A device and method for determining toxicity of antibiotics and intermediates in the process of treating the same in water

Abstract

The present application relates to a kind of water body antibiotic and its degradation intermediate toxicity determination device and method, belong to the detection technical field of water antibiotic.The determination device includes: degradation reaction chamber, degradation reaction chamber is horizontally arranged flat plug flow reactor, the two ends of flat plug flow reactor are continuous water inlet and continuous water outlet respectively;Degradation reaction chamber is provided with fixed matrix, and microbial membrane or photodegradation material is attached on fixed matrix, or continuous inlet section is connected with chemical oxidant;The bottom of degradation reaction chamber is provided with multiple low-flow water outlets at the distance set along length direction;Low-flow water outlet is connected with toxicity detection device;The flow ratio of single low-flow water outlet and continuous water outlet is 1:(300-1000), and the number of low-flow water outlet is 3-10.In flat plug flow reactor, the time difference of antibiotic degradation process can be reflected from different low-flow water outlet position, so toxicity is determined at each point, and the toxicity of antibiotic matrix and intermediate product can be more accurately obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of detection of antibiotics in water, and particularly relates to a device and method for determining the toxicity of antibiotics and intermediate products in the treatment process of the antibiotics in water. BACKGROUND

[0002] The information disclosed in this BACKGROUND section is only for the purpose of increasing the understanding of the background of the present application and therefore it should not be taken as an acknowledgement or any form of suggestion that it forms prior art with respect to any country.

[0003] Antibiotics are mainly used for treating and preventing various bacterial or pathogenic microbial infection diseases and promoting animal growth. There are many types of antibiotics, which are mainly divided into β-lactam, macrolide, sulfonamide, fluoroquinolone, tetracycline, polypeptide, lincomycin and aminoglycoside. Although the concentration of antibiotics is low, they cannot be completely metabolized by the human body and other animals, and a large amount of residual antibiotics and their metabolites will enter the water environment through various channels, affect the structure and function of microbial communities in water, induce the production of antibiotic resistance genes, and affect the cycling of nitrogen, carbon, phosphorus and other elements, which poses a potential threat to human health and the sustainable development of the ecological system. Therefore, the evaluation of the toxicity of antibiotics at an environmental concentration cannot be ignored.

[0004] In existing toxicity evaluation experiments, in order to ensure that the reaction substances are mixed uniformly and improve the reaction efficiency, the reaction is generally carried out in a complete mixing flow reactor. The steps include: culturing microorganisms in a complete mixing flow reactor, adding a certain concentration of antibiotics to the system after the system is stable, and fully contacting the microorganisms for a certain period of time, and then evaluating the toxicity degree of the antibiotics through a toxicity determination method.

[0005] However, in the process of toxicity detection, microorganisms can degrade antibiotics to produce intermediate products, resulting in a difference between the composition of the solution and the original solution. The intermediate products may be more toxic than the parent antibiotics, and therefore it is difficult to determine the toxicity of the set concentration of antibiotics itself when the intermediate products and the parent antibiotics are mixed together.

[0006] On the other hand, natural environment water bodies are contaminated by point sources and non-point sources, and this pollution is a continuous process with relatively constant pollutant concentration; however, in experiments, the pollutants are generally added once, and there are mutual reactions over time, so the experiment often cannot reflect the state of the water body being constantly polluted in nature.

[0007] In addition, the antibiotics and intermediate products are mixed in the solution, and the toxicity of the intermediate products is generally simulated and analyzed by structure-activity relationship software, and there is still a lack of direct characterization means for experimental determination. SUMMARY

[0008] In view of the deficiencies of the prior art, the purpose of the present application is to provide a device and method for determining the toxicity of antibiotics and degradation intermediates thereof in a water body, in the reaction chamber, the sewage is mainly transported in the form of a plug flow, and a series of low-flow water outlets are arranged at different points; so that the toxicity test organisms (test organisms) at different points respectively contact the relatively stable water quality. The initial point simulates the state of continuous pollution of the water body in nature, and the subsequent points can reflect the toxicity of antibiotic intermediates at different processing stages.

[0009] In order to achieve the above-mentioned purpose, the technical scheme of the present application is:

[0010] In a first aspect, a device for determining the toxicity of antibiotics and intermediates thereof in a water body, comprising: a degradation reaction chamber, the degradation reaction chamber is a horizontally arranged plug flow reaction chamber, and the two ends of the plug flow reaction chamber are respectively a continuous water inlet and a continuous water outlet;

[0011] A fixed substrate is arranged in the degradation reaction chamber, and the fixed substrate is attached with antibiotic degradation organisms and / or photocatalytic materials;

[0012] A plurality of low-flow water outlets are arranged at intervals along the length direction at the bottom of the degradation reaction chamber; the low-flow water outlets are connected to a toxicity detection device;

[0013] The flow rate of a single low-flow water outlet to the flow rate of the continuous water outlet is 1:(300-1000), and the number of low-flow water outlets is 3-10.

