the nylon rope with a float, a double-loop tension spring and a float above the uppermost resin-filled adsorption disc to form an adsorption device; the conical traction device is arranged to facilitate the positioning and recovery of the adsorption device in the water body, and the purpose of arranging the buoyancy plastic sealing disc is to adjust the relationship between the buoyancy and the gravity to make the adsorption device suspended in the water body.

[0047] The material of the conical traction device is iron.

[0048] Fourthly, place the assembled adsorption device into the fishery culture water body. The density of placement is adjusted according to the concentration of diazepam in the fishery culture water body and the flowability of the water body, and the distribution density and adsorption time of the adsorption device are adjusted to achieve efficient adsorption and obtain the fishery culture water body with diazepam removed.

[0049] After the adsorption process is completed, the adsorption device is recovered by the conical traction device, and the adsorbed diazepam is treated to achieve purification of the fishery culture water body and resource utilization of diazepam.

[0050] The resin filled in the adsorption disc after adsorption is subjected to necessary regeneration treatment to restore its adsorption capacity, realize cyclic use, and reduce long-term operation cost.

[0051] The concentration of diazepam in the fishery culture water body is regularly monitored to evaluate the adsorption effect, and the density and placement time of the adsorption device are adjusted according to the monitoring results.

[0052] Application Example 1

[0053] A method for removing diazepam in a fishery culture water body, comprising the following steps:

[0054] The method is to test the adsorption effect of the resin filled adsorption disc in adsorbing and treating diazepam in the water body for raising prawns. Three treatment groups are set in the experiment: static adsorption group (S1), dynamic adsorption group (S2) and blank control group (S3). These treatment groups simulate different water circulation states to obtain the adsorption effect of the resin filled adsorption disc under different conditions.

[0055] Static adsorption group (S1): without starting the circulating water pump, simulating a static water body.

[0056] Dynamic adsorption group (S2): start the circulating water pump, simulating the actual environment water circulation.

[0057] Blank control group (S3): without using the resin filled adsorption disc for adsorption, only as a control group.

[0058] Experimental environment and water sample collection: a 200 liter blue aquarium (cylindrical barrel, size: 90 cm high, bottom is a circle with a diameter of 130 cm) is used for each treatment group, and the temperature is maintained at 20℃.

[0059] The preparation method of the adsorption device comprises the following steps:

[0060] Firstly, melamine resin, urea-formaldehyde resin and polyurethane resin with a mass ratio of 1:1:1 are mixed to obtain the adsorption resin, 30g of the adsorption resin is loaded into a porous disc, and then the porous disc is packaged with non-woven fabric to obtain a resin-filled adsorption disc.

[0061] The adsorption resin has a milky white translucent spherical appearance, 95% of the particles in the adsorption resin have a particle size of 0.3-1.25mm, the mesh number is 60-16, the water content is 60-70%, the specific surface area is 480-520m 2 / g, the wet apparent density (wet state) of the resin-filled particles is 1.05-1.07g / ml; and the wet apparent density (wet state) of the resin-filled particles is 0.67-0.73g / ml.

[0062] The material of the porous disc is plastic (polypropylene plastic).

[0063] The size of the porous disc is that the bottom is a circle with a diameter of 20cm and a height of 0.8cm.

[0064] Secondly, a buoyant plastic sealing disc is prepared on the top of the porous disc:

[0065] The size of the buoyant plastic sealing disc is that the bottom is a circle with a diameter of 20cm and a height of 10cm, and the material is hard PVC foam.

[0066] Thirdly, three resin-filled adsorption discs are connected in sequence, the distance between every two resin-filled adsorption discs is 20cm, the two resin-filled adsorption discs are connected by a nylon rope, and the nylon rope is sequentially connected with a float, a double-loop tension spring and a float; a conical traction device is connected to the lowermost resin-filled adsorption disc by a nylon rope sequentially connected with a float, a double-loop tension spring and a float, and a buoyant plastic sealing disc is connected to the uppermost resin-filled adsorption disc by a nylon rope sequentially connected with a float, a double-loop tension spring and a float, to form an adsorption device. The material of the conical traction device is iron.

