A method for screening fishery disinfectant based on dehydration erythromycin reaction process analysis

By setting up a reaction system in aquaculture water and adding fish disinfectant, the optimal disinfectant was screened out, solving the problem of antibiotic degradation in aquaculture, achieving efficient degradation of dehydrated erythromycin, and ensuring the health of aquatic products and the quality and safety of aquatic products.

CN118883738BActive Publication Date: 2026-05-29SOUTH CHINA SEA FISHERIES RES INST CHINESE ACAD OF FISHERY SCI +1
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
SOUTH CHINA SEA FISHERIES RES INST CHINESE ACAD OF FISHERY SCI
Filing Date
2024-06-25
Publication Date
2026-05-29

AI Technical Summary

Technical Problem

Existing technologies have not been effectively applied to the degradation and elimination of antibiotics in aquaculture, leading to pollution of aquaculture water sources and threatening the health of aquatic animals and the quality and safety of aquatic products.

Method used

Two reaction systems were set up: one for ultrapure water and the other for aquaculture. Calcium oxide was added to adjust the pH, and fishery disinfectants such as potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium persulfate, and strong chlorine were added for reaction analysis. The concentration of dehydrated erythromycin was detected by UPLC-MS/MS, and the disinfectant with the optimal degradation rate was screened out.

Benefits of technology

It achieves efficient degradation of dehydrated erythromycin, screens out the optimal disinfectant for fisheries, reduces antibiotic residues in aquaculture water, and ensures the health of aquatic products and the quality and safety of aquatic products.

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Abstract

The application discloses a method for screening fishery disinfectants based on analysis of erythromycin dehydration reaction process, which comprises the following steps: setting two reaction systems of ultrapure water and aquaculture water source water, and making the concentration of erythromycin dehydration in the systems be 5000 ng / L; adding calcium oxide into the two reaction systems for 8 hours, and then adding dilute hydrochloric acid to neutralize the two reaction systems to pH 7.2; adding potassium permanganate, dibromine, sodium hypochlorite, potassium hydrogen persulfate and strong chlorine into the different reaction systems respectively for different reaction analysis, and setting the reaction concentration of the above fishery disinfectants be 15 mg / L and 30 mg / L; detecting the concentration of erythromycin dehydration after reaction of the two systems by UPLC-MS / MS; and screening the fishery disinfectants with the optimal degradation rate based on fitting the concentration change by using a monadic three-parameter attenuation equation.
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Description

Technical Field

[0001] This invention relates to the field of water pollution analysis, and more specifically, to a method for screening fishery disinfectants based on the analysis of the dehydrated erythromycin reaction process. Background Technology

[0002] Antibiotic contamination has become a major concern for researchers and government departments. The issue of antibiotic residues in aquaculture urgently needs attention. Studies have shown that antibiotics at concentrations of 1000–5000 ng / L can be detected in aquaculture water sources and ponds, with erythromycin at the highest concentration. Even low levels of antibiotics (sub-minimum inhibitory concentration) can induce high levels of antibiotic resistance, posing a serious threat to the health of aquatic animals and aquaculture workers. Furthermore, antibiotic residues in aquaculture can be transmitted to humans through consumption, seriously endangering the quality and safety of aquatic products and human health.

[0003] Antibiotic removal primarily involves photoelectrochemical degradation, photodegradation, biosorption degradation, and advanced oxidative degradation. Although research on the elimination and degradation mechanisms of antibiotics has been reported, these technologies are currently only in the laboratory research stage and have not yet been widely applied in the aquaculture industry. Furthermore, aquaculture consumes a huge amount of water, making it difficult to widely apply these antibiotic elimination and degradation technologies. In addition, antibiotic degradation and elimination at wastewater treatment plants are incomplete; some antibiotics are still discharged into rivers and other receiving water bodies with the wastewater, potentially accumulating in aquaculture water sources and posing risks to healthy aquaculture and the safety of aquatic products. Therefore, given the large water consumption and antibiotic contamination of aquaculture water sources, there is an urgent need to research antibiotic degradation and elimination technologies suitable for widespread application in the aquaculture industry to ensure ecological safety and food safety.

[0004] Disinfectants for aquaculture are widely used in aquaculture. From early-stage pond cleaning and water disinfection to pre-stocking medicated baths, mid-to-late-stage disease prevention and control, and even daily water quality management, disinfectants are indispensable. Their mechanism of action involves destroying the chemical structure of substances or binding to the biochemical structure of pathogens through oxidation or other chemical reactions, thus inactivating the chemical substances and microorganisms. Commonly used disinfectants in aquaculture are generally classified into aldehydes, halogens, quaternary ammonium salts, potassium persulfate, and potassium permanganate. Therefore, based on the widespread use of disinfectants in aquaculture, and combined with necessary aquaculture measures such as early-stage pond cleaning and water disinfection, this study explores the effects of disinfectants on the degradation and elimination of antibiotics in aquaculture. This can effectively reduce the threat of antibiotic residue pollution to healthy aquaculture and the quality and safety of aquatic products. However, due to current technology limitations, there is a lack of techniques for using disinfectants to remove antibiotics from aquaculture water. Summary of the Invention

[0005] This invention overcomes the shortcomings of the prior art and proposes a method for screening fish disinfectants based on the analysis of the dehydrated erythromycin reaction process.