[0014] Optionally, the fixed substrate is selected from one or more of agar and sponge materials.

[0015] Optionally, the permeability of the fixed substrate is 10 -2 ~ 10 -6 cm / s, and the fixed substrate is filled in the degradation reaction chamber from bottom to top at a filling rate of 30-50%.

[0016] Optionally, the degradation reaction chamber is made of a light-transmitting material.

[0017] Optionally, a light source is arranged outside the degradation reaction chamber, and the light emitted by the light source irradiates on the antibiotic degradation organisms and / or photocatalytic materials.

[0018] Optionally, the degradation reaction chamber is provided with a high-level oxidation interface, the high-level oxidation interface is used for introducing a high-level oxidation reagent into the degradation reaction chamber, and the high-level oxidation reagent includes ozone, persulfate, hydrogen peroxide, etc.

[0019] Optionally, the toxicity detection device comprises a toxicity determination pool, a filter membrane is arranged in the toxicity determination pool, and toxicity test organisms are intercepted on the filter membrane, and the toxicity test organisms include one or more of microalgae and luminous bacteria.

[0020] Optionally, the toxicity detection device comprises a toxicity detection chamber for collecting the sewage to be detected and detecting the toxicity.

[0021] In a second aspect, a method for detecting the toxicity of antibiotics and degradation intermediates thereof in a water body using the toxicity detection device for detecting the toxicity of antibiotics and degradation intermediates thereof in a water body is provided, comprising the following steps:

[0022] S1, after the main flow of sewage containing antibiotics is treated, the sewage is split and flows into the degradation reaction chamber through the continuous water inlet, flows through the degradation reaction chamber in a plug flow state, and is continuously discharged through the continuous water outlet;

[0023] S2, after the sewage is continuously transported into the degradation reaction chamber, the antibiotics are degraded on the surface of the fixed substrate by antibiotic-degrading organisms and / or photocatalytic materials;

[0024] S3, after the degradation state of the antibiotics in S2 is stable, the low-flow water outlet at the bottom of the degradation reaction chamber is opened, so that the treated sewage flows downward in a trickling manner and flows out of the constant water quality sewage to be detected at a constant flow rate through the low-flow water outlet;

[0025] S4, the low-flow water outlets at different positions correspond to different sewage treatment times, and the toxicity of the sewage corresponding to the degradation time is detected by detecting the sewage to be detected at the low-flow water outlets at different positions. The low-flow water outlet near the water inlet end can reflect the toxicity of the untreated antibiotics.

[0026] Optionally, in S1, the concentration of antibiotics in the split sewage is in the range of 1.0 ug / L to 50.0 mg / L; the hydraulic retention time in the degradation reactor is 30 min to 7 days; and the water inlet flow rate of the continuous water inlet is determined according to the hydraulic retention time.

[0027] Optionally, during the process of continuously transporting the sewage into the degradation reaction chamber, the light source outside the degradation reaction chamber is turned on to irradiate the antibiotic-degrading organisms and / or photocatalytic materials on the fixed substrate to degrade the antibiotics in the sewage.

[0028] Optionally, in S2, advanced oxidation reagents such as ozone, persulfate, and hydrogen peroxide are input into the degradation reaction chamber through the advanced oxidation interface to perform advanced oxidation on the sewage.

[0029] Optionally, in S4, a biological detection pool to be detected is arranged below the low-flow water outlet, and the toxicity of the antibiotics and their treatment products is determined by continuously contacting the sewage of constant water quality with the toxicity test organisms (organisms to be detected) and judging the toxicity of the antibiotics and their treatment products through the growth status of the organisms to be detected or the luminosity of the bacteria.

[0030] Optionally, in S4, the sewage to be determined is collected in the toxicity determination chamber below the low-flow water outlet, and the toxicity of the antibiotic and its treatment product is analyzed by using a liquid chromatography-mass spectrometry instrument, an enzyme marker instrument, or the like.