[0067] Five adsorption devices are placed in a blue aquarium and evenly distributed.

[0068] Water samples are collected from the first day of the experiment (D0) and at different time points thereafter. To ensure the integrity of the samples, the sampling bottle is rinsed before collecting the water sample to ensure that there are no air bubbles, and then placed about 5cm below the water surface to avoid suspended matter entering the bottle. After collection, the water sample is stored in a refrigerator and immediately sent to the laboratory for water quality analysis.

[0069] Diazepam concentration analysis: liquid chromatography tandem mass spectrometry analysis method is used, and the specific method is as follows:

[0070] Pre-treatment method: accurately pipette 100 mL of water sample into a separatory funnel, add 20 mL of dichloromethane and 10 mL of 10% Na2CO3 solution, then add 5 ng of internal standard solution, shake for 5 min, stand for separation, collect the lower clear liquid in a core bottle. Add 20 mL of dichloromethane and repeat the extraction once. Combine the extract, rotary evaporate at 45°C to near dryness, add 1 mL of 80% acetonitrile solution for dissolution, transfer the solution to a 2 mL centrifuge tube, add 100 mg of N-propyl ethylenediamine, vortex for 1 min, centrifuge at 10000 r / min at 4°C for 10 min, take the supernatant through a 0.22 um organic phase microporous filter, and supply for liquid chromatography tandem mass spectrometry determination.

[0071] Instrument conditions: ultra-high performance liquid system UltiMateTM 3000, Thermo Fisher Corporation, high-resolution mass spectrometer Q-Exactive, Thermo Fisher Corporation.

[0072] Liquid chromatography conditions: mobile phase: A: water (5 mmol / L ammonium acetate and 0.2% formic acid), B: acetonitrile, chromatographic column: ZORBAX Eclipus Plus C18 RRHD (3.0 x 150 mm 1.8 um), column temperature: 35°C; injection volume: 4 uL; flow rate: 0.5 mL / min, gradient elution program: 0-1.5 min: 1% B; 1.5-4 min: 90% B; 4-6 min: 95% B; 6-6.15 min: 99% B; 6.15-8.5 min: 99% B; 8.5-8.65 min: 1% B; 8.65-10 min: 1% B.

[0073] Mass spectrometry conditions: HESI ion source: sheath gas flow rate is 50 L / min, aux gas flow rate is 15 L / min, spray voltage (kV) is 3.50 kV, ion transmission tube temperature (capillary temp) is 320°C, S-lens RF level is 50%, aux gas heater temp is 350°C.

[0074] Quality control standards: when comparing the actual sample with the drug standard, the relative deviation of the standard and the parent ion mass-to-charge ratio is less than 3 x 10 -6 ; the retention time difference is less than 0.10 min; the relative deviation of the isotopic mass-to-charge ratio is less than 1 x 10 -5Isotope relative abundance deviation < 25%. Data acquisition software Xcalibur, information comparison by Tracefinder software to establish drug database. Blank matrix liquid was used to prepare positive drug standard solution, and the compound recovery rate was between 80% and 110%.

[0075] Data analysis: The experimental data analysis is based on tables and charts, including the following:

[0076] Diazepam initial concentration: The initial concentration of diazepam in the static adsorption group (S1), the dynamic adsorption group (S2), and the blank control group (S3) is the same, which is 302.5 ng / L.

[0077] Diazepam concentration in water after adsorption: The concentration change of diazepam in each treatment group is recorded within 1 to 7 days.

[0078] At 1 day (1d), the concentration of diazepam in the static adsorption group (S1) decreased to 210.5 ng / L, and the dynamic adsorption group (S2) decreased to 184.6 ng / L, while the blank control group (S3) remained at 301.2 ng / L.