[0006] The first aspect of this invention provides a method for screening fishery disinfectants based on the analysis of the dehydrated erythromycin reaction process, comprising:

[0007] Two reaction systems were set up: one for ultrapure water and the other for aquaculture water.

[0008] In both reaction systems, the concentration of dehydrated erythromycin was set at 5000 ng / L. Calcium oxide was added to both reaction systems to make the concentration of calcium hydroxide in the reaction system reach 0.01%.

[0009] Add calcium oxide and react for 8 hours, then add dilute hydrochloric acid to neutralize and bring both reaction systems to pH 7.2;

[0010] Potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium peroxymonosulfate, and strong chlorine were added to different reaction systems for different reaction analyses, and the reaction concentrations of the above-mentioned fish disinfectants were set at 15 mg / L and 30 mg / L.

[0011] Sodium thiosulfate solution was added immediately after the reaction in the ultrapure water system for 12 hours and the reaction in the aquaculture water source system for 24 hours. The molar concentration of the sodium thiosulfate solution was 20 times that of the corresponding fish disinfectant. The reaction was stopped by adding sodium thiosulfate solution.

[0012] The concentrations of dehydrated erythromycin in the two systems after the reaction were determined by UPLC-MS / MS.

[0013] In this scheme, the fish disinfectant includes potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium peroxymonosulfate, and strong chlorine, and the two reaction systems include an ultrapure water system and an aquaculture source water system.

[0014] This scheme also includes: collecting the concentration changes of dehydrated erythromycin at 15 mg / L and 30 mg / L in an ultrapure water reaction system, based on the univariate three-parameter decay equation y=a*e -bx +c, fit the concentration change of fish disinfectant in the process of removing dehydrated erythromycin in ultrapure water system, and form the degradation kinetic equation of fish disinfectant on dehydrated erythromycin. From the degradation kinetic equation, screen out the fish disinfectant corresponding to the optimal degradation rate.

[0015] This invention discloses a method for screening fishery disinfectants based on the reaction process analysis of dehydrated erythromycin. Two reaction systems are set up: ultrapure water and aquaculture source water, with the concentration of dehydrated erythromycin in each system set at 5000 ng / L. Calcium oxide is added to both reaction systems and reacted for 8 hours, followed by neutralization with dilute hydrochloric acid to pH 7.2. Potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium persulfate, and strong chlorine are added to different reaction systems for different reaction analyses, with the reaction concentrations of the aforementioned fishery disinfectants set at 15 mg / L and 30 mg / L. The concentration of dehydrated erythromycin after the reaction in both systems is detected by UPLC-MS / MS. The optimal fishery disinfectant corresponding to the optimal degradation rate is screened based on a univariate three-parameter decay equation fitting the concentration change. Attached Figure Description

[0016] Figure 1 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 15 mg / L for dehydrated erythromycin in an ultrapure water system.

[0017] Figure 2 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 30 mg / L for dehydrated erythromycin in an ultrapure water system.

[0018] Figure 3 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 15 mg / L for dehydrated erythromycin in aquaculture water systems according to the present invention.

[0019] Figure 4 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 30 mg / L for dehydrated erythromycin in aquaculture water systems. Detailed Implementation

[0020] To better understand the above-mentioned objectives, features, and advantages of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.

[0021] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and therefore the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0022] The first aspect of this invention provides a method for screening fishery disinfectants based on the analysis of the dehydrated erythromycin reaction process, comprising:

[0023] Two reaction systems were set up: one for ultrapure water and the other for aquaculture water.

[0024] In both reaction systems, the concentration of dehydrated erythromycin was set at 5000 ng / L. Calcium oxide was added to both reaction systems to make the concentration of calcium hydroxide in the reaction system reach 0.01%.

[0025] Add calcium oxide and react for 8 hours, then add dilute hydrochloric acid to neutralize and bring both reaction systems to pH 7.2;

[0026] Potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium peroxymonosulfate, and strong chlorine were added to different reaction systems for different reaction analyses, and the reaction concentrations of the above-mentioned fish disinfectants were set at 15 mg / L and 30 mg / L.

[0027] Sodium thiosulfate solution was added immediately after the reaction in the ultrapure water system for 12 hours and the reaction in the aquaculture water source system for 24 hours. The molar concentration of the sodium thiosulfate solution was 20 times that of the corresponding fish disinfectant. The reaction was stopped by adding sodium thiosulfate solution.

[0028] The concentrations of dehydrated erythromycin in the two systems after the reaction were determined by UPLC-MS / MS.