[0031] The present application has the following advantages:

[0032] 1. The present application adopts a plug flow reaction chamber, in which the water body achieves complete mixing in the radial direction, and the flow rate and concentration remain uniform in the cross section perpendicular to the flow direction. Therefore, in the plug flow reaction chamber, a longer degradation time corresponds to a more distant position along the water flow direction, so that the time difference of substances during antibiotic degradation can be reflected from different low-flow water outlet positions. Moreover, the flow rate of the series of water outlets at the lower part of the reaction chamber is much smaller than the flow rate of the continuous water inlet, so as to ensure that the plug flow state of the entire reaction system will not be affected by the water outlets at the lower part. During the degradation process, different intermediate products will be produced in different degradation time periods, and the toxicity of different intermediate products will be different. Therefore, by determining the toxicity at each point, the toxicity of the antibiotic mother substance and the intermediate products can be more accurately obtained.

[0033] 2. The present application adopts a fixed substrate culture microbial membrane or attached photocatalytic material, which has higher stability than the suspended culture mode, and the growth of antibiotic degradation organisms in the system is more stable, and is resistant to water quality and water volume fluctuation impact, thereby reducing the exchange of substances at different positions along the water flow. It can avoid a large number of toxicity test organisms (test organisms) from entering the low-flow water outlet, causing internal blockage of the structure, and at the same time, it can retain most of the degradation organisms as seeds to start the next cycle of treatment process, and itself can be sustainable and easy to maintain.

[0034] 3. In the present application, independent toxicity detection devices are arranged below the plurality of low-flow water outlets, so that the toxicity test organisms at different positions (low-flow water outlets) are all in contact with water of the same concentration, which represents the water quality characteristics of different time periods of biological degradation of antibiotics. By measuring the OD, enzyme activity, and the like of the toxicity determination organisms such as luminescent bacteria and microalgae in the lower toxicity determination chamber, the biological toxicity of the continuously received water can be truly reflected. Therefore, the state of the continuous pollution of the water body in the natural environment can be accurately simulated.

[0035] 4. In the field of toxicity characterization of intermediate products, in addition to the simulation analysis by using a structure-activity relationship software, the present application provides a direct characterization means for experimental determination, which can accurately analyze the toxicity of different intermediate products. BRIEF DESCRIPTION OF DRAWINGS

[0036] The drawings accompanying the specification of the present application serve to provide a further understanding of the present application, and the illustrative embodiments of the present application and their descriptions serve to explain the present application, and do not constitute an improper limitation on the present application.

[0037] Figure 1 Figure 1 is a schematic diagram of a device for determining the toxicity of antibiotic degradation intermediates in water bodies according to an embodiment of the present application.

[0038] Figure 2 Figure 4 is a graph of the results of the detection of sulfamethoxazole in Example 1.

[0039] Figure 3 Figure 5 is a graph of the results of the detection of sulfisoxazole in Example 1.

[0040] Figure 4 Figure 6 is a graph of the results of the detection of sulfadiazine in Example 1.

[0041] Figure 1 is a schematic diagram of a device for determining the toxicity of antibiotic degradation intermediates in water bodies according to an embodiment of the present application. In Figure 1, 1 is a degradation reaction chamber; 2 is a continuous water inlet; 3 is an antibiotic degradation organism and / or photocatalytic material; 4 is a continuous water outlet; 5 is a fixed substrate; 6 is a target antibiotic; 7 is an antibiotic degradation product a; 8 is an antibiotic degradation product b; 9 is a light source; 10 is a low-flow water outlet; 11 is a toxicity test organism; 12 is a filter membrane; and 13 is a toxicity determination chamber. DETAILED DESCRIPTION

[0042] It should be noted that the following detailed description is merely exemplary in nature and is intended to provide further description of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0043] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0044] The toxicity of antibiotics to organisms mainly includes the following aspects:

[0045] Cell wall and membrane damage: Antibiotics can damage the cell wall and membrane structure of organisms, leading to the leakage of cell contents and ultimately leading to cell death.

[0046] Inhibition of protein synthesis: Antibiotics can inhibit protein synthesis in microorganisms, affecting their growth and reproduction, and ultimately leading to cell death.

[0047] DNA or RNA damage: Certain antibiotics can directly affect the stability of DNA or RNA in microorganisms, leading to inhibition of the expression of mutant genes, thereby producing toxicity to cells.

[0048] Oxidative stress: Some antibiotics can cause oxidative stress in cells, leading to oxidative damage and affecting cell function and survival.

[0049] Moreover, overuse of antibiotics in water bodies can lead to increased antibiotic resistance in aquatic organisms, causing harm to their ecosystems; by conducting antibiotic toxicity tests, the ecological risk of antibiotics to aquatic organisms can be assessed, and appropriate measures can be taken to protect the health of aquatic organisms and ecosystems; if there are antibiotic residues in water bodies and they are toxic to aquatic organisms, they may be transmitted through the food chain to humans, posing potential risks to human health.