[0079] By the 7th day (7d), the concentration of diazepam in the static adsorption group was 9.5 ng / L, the dynamic adsorption group was 8.6 ng / L, and the blank control group (S3) was 300.8 ng / L.

[0080] Elimination rate: The elimination rate of diazepam at 3 days and 7 days was calculated.

[0081] At 3 days, the elimination rate of the static adsorption group was 78.7%, the dynamic adsorption group was 81.3%, and the blank control group was 0.6%.

[0082] By the 7th day, the elimination rate of the static adsorption group was 96.9%, the dynamic adsorption group was 97.2%, and the blank control group was still 0.6%.

[0083] Table 1 Residual concentration of diazepam in shrimp water adsorbed by resin

[0084]

[0085]

[0086] Chart analysis: The chart shows the relationship between time and diazepam concentration, highlighting the significant differences between different treatment groups in adsorbing diazepam. The results are shown as Figure 2 Figure 2 ​is a schematic diagram of the results of the dynamic residual concentration of diazepam in the water body of shrimp adsorbed by the resin. It can be seen from the figure that the concentration of diazepam in the water body of shrimp is significantly reduced under the action of the resin filled adsorption disc, which shows that the adsorption effect of the resin filled adsorption disc on diazepam in the water body of shrimp is significant, especially in the dynamic environment, and the adsorption effect is more significant due to the increase of water flow exchange.

[0087] The concentration of diazepam in the dynamic adsorption group decreases the fastest, followed by the static adsorption group, and the concentration of the blank control group almost does not change.

[0088] The results show that the resin filled adsorption disc used in the present application has obvious effect on reducing the concentration of diazepam, and the adsorption effect in the dynamic environment is more significant.

[0089] These analysis results show that the adsorption effect of the resin filled adsorption disc used in the present application in the water body is significant, and the adsorption effect in the dynamic environment is better than that in the static environment. The concentration of diazepam in the blank control group almost does not change, which shows that when there is no resin adsorption, the concentration of diazepam in the water body remains unchanged.

[0090] Application Example 2

[0091] A method for removing diazepam in a fishery aquaculture water body, comprising the following steps:

[0092] The method is to test the adsorption effect of the resin filled adsorption disc on the adsorption treatment of diazepam in the water body of fish. Three treatment groups are set: static adsorption group (S1), dynamic adsorption group (S2) and blank control group (S3). These treatment groups simulate different water circulation states to obtain the adsorption effect of the resin filled adsorption disc under different conditions.

[0093] Static adsorption group (S1): without circulating water pump, simulating static water body.

[0094] Dynamic adsorption group (S2): start the circulating water pump, simulate the actual environment water circulation.

[0095] Blank control group (S3): without using resin filled adsorption disc for adsorption, only as a control group.

[0096] Experimental environment and water sample collection: a 200 liter blue aquarium (cylindrical barrel, size: 90 cm high, bottom is a circle with a diameter of 130 cm) is used for each treatment group, and the temperature is kept at 20℃.

[0097] The preparation method of the adsorption device comprises the following steps:

[0098] In the first step, melamine resin, urea-formaldehyde resin and polyurethane resin with a mass ratio of 1:1:1 are mixed to obtain the adsorption resin, 30 g of the adsorption resin is loaded into a porous disc, and the porous disc is packaged with non-woven fabric after shaking to obtain a resin-filled adsorption disc.

[0099] The adsorption resin has a milky white translucent spherical appearance, 95% of the particles in the adsorption resin have a particle size of 0.3-1.25 mm, the mesh number is 60-16, the water content is 60-70%, the specific surface area is 480-520 m 2 / g, the wet true density of the resin-filled particles (wet state) is 1.05-1.07 g / ml, and the wet apparent density of the resin-filled particles (wet state) is 0.67-0.73 g / ml.