[0050] In summary, water body antibiotic toxicity testing is of great significance for ensuring water quality safety, ecological risk assessment, regulatory compliance, and preventing human health risks, and is a necessary step for protecting water environment and ecosystems.

[0051] Antibiotic toxicity testing is an important method for assessing the toxicity of antibiotics to organisms. Common methods include:

[0052] Bacterial toxicity testing: Using bacteria (such as E. coli) as model organisms, by culturing bacteria in culture media containing different concentrations of antibiotics, observing the growth of bacteria and changes in bacterial numbers, to evaluate the toxicity level of antibiotics.

[0053] Cell toxicity testing: Using cell culture technology, exposing specific types of cells (such as human cell lines or animal cells) to different concentrations of antibiotics, observing changes in cell morphology, growth and metabolic function, etc., to evaluate the toxicity of antibiotics to cells.

[0054] Fish toxicity testing: Using fish (such as zebrafish) as model organisms, exposing fish to water containing different concentrations of antibiotics, observing changes in fish behavior, growth and survival rate, etc., to evaluate the toxicity of antibiotics to fish.

[0055] Aquatic organism toxicity testing: In addition to fish, other aquatic organisms (such as algae, water fleas, crustaceans, etc.) can also be used for toxicity testing to evaluate the toxicity of antibiotics to aquatic organisms.

[0056] Ecological toxicology testing: Considering the toxicity of antibiotics to different organisms and their potential impact on ecosystems, through experimental design simulating natural environments, to evaluate the toxicity of antibiotics to the entire ecosystem.

[0057] Instrument testing: with the help of liquid chromatography-mass spectrometry, enzyme marker instrument, etc., combined with experimental design and data analysis, the concentration and absorbance or fluorescence intensity change of antibiotics in biological samples are determined, so as to evaluate the toxicity of antibiotics and its influence on biological system. In addition, some computer software can also be used to predict the toxicity of different degradation products of antibiotics.

[0058] The present application provides a device for determining the toxicity of antibiotics and intermediates in the process of treating antibiotics in water bodies, as shown in the figure, comprising: a degradation reaction chamber 1, the degradation reaction chamber 1 is a horizontal push flow reaction chamber, and the two ends of the push flow reaction chamber are respectively a continuous water inlet 2 and a continuous water outlet 4; Figure 1

[0059] The degradation reaction chamber 1 is provided with a fixed substrate 5, and the fixed substrate 5 is attached with antibiotic degradation organisms and / or photocatalytic materials 3;

[0060] The bottom of the degradation reaction chamber 1 is provided with a plurality of low-flow water outlets 10 at intervals along the length direction; the low-flow water outlets 10 are connected to the toxicity detection device;

[0061] The flow ratio of a single low-flow water outlet 10 to the continuous water outlet 4 is 1:(300-1000), the number of low-flow water outlets is 3-10, and the flow sum of all low-flow water outlets 10 is not more than 1% of the flow of the continuous water outlet 4.

[0062] Through the above setting, the water body in the push flow reaction chamber reaches complete mixing in the radial direction, and the flow rate and concentration remain uniform in the cross section perpendicular to the flow direction, so that the time difference of substances in the antibiotic degradation process can be reflected from different low-flow water outlet 10 positions; and the flow of a series of low-flow water outlets 10 at the lower part of the degradation reaction chamber 1 is much smaller than the flow of the continuous water inlet, which ensures that the push flow state of the whole reaction system will not be affected by the lower water outlet; therefore, the sewage collected at different low-flow water outlets 10 corresponds to different degradation time / stages, which contains different intermediate products produced due to different degradation time periods, for example, the water body near the continuous water inlet 2 position contains the target antibiotic 6, the target antibiotic is gradually degraded downstream, producing antibiotic degradation product a 7, and near the continuous water outlet 4 position, the antibiotic is degraded into antibiotic degradation product b 8, so that the toxicity is measured at each point (the position of the low-flow water outlet 10), the toxicity of the target antibiotic 6, antibiotic degradation product a 7 and antibiotic degradation product b 8 can be detected respectively, and the toxicity of the antibiotic mother body and the intermediate product can be obtained respectively more accurately.

[0063] ​The fixed matrix 5 is selected from one or more of agar, sponge and filter paper matrix, and has good fixation according to the porosity selection, which is conducive to the stable adhesion / growth of the antibiotic degrading organisms and / or photocatalytic materials 3 on the fixed matrix 5 and the treatment of antibiotics, thereby forming a stable water body state.

[0064] The permeability of the fixed matrix 5 is 10 -2 ~ 10 -6 cm / s, the fixed matrix 5 is filled in the degradation reaction chamber 1 from bottom to top according to a filling rate of 30-50%, above the fixed matrix 5, the cultivated antibiotic degrading organisms and / or photocatalytic materials 3 gradually degrade the antibiotics, in the fixed matrix 5, the sewage with the same water quality flows downward in a free trickling manner and is discharged through the low-flow water outlet 10.

[0065] The degradation reaction chamber 1 is made of a light-transmitting material, which facilitates the increase of external light sources and the growth of the antibiotic treatment microorganisms under light or the degradation of the sewage containing antibiotics by the photocatalytic materials.

[0066] The degradation reaction chamber 1 is provided with a light source 9 outside, the light emitted by the light source 9 irradiates on the photocatalytic materials; the photocatalytic materials can be selected from one or more of materials with catalytic conditions such as TiO2, nano-composite materials (such as ore / g-C3N4).

[0067] The degradation reaction chamber 1 is provided with an advanced oxidation interface at the top, the advanced oxidation interface is used to introduce ozone and other advanced oxidation reagents into the degradation reaction chamber 1, and the advanced oxidation method is used to treat the antibiotics, specifically, the advanced oxidation reagents include one or more of ozone, persulfate and hydrogen peroxide.

[0068] Chemical oxidation reagents can also be introduced into the degradation reaction chamber 1 along with the water at the water inlet end to investigate the toxicity of the intermediate products of antibiotic chemical oxidation.

[0069] The toxicity detection device includes a toxicity determination pool, the toxicity determination pool receives the sewage to be detected flowing out of the low-flow water outlet 10, a filter membrane 12 is arranged in the toxicity determination pool, and a toxicity test organism 11 is intercepted above the filter membrane 12, the toxicity test organism 11 includes one or more of microalgae and luminous bacteria, wherein the microalgae can be selected from algae species (such as chlorella) with characteristics such as sensitivity to toxic substances, fast growth rate, easy cultivation and low cost; the luminous bacteria can be selected from luminous bacteria (such as Vibrio fischeri) with characteristics such as visibility, high sensitivity and good biological relativity or other antibiotic-tolerant bacteria.

[0070] The toxicity determination chamber 13 is used to collect the sewage to be detected, so as to analyze the composition of the sewage to be detected by using detection devices (including liquid chromatography-mass spectrometry and enzyme labeling instrument).

[0071] The application provides a method for determining the toxicity of antibiotics and degradation intermediates thereof in a water body by using the device for determining the toxicity of antibiotics and degradation intermediates thereof in a water body.

[0072] S1, the main flow of sewage containing antibiotics is divided into sewage after treatment, and the sewage is transported into the degradation reaction chamber 1 through the continuous water inlet 2, flows through the degradation reaction chamber 1 in a plug flow state, and is continuously discharged through the continuous water outlet 4.

[0073] S2, after the sewage is continuously transported into the degradation reaction chamber 1, the antibiotics are degraded on the surface of the fixed substrate 5 by the antibiotic-degrading organisms and / or the photocatalytic material 3.

[0074] S3, after the antibiotic-degrading organisms and / or the photocatalytic material 3 in S2 are stable and the degradation state of the antibiotics is stable, the low-flow water outlet 10 at the bottom of the degradation reaction chamber 1 is opened, so that the treated sewage flows downward along the fixed substrate 5 in a trickling manner, and flows out of the constant water quality sewage to be determined at a constant flow rate through the low-flow water outlet 10.

[0075] S4, the low-flow water outlets 10 at different positions correspond to different sewage degradation times, and the toxicity of the sewage corresponding to the degradation time is determined by detecting the sewage to be determined at the low-flow water outlets 10 at different positions; wherein the low-flow water outlet 10 closest to the continuous water inlet 2 receives the water quality, representing the untreated antibiotic solution, and is used for determining the toxicity of the antibiotics.

[0076] Through the above method, the antibiotic-degrading organisms and / or the photocatalytic material 3 are used for the degradation of the antibiotics; the water inlet is treated by the antibiotic-degrading organisms and / or the photocatalytic material 3, and then is collected by a series of water outlets at the lower part of the reactor, and is subjected to the toxicity test of the continuous flow, respectively, so that the biomass of the toxicity test organisms, i.e. OD, or the determination of physiological and biochemical indexes such as enzyme activity, reflects the biological toxicity in different stages of the antibiotic degradation.