[0100] The material of the porous disc is plastic (polypropylene plastic);

[0101] The size of the porous disc is that the bottom is a circle with a diameter of 20 cm and a height of 0.8 cm.

[0102] In the second step, a buoyant plastic sealing disc is prepared on the top of the porous disc:

[0103] The size of the buoyant plastic sealing disc is that the bottom is a circle with a diameter of 20 cm and a height of 10 cm, and the material is hard PVC foam.

[0104] In the third step, three resin-filled adsorption discs are connected in sequence, the distance between every two resin-filled adsorption discs is 20 cm, the two resin-filled adsorption discs are connected by a nylon rope, and the nylon rope is sequentially connected with a float, a double-loop tension spring and a float; a conical traction device is connected to the lowermost resin-filled adsorption disc by a nylon rope sequentially connected with a float, a double-loop tension spring and a float, and a buoyant plastic sealing disc is connected to the uppermost resin-filled adsorption disc by a nylon rope sequentially connected with a float, a double-loop tension spring and a float, to form an adsorption device. The material of the conical traction device is iron.

[0105] Five adsorption devices are placed in a blue aquarium and evenly distributed.

[0106] Water sampling starts from the first day (1d) of the experiment, and the concentration of diazepam at different time points during the experiment is recorded. In order to ensure the accuracy and integrity of the samples, the water samples are collected according to the standard operation procedure and immediately sent to the laboratory for water quality analysis.

[0107] Table 2 Residual concentration of diazepam in fish breeding water adsorbed by resin

[0108]

[0109]

[0110] Diazepam concentration analysis: liquid chromatography tandem mass spectrometry analysis, as follows:

[0111] Pre-treatment method: accurately pipette 100 mL of water sample into a separatory funnel, add 20 mL of dichloromethane and 10 mL of 10% Na2CO3 solution, then add 5 ng of internal standard solution, shake and extract for 5 min, stand to separate layers, collect the lower clear liquid in a core bottle. Add 20 mL of dichloromethane and repeat the extraction once. Combine the extract, rotary evaporate at 45°C to near dryness, add 1 mL of 80% acetonitrile solution to dissolve, transfer the solution to a 2 mL centrifuge tube, add 100 mg of N-propyl ethylenediamine, vortex mix for 1 min, centrifuge at 10000 r / min at 4°C for 10 min, take the supernatant through a 0.22 um organic phase microporous filter membrane, and supply for liquid chromatography tandem mass spectrometry determination.

[0112] Instrument conditions: ultra-high performance liquid system UltiMateTM 3000, Thermo Fisher Corporation, high-resolution mass spectrometer Q-Exactive, Thermo Fisher Corporation.

[0113] Liquid chromatography conditions: mobile phase: A: water (5 mmol / L ammonium acetate and 0.2% formic acid), B: acetonitrile, chromatographic column: ZORBAX Eclipus Plus C18 RRHD (3.0 x 150 mm 1.8 um), column temperature: 35°C; injection volume: 4 uL; flow rate: 0.5 mL / min, gradient elution program: 0-1.5 min: 1% B; 1.5-4 min: 90% B; 4-6 min: 95% B; 6-6.15 min: 99% B; 6.15-8.5 min: 99% B; 8.5-8.65 min: 1% B; 8.65-10 min: 1% B.

[0114] Mass spectrometry conditions: HESI ion source: sheath gas flow rate 50 L / min, aux gas flow rate 15 L / min, spray voltage (kV) 3.50 kV, ion transmission tube temperature (capillary temp) 320°C, radio frequency prism voltage (S-lens RF level) 50%, aux gas heater temperature (aux gas heater temp) 350°C.

[0115] Quality control standards: when comparing and analyzing actual samples and drug standards, the relative deviation of the standard and the parent ion mass-to-charge ratio is <3 x 10 -6 ; the retention time difference is <0.10 min; the relative deviation of the isotopic mass-to-charge ratio is <1 x 10 -5The relative abundance deviation of isotopes was <25%. Data acquisition software Xcalibur was used, and a drug database was established using Tracefinder software for information comparison. Positive drug standard solutions were prepared using blank matrix solutions, and the compound recoveries ranged from 80% to 110%.