[0077] In the process of continuously transporting the sewage into the degradation reaction chamber 1, the light source 9 outside the degradation reaction chamber 1 is opened to irradiate the antibiotic-degrading organisms and / or the photocatalytic material 3 on the fixed substrate 5, so as to provide the light required by the antibiotic-degrading organisms and / or promote the photocatalytic reaction of the photocatalytic material to treat the antibiotics in the sewage.

[0078] In S1, the concentration of the antibiotics in the divided sewage ranges from 1.0 ug / L to 50.0 mg / L.

[0079] In S1, the water inlet amount needs to be adjusted according to the volume of the degradation reaction chamber 1 and the degradation means adopted, and the degradation time of the antibiotics in S3 and the time to reach the stable state of the system are different for different degradation means.

[0080] In S3, the required time for the degradation state of the antibiotic to be stable varies depending on the treatment object and the treatment method. When an antibiotic-degrading microorganism is used, the microorganism needs to grow to a stable state. When a microalgae is used as the antibiotic-degrading microorganism, about 1 day is required for the degradation state of the antibiotic to be stable. When a photocatalytic material is used, the water quality can reach a stable state after about several hours.

[0081] In S4, a biological assay tank is arranged below the low-flow outlet 10, and the toxic test organism 11 on the filter membrane 12 is continuously exposed to the sewage with constant water quality. The toxicity of the antibiotic and its treatment products is determined by the growth condition of the toxic test organism 11 (the test organism) or the luminosity of the bacteria.

[0082] In S4, the sewage to be determined is collected in the toxicity determination chamber 13 below the low-flow outlet 10. The toxicity of the antibiotic and its treatment products is analyzed by using a liquid chromatograph-mass spectrometer, an enzyme marker instrument, or the like.

[0083] Embodiment 1

[0084] A device for determining the toxicity of an antibiotic and an intermediate product in the treatment process of the antibiotic in a water body, comprising: a degradation reaction chamber 1, the degradation reaction chamber 1 being a horizontally arranged plug flow reaction chamber, the plug flow reaction chamber being made of a light-transmitting material, and the plug flow reaction chamber having a continuous water inlet 2 and a continuous water outlet 4 at two ends thereof, respectively; the length of the degradation reaction chamber 1 between the continuous water inlet 2 and the continuous water outlet 4 is 1 m, and the length-width ratio of the degradation reaction chamber 1 is 10:1.

[0085] A sponge is used as a fixed substrate 5 in the degradation reaction chamber 1, and microalgae are attached to the fixed substrate 5.

[0086] A plurality of low-flow outlets 10 are arranged at the bottom of the degradation reaction chamber 1 at intervals of 30 cm along the length direction; and the first low-flow outlet 10 is arranged close to the continuous water inlet 2, and the low-flow outlets 10 are connected to a toxicity detection device.

[0087] The flow rate of a single low-flow outlet 10 to the flow rate of the continuous water outlet 4 is 1:300, and the flow rate of all the low-flow outlets 10 to the flow rate of the continuous water outlet 4 is 1:100.

[0088] The permeability of the sponge is 10 cm / s, which can ensure that the plug flow water above the microbial membrane trickles down, and the sponge is filled in the degradation reaction chamber 1 from bottom to top at a filling rate of 50%. -4 The degradation microorganism is cultured on the fixed substrate 5 to form a stable antibiotic-degrading microorganism, which gradually degrades the antibiotic. The sewage with constant water quality flows downward in a free trickling manner in the fixed substrate 5 and is discharged through the low-flow outlets 10.

[0089] A light source 9 is arranged outside the degradation reaction chamber 1.

[0090] The toxicity detection device comprises a toxicity detection pool and a toxicity detection chamber 13; a filter membrane 12 is arranged in the toxicity detection pool, and the toxicity test organisms 11 trapped on the filter membrane 12 are selected as Chlorella, and the growth condition of Chlorella is used to detect the toxicity; the toxicity detection chamber 13 is used to collect the sewage to be detected, and centralized detection is performed when the sewage to be detected is collected to a set amount.

[0091] The determination method of the toxicity detection device for antibiotics in the water body and intermediate products in the treatment process in the embodiment is as follows:

[0092] The water inlet of the degradation reaction chamber 1 is BG11 culture solution containing antibiotics (one of sulfamethoxazole SMX, sulfadimidine SM2 and sulfadiazine SDZ is used as a detection object respectively), and tap water is used as raw material to configure the BG11 culture solution by using sodium carbonate, sodium nitrate, dipotassium hydrogen phosphate and some trace elements. The antibiotic content is 5 mg / L, and the water inlet flow is about 0.001 m 3 / d;

[0093] Chlorella is inoculated on the sponge material fixed matrix 5 as antibiotic degradation organisms, and the initial inoculation amount is 5-8.5×10 6 / mL.