[0116] Data Analysis: Based on the data in Table 2, the following shows the changes in diazepam across the three treatment groups:

[0117] Initial concentration of diazepam: The initial concentrations of the static adsorption group (S1), dynamic adsorption group (S2), and blank control group (S3) were the same, all being 956.4 ng / L.

[0118] Diazepam concentration in water after adsorption: On day 1 of the experiment, the concentration of diazepam in the static adsorption group (S1) decreased to 824.3 ng / L, the concentration of diazepam in the dynamic adsorption group (S2) decreased to 810.3 ng / L, while the concentration of diazepam in the blank control group (S3) remained almost unchanged.

[0119] On the 7th day of the experiment, the concentration of diazepam in the static adsorption group decreased to 48.2 ng / L, the concentration in the dynamic adsorption group decreased to 18.2 ng / L, while the blank control group remained close to the initial concentration of 954.8 ng / L.

[0120] Elimination rate: By calculating the elimination rate of diazepam, the adsorption effect of the resin in different environments can be analyzed.

[0121] On day 3, the elimination rate was 36.2% in the static adsorption group, 57.1% in the dynamic adsorption group, and only 0.39% in the blank control group.

[0122] By day 7, the elimination rate of the static adsorption group reached 95.0%, while the dynamic adsorption group was even higher, reaching 98.1%. The blank control group had an elimination rate of only 0.17%.

[0123] Chart Analysis: Figure 3 The relationship between time and diazepam concentration was shown, highlighting the significant differences in adsorption efficiency among different treatment groups. Results are as follows... Figure 3 As shown, Figure 3 This is a schematic diagram showing the dynamic residual concentration of diazepam in fish farming water after adsorption by resin. The diagram shows that the concentration of diazepam in the fish farming water significantly decreased under the action of the resin-filled adsorption discs. This indicates that the resin-filled adsorption discs have a significant adsorption effect on diazepam in fish farming water, especially under dynamic conditions where increased water exchange further enhances the adsorption effect.

[0124] It can be seen that:

[0125] The diazepam concentration decreased the fastest in the dynamic adsorption group (S2), indicating that the resin-filled adsorption discs have a better adsorption effect in a dynamic environment.

[0126] The concentration of diazepam in the static adsorption group (S1) decreased slightly slower, but still decreased significantly.

[0127] The concentration of diazepam in the blank control group (S3) hardly changed, indicating that the concentration of diazepam in the water body did not decrease when there was no resin-filled adsorption disc adsorption.

[0128] These data and graphs show that the resin-filled adsorption disc has a significant adsorption effect on diazepam in fish farming water bodies, especially in a dynamic environment. The results of the blank control group show that there is no significant change in the concentration of diazepam in the water body without the adsorption of the resin-filled adsorption disc.

[0129] Application Example 3

[0130] A method for removing diazepam in fish farming water bodies, comprising the following steps:

[0131] The method is to test the adsorption effect of the resin-filled adsorption disc on diazepam in crab farming water bodies. Three treatment groups are set up: static adsorption group (S1), dynamic adsorption group (S2) and blank control group (S3). These treatment groups simulate different water circulation states to obtain the adsorption effect of the resin-filled adsorption disc under different conditions.

[0132] Static adsorption group (S1): no circulating water pump, simulating a static water body.

[0133] Dynamic adsorption group (S2): turn on the circulating water pump, simulate the actual environment water circulation.

[0134] Blank control group (S3): no adsorption of resin-filled adsorption disc, only as a control group.

[0135] Experimental environment and water sample collection: a 200-liter blue aquarium (cylindrical barrel, size: 90 cm high, bottom is a circle with a diameter of 130 cm) is used for each treatment group, and the temperature is maintained at 20°C.