[0094] The microalgae on the fixed matrix 5 are cultured under the conditions of light intensity of 4000 lux, temperature of 25℃, and light-dark ratio of 12:12.

[0095] After about one week, the microbial membrane on the fixed matrix 5 reaches stability and can be used as antibiotic degradation organisms to treat sewage. At this time, the low-flow water outlet 10 below the degradation reaction chamber 1 is opened, and the sewage to be determined is collected.

[0096] By calculating the difference between the specific growth rate of the Chlorella as the toxicity test organisms 11 on the filter membrane 12 in the toxicity detection pool on the 5th day and the 7th day and the blank control group, the toxicity of the antibiotic to the microalgae can be reflected.

[0097] The full-mix flow reactor is used for comparison, and the growth curve of Chlorella is also determined, and the specific growth rate is calculated.

[0098] The toxicity test results of the first water outlet are shown in Table 1, Figures 2 to 4 Table 1 shows the detection results of sulfamethoxazole SMX, Figure 2 Table 2 shows the detection results of sulfadimidine SM2, Figure 3 and Table 3 shows the detection results of sulfadiazine SDZ. Figure 4The detection result of sulfadiazine SDZ is shown in the figure. The difference (△r) is positive, indicating that the antibiotic inhibits the growth of microalgae; otherwise, it indicates that the antibiotic promotes the growth of microalgae; the greater the difference, the greater the influence of the antibiotic on the microalgae.

[0099] In the reaction for 5-7 days, the specific growth rate difference of microalgae in the first low-flow effluent (i.e. untreated antibiotic) of the three different antibiotics (P in the figure) is greater than that of the microalgae in the control group (M in the figure); the results show that whether the antibiotic promotes or inhibits the microalgae, the evaluation of the antibiotic toxicity of the complete mixing flow reactor is lower than that of the plug flow reactor. It is further verified that the method of measuring the toxicity of the new plug flow reactor for determining the toxicity of the antibiotic is more accurate.

[0100] In addition to the first low-flow effluent 10, the growth of the toxicity test organisms 11 in the subsequent effluents is slightly worse than that of the control group, and the toxicity of the intermediate products of the biological degradation of the experimental antibiotic is: 3%-5% of the microalgae growth inhibition, but it does not mean that the intermediate products of other treatment methods or other antibiotics have low toxicity.

[0101] It can be seen that, compared with the complete mixing flow reactor, the content of antibiotics and intermediate products in the sewage of the low-flow effluent 10 at different positions in the plug flow reactor in the embodiment has a spatial difference, and remains stable for a long time, so that the plug flow reactor in the embodiment can simulate the flow state of the natural water body;

[0102] And, by arranging the low-flow effluent 10 at different positions, the treated sewage containing different intermediate products and proportions can be effectively obtained, different intermediate products and concentrations correspond to different time stages of antibiotic degradation, and the method of the embodiment can effectively reflect the state of the water body being constantly polluted in nature. In addition, the toxicity of the antibiotics and intermediate products in the separated solution can be directly characterized by using the experimental determination means.

[0103] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A device for measuring the toxicity of antibiotics in water and intermediate products thereof during treatment, characterized in that: The application relates to a wastewater degradation device and a wastewater degradation method. The degradation reaction chamber is a horizontal planar plug flow reaction chamber, and the two ends of the planar plug flow reaction chamber are respectively provided with a continuous water inlet and a continuous water outlet. A fixed substrate is arranged in the degradation reaction chamber, and antibiotic degradation organisms and / or photocatalytic materials are attached to the fixed substrate. A plurality of low-flow water outlets are arranged at intervals along the length direction of the bottom of the degradation reaction chamber at a certain distance. The flow rate of a single low-flow water outlet to the flow rate of the continuous water outlet is 1: (300-1000), and the number of low-flow water outlets is 3-10. In the fixed substrate, wastewater with constant water quality flows downward in a free trickling manner and is discharged through the low-flow water outlets.

2. The apparatus for determining toxicity of an antibiotic and an intermediate product in a process for treating the antibiotic in a water body according to claim 1, wherein The fixed substrate is selected from one or more of agar and sponge materials.