[0136] The preparation method of the adsorption device comprises the following steps:

[0137] Firstly, melamine resin, urea-formaldehyde resin and polyurethane resin with a mass ratio of 1:1:1 are mixed to obtain adsorption resin, 30g of the adsorption resin is loaded into a porous disc, and after shaking, non-woven fabric is used for packaging to obtain a resin-filled adsorption disc.

[0138] The appearance of the adsorption resin is milky white translucent spherical particles, 95% of the particles in the adsorption resin have a particle size of 0.3-1.25mm, a mesh number of 60-16, a water content of 60-70%, and a specific surface area of 480-520m 2The wet true density (wet state) of the resin filling particles is 1.05-1.07 g / ml; the wet apparent density (wet state) of the resin filling particles is 0.67-0.73 g / ml.

[0139] The material of the porous disc is plastic (polypropylene plastic);

[0140] The size of the porous disc is: the bottom is a circle with a diameter of 20 cm, and the height is 0.8 cm.

[0141] Second step, prepare the buoyant plastic sealing disc on the top of the porous disc:

[0142] The size of the buoyant plastic sealing disc is: the bottom is a circle with a diameter of 20 cm, and the height is 10 cm, and the material is hard PVC foam.

[0143] Third step, connect the three resin filling and adsorbing discs in sequence, the distance between every two resin filling and adsorbing discs is 20 cm, and the two resin filling and adsorbing discs are connected by a nylon rope, and the nylon rope is sequentially connected with a float, a double coil spring and a float; under the lowermost resin filling and adsorbing disc, a conical traction device is connected by a nylon rope sequentially connected with a float, a double coil spring and a float, and on the uppermost resin filling and adsorbing disc, a buoyant plastic sealing disc is connected by a nylon rope sequentially connected with a float, a double coil spring and a float, to form an adsorbing device. The material of the conical traction device is iron.

[0144] Five adsorbing devices are placed in the blue aquarium and evenly distributed.

[0145] Water samples are collected from the first day of the experiment (1d) and regularly collected during the experiment. In order to ensure the accuracy and integrity of the data, avoid external pollution when collecting water samples, ensure that the water sample has no suspended matter and no bubbles. Then the water sample in the sampling bottle is sent to the laboratory in time for water quality analysis.

[0146] Table 3 Residual concentration of diazepam in water for breeding crabs by resin adsorption

[0147]

[0148]

[0149] Diazepam concentration analysis: liquid chromatography tandem mass spectrometry analysis method is adopted, and the specific method is as follows:

[0150] Pre-treatment method: accurately pipette 100 mL of water sample into a separatory funnel, add 20 mL of dichloromethane and 10 mL of 10% Na2CO3 solution, then add 5 ng of internal standard solution, shake for 5 min, stand for separation, collect the lower clear liquid in a core bottle. Add 20 mL of dichloromethane and repeat the extraction once. Combine the extract, rotary evaporate at 45°C to near dryness, add 1 mL of 80% acetonitrile solution for dissolution, transfer the solution to a 2 mL centrifuge tube, add 100 mg of N-propyl ethylenediamine, vortex for 1 min, centrifuge at 10000 r / min at 4°C for 10 min, take the supernatant through a 0.22 um organic phase microporous filter, and supply for liquid chromatography tandem mass spectrometry determination.

[0151] Instrument conditions: ultra-high performance liquid system UltiMateTM 3000, Thermo Fisher Corporation, high-resolution mass spectrometer Q-Exactive, Thermo Fisher Corporation.

[0152] Liquid chromatography conditions: mobile phase: A: water (5 mmol / L ammonium acetate and 0.2% formic acid), B: acetonitrile, chromatographic column: ZORBAX Eclipus Plus C18 RRHD (3.0 x 150 mm 1.8 um), column temperature: 35°C; injection volume: 4 uL; flow rate: 0.5 mL / min, gradient elution program: 0-1.5 min: 1% B; 1.5-4 min: 90% B; 4-6 min: 95% B; 6-6.15 min: 99% B; 6.15-8.5 min: 99% B; 8.5-8.65 min: 1% B; 8.65-10 min: 1% B.

[0153] Mass spectrometry conditions: HESI ion source: sheath gas flow rate is 50 L / min, aux gas flow rate is 15 L / min, spray voltage (kV) is 3.50 kV, ion transmission tube temperature (capillary temp) is 320°C, S-lens RF level is 50%, aux gas heater temp is 350°C.

[0154] Quality control standards: when comparing the actual sample with the drug standard, the relative deviation of the standard and the parent ion mass-to-charge ratio is less than 3 x 10 -6 ; the retention time difference is less than 0.10 min; the relative deviation of the isotopic mass-to-charge ratio is less than 1 x 10 -5Isotope relative abundance deviation < 25%. Data acquisition software Xcalibur, information comparison by Tracefinder software to establish drug database. Blank matrix liquid was used to prepare positive drug standard solution, and the compound recovery rate was between 80% and 110%.

[0155] Data analysis: According to the data in Table 3, the following is the change of diazepam in the three treatment groups:

[0156] Initial concentration of diazepam: The initial concentration of static adsorption group (S1), dynamic adsorption group (S2) and blank control group (S3) was 220.5 ng / L.

[0157] Diazepam concentration in water after adsorption: On the first day of the experiment, the diazepam concentration in the static adsorption group (S1) was 130.6 ng / L, the dynamic adsorption group (S2) was 121.3 ng / L, and the blank control group (S3) had almost no change, remaining at 219.6 ng / L.

[0158] On the 7th day of the experiment, the diazepam concentration in the static adsorption group decreased to 8.9 ng / L, the dynamic adsorption group was 5.9 ng / L, and the blank control group was 216.6 ng / L.

[0159] Elimination rate: By calculating the elimination rate of diazepam on the 3rd and 7th days, the effects of different treatment groups were compared.

[0160] On the 3rd day, the elimination rate of the static adsorption group was 72.4%, the dynamic adsorption group was 74.4%, and the blank control group was only 0.5%.

[0161] On the 7th day, the elimination rate of the static adsorption group reached 96.0%, the dynamic adsorption group reached 97.3%, and the blank control group was only 1.8%.

[0162] Chart analysis: Figure 4 The relationship between time and diazepam concentration is shown by curve comparison of adsorption effects of different treatment groups: the results are shown in Figure 4 , Figure 4 is a schematic diagram showing the dynamic residual concentration of diazepam in crab water adsorbed by resin. It can be seen from the figure that under the action of resin filled adsorption disc, the concentration of diazepam in crab water is significantly reduced, indicating that the resin filled adsorption disc has significant adsorption effect on diazepam in crab water, especially in dynamic environment, the effect of water flow exchange is increased, and the adsorption effect is more significant.

[0163] The diazepam concentration in the dynamic adsorption group (S2) decreased the fastest, indicating that the adsorption effect of the resin filled adsorption disc in the dynamic environment was better.

[0164] The static adsorption group (S1) also showed significant adsorption effect, but slightly slower than the dynamic adsorption group.

[0165] The diazepam concentration of the blank control group (S3) changed little, which indicated that the diazepam concentration in the water body changed little without the resin-filled adsorption disc adsorbing.

[0166] From these data, it can be seen that the resin-filled adsorption disc has obvious adsorption effect on diazepam in the crab culture water body, especially in the dynamic environment. This indicates the potential application value of the resin used in the resin-filled adsorption disc in water body treatment, especially in the environment requiring rapid adsorption.

[0167] The above merely describes preferred embodiments of the present application and is not intended to limit the present application in any form. Although the present application has been disclosed as above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above-mentioned technical content with slight changes or equivalent embodiments without departing from the technical solution of the present application. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application are still within the scope of the present application.