3. The apparatus for determining toxicity of an antibiotic and an intermediate product in a process for treating the antibiotic in a water body according to claim 1, wherein The permeability of the stationary matrix is 10 -2 -10 -6 cm / s, the stationary matrix is filled in the degradation reaction chamber from bottom to top with a filling rate of 30-50%.

4. The apparatus for determining toxicity of an antibiotic and an intermediate product in a process for treating the antibiotic in a water body according to claim 1, wherein The degradation reaction chamber is made of a light-transmitting material.

5. The apparatus for determining toxicity of an antibiotic and intermediates thereof in a water body and in a process for treating the same according to claim 4, wherein A light source is arranged outside the degradation reaction chamber, and the light emitted by the light source irradiates the antibiotic degradation organisms and / or photocatalytic materials.

6. The apparatus for determining toxicity of an antibiotic and intermediates thereof in a water body and in a process for treating the same according to claim 1, wherein The degradation reaction chamber is provided with a high-level oxidation interface, and the high-level oxidation interface is used for inputting a high-level oxidation reagent into the degradation reaction chamber.

7. The apparatus for determining toxicity of an antibiotic and intermediates thereof in a water body and in a process for treating the same according to claim 1, wherein The toxicity detection device comprises a toxicity determination pool, a filter membrane is arranged in the toxicity determination pool, and toxicity test organisms are intercepted on the filter membrane, wherein the toxicity test organisms comprise one or more of microalgae and luminous bacteria.

8. The apparatus for determining toxicity of an antibiotic and intermediates thereof in a water body and in a process for treating the same according to claim 1, wherein The toxicity detection device comprises a toxicity determination chamber, which is used for collecting wastewater to be detected and performing toxicity detection.

9. A method for measuring toxicity of an antibiotic in a water body and an intermediate product in a treatment process thereof using the apparatus for measuring toxicity of an antibiotic in a water body and an intermediate product in a treatment process thereof according to any one of claims 1 to 8, characterized by, The application further discloses a wastewater degradation method. S1: After the main flow of wastewater containing antibiotics is treated, the wastewater is branched out, enters the degradation reaction chamber through the continuous water inlet, flows through the degradation reaction chamber in a planar plug flow state, and is continuously discharged through the continuous water outlet. S2: After the wastewater is continuously transported into the degradation reaction chamber, the wastewater is degraded by the antibiotic degradation organisms and / or photocatalytic materials on the surface of the fixed substrate. S3: After the degradation state of the antibiotics in S2 is stable, the low-flow water outlets at the bottom of the degradation reaction chamber are opened, so that the treated wastewater flows downward in a trickling manner and flows out from the low-flow water outlets at a constant flow rate to obtain wastewater with constant water quality to be determined. S4: Different low-flow water outlets correspond to different wastewater degradation times, and the toxicity of the wastewater corresponding to the degradation times is determined by detecting the wastewater to be determined from the low-flow water outlets.

10. The method for determining toxicity of antibiotics and intermediates in their processing in water bodies according to claim 9, characterized in that, In the process of continuously transporting the wastewater into the degradation reaction chamber, the light source outside the degradation reaction chamber is turned on to irradiate the antibiotic degradation organisms and / or photocatalytic materials on the fixed substrate to degrade the antibiotics in the wastewater.

11. The method for determining toxicity of antibiotics and intermediates in their processing in water bodies according to claim 9, characterized in that, In S1, the concentration of the antibiotics in the branched-out wastewater ranges from 1.0 ug / L to 50.0 mg / L, the hydraulic retention time in the degradation reaction chamber ranges from 30 min to 7 days, and the water inlet flow rate of the continuous water inlet is determined according to the hydraulic retention time.

12. The method for determining toxicity of antibiotics and intermediates thereof in the process of treating the same in water bodies as claimed in claim 9, wherein, In S2, the high-level oxidation reagent is inputted into the degradation reaction chamber through the high-level oxidation interface to perform high-level oxidation on the wastewater.

13. The method for determining toxicity of antibiotics and intermediates thereof in the process of treating the same in water bodies as claimed in claim 9, wherein, In S4, the sewage to be determined is collected in the toxicity determination chamber below the low-flow outlet, and the toxicity of the antibiotic and its treatment product is analyzed by liquid chromatography-mass spectrometry and enzyme labeling instrument. ​ 14. The method for determining toxicity of antibiotics and intermediates thereof in the process of treating the same in water bodies as claimed in claim 9, wherein, In S4, the sewage to be determined is collected in the toxicity determination chamber below the low-flow outlet, and the toxicity of the antibiotic and its treatment product is analyzed by liquid chromatography-mass spectrometry and enzyme labeling instrument. ​

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