Claims

1. A method for the removal of diazepam from an aquaculture water body, characterized in that, The method comprises the following steps: In the first step, melamine resin, urea-formaldehyde resin and polyurethane resin with a mass ratio of 1:1:1 are mixed to obtain an adsorption resin; 25-40 g of the adsorption resin is loaded into a porous disc, which is sealed after being shaken to obtain a resin-filled adsorption disc; In the second step, a plurality of resin-filled adsorption discs are connected together, the distance between every two resin-filled adsorption discs is 20-50 cm, and the two resin-filled adsorption discs are connected by a nylon rope, which is sequentially connected with a float, a double-loop tension spring and a float; a conical traction device is connected to the nylon rope sequentially connected with a float, a double-loop tension spring and a float below the lowermost resin-filled adsorption disc, and a buoyant plastic sealed round cake is connected to the nylon rope sequentially connected with a float, a double-loop tension spring and a float above the uppermost resin-filled adsorption disc to form an adsorption device; In the third step, the obtained adsorption device is placed in a fishery breeding water body to adsorb diazepam, and a fishery breeding water body with diazepam removed is obtained.

2. The method for removal of diazepam from a fish farming water body according to claim 1, characterized in that, The appearance of the adsorption resin is milky white translucent spherical particles, 95% of the particles in the adsorption resin have a particle size of 0.3-1.25 mm, a mesh number of 60-16 meshes, a water content of 60-70%, a specific surface area of 480-520 m 2 / g, the wet true density of the resin filling particles is 1.05-1.07 g / ml; and the wet apparent density of the resin filling particles is 0.67-0.73 g / ml.

3. The method for removal of diazepam from a fish farming water body according to claim 1, characterized in that, The material of the porous disc is plastic.

4. The method for removal of diazepam from a fish farming water body according to claim 1, characterized in that, The size of the porous disc is that the bottom is a circle with a diameter of 15-25 cm and a height of 0.5-2 cm.

5. The method for removal of diazepam from a fish farming water body as claimed in claim 1, wherein, The size of the buoyant plastic sealed round cake is that the bottom is a circle with a diameter of 15-25 cm and a height of 5-15 cm, and the material is hard PVC foam.

6. The method for removal of diazepam from a fish farming water body as claimed in claim 1, wherein, The material of the conical traction device is iron.

7. The method for removal of diazepam from a fish farming water body as claimed in claim 1, wherein, The fishery breeding water body is selected from shrimp breeding water, fish breeding water and crab breeding water.

8. The method for removal of diazepam from a fish farming water body as claimed in claim 1, wherein, The time for adsorbing diazepam is 1-30 days.

9. The method for removal of diazepam from a fish farming water body as claimed in claim 1, wherein, The method for analyzing the concentration of diazepam is as follows: after water samples are collected, they are pretreated and analyzed by liquid chromatography tandem mass spectrometry to obtain the concentration of diazepam.

10. The method for removal of diazepam from a fish farming water body according to claim 9, characterized in that, The liquid chromatography conditions are as follows: mobile phase: A: water containing 5 mmol / L ammonium acetate and 0.2% formic acid, B: acetonitrile, column temperature: 35℃; injection volume: 4 μL; flow rate: 0.5 mL / min, gradient elution program: 0-1.5 min: 1% B; 1.5-4 min: 90% B; 4-6 min: 95% B; 6-6.15 min: 99% B; 6.15-8.5 min: 99% B; 8.5-8.65 min: 1% B; 8.65-10 min: 1% B. The mass spectrometry conditions are as follows: HESI ion source: sheath gas flow rate is 50 L / min, auxiliary gas flow rate is 15 L / min, spray voltage is 3.50 kV, ion transmission tube temperature is 320℃, radio frequency prism voltage is 50%, auxiliary gas heating temperature is 350℃. ​

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