[0029] It should be noted that the ultrapure water, also known as UP water, refers to water with a resistivity of 18 MΩ*cm (25℃).

[0030] According to an embodiment of the present invention, the fish disinfectant includes potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium peroxymonosulfate, and strong chlorine, and the two reaction systems include an ultrapure water system and an aquaculture source water system.

[0031] The removal efficiency (%) of dehydrated erythromycin by various concentrations of fish disinfectant in ultrapure water system is shown in Table 1 below:

[0032] ;

[0033] Figure 1 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 15 mg / L for dehydrated erythromycin in an ultrapure water system.

[0034] Based on the concentration change graph corresponding to Table 1 (at a concentration of 15 mg / L), see below. Figure 1 As shown;

[0035] like Figure 1 As shown in Table 1, in the ultrapure water system, after 12 hours of oxidation, the various fish disinfectants at a concentration of 15 mg / L showed the best removal effects on dehydrated erythromycin, with removal effects reaching 93.8%, 96.23%, and 95.73%, respectively.

[0036] Based on the concentration change graph corresponding to Table 1 (at a concentration of 30 mg / L), see below. Figure 2 As shown:

[0037] In an ultrapure water system, at a concentration of 30 mg / L, after 12 hours, three fishery disinfectants—strong chlorine, dibromohydantoin, and sodium hypochlorite—almost completely removed dehydrated erythromycin. Sodium hypochlorite achieved a 97.02% removal rate for the antibiotic.

[0038] exist Figure 1 , 2 In sections 3 and 4, the order of the concentration bars within a given time period is as follows: blank (group), control (group), potassium persulfate, potassium permanganate, dibromohydantoin, strong chlorine, and sodium hypochlorite. These are labeled in the upper right corner of the graphs.

[0039] The removal efficiencies (%) of various concentrations of fishery disinfectants for dehydrated erythromycin in aquaculture water systems are shown in Table 2 below:

[0040] ;

[0041] Figure 3 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 15 mg / L for dehydrated erythromycin in aquaculture water systems according to the present invention.

[0042] Based on the concentration change graph corresponding to Table 2 (at a concentration of 15 mg / L), see below. Figure 3 As shown;

[0043] In aquaculture water systems, at a concentration of 15 mg / L, after 24 hours, strong chlorine, potassium permanganate, and potassium persulfate can almost completely remove dehydrated erythromycin, with a removal efficiency of over 92%.

[0044] Figure 4 The graph shows the changes in the removal efficiency of various fish disinfectants at a concentration of 30 mg / L for dehydrated erythromycin in aquaculture water systems.

[0045] Based on the concentration change graph corresponding to Table 2 (at a concentration of 15 mg / L), see below. Figure 4 As shown;

[0046] like Figure 4 As shown, in the aquaculture water source system, at a concentration of 30 mg / L, after 24 hours, strong chlorine, sodium hypochlorite, potassium permanganate and potassium persulfate can almost completely remove dehydrated erythromycin, with a removal efficiency of over 92.92%, strong chlorine reaching 96% and potassium permanganate reaching 95.85%.

[0047] According to an embodiment of the present invention, the method further includes: collecting the concentration changes of dehydrated erythromycin at 15 mg / L and 30 mg / L in an ultrapure water reaction system, and basing the data on the univariate three-parameter attenuation equation y=a*e -bx The concentration change of fish disinfectant in the process of removing dehydrated erythromycin in an ultrapure water system was fitted using b, and a and c were used to form a degradation kinetic equation for the fish disinfectant on dehydrated erythromycin. The fish disinfectant with the optimal degradation rate was selected from the degradation kinetic equation. Here, b is the degradation rate constant, a and c are the fitting parameters, and y and x are the dependent and independent variables of the fitted equation.

[0048] The degradation kinetic equations formed by the fitting are shown in Table 3. As can be seen from Table 3, 30 mg / L sodium hypochlorite showed the fastest degradation rate for dehydrated erythromycin, with a degradation rate constant of 0.56.

[0049]

[0050] This invention discloses a method for screening fishery disinfectants based on the reaction process analysis of dehydrated erythromycin. Two reaction systems are set up: ultrapure water and aquaculture source water, with the concentration of dehydrated erythromycin in each system set at 5000 ng / L. Calcium oxide is added to both reaction systems and reacted for 8 hours, followed by neutralization with dilute hydrochloric acid to pH 7.2. Potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium persulfate, and strong chlorine are added to different reaction systems for different reaction analyses, with the reaction concentrations of the aforementioned fishery disinfectants set at 15 mg / L and 30 mg / L. The concentration of dehydrated erythromycin after the reaction in both systems is detected by UPLC-MS / MS. The optimal fishery disinfectant corresponding to the optimal degradation rate is screened based on a univariate three-parameter decay equation fitting the concentration change.

[0051] In the embodiments provided in this application, it should be understood that the disclosed methods can be implemented in other ways. The embodiments described above are merely illustrative. For example, the division of units is only a logical functional division, and in actual implementation, there may be other division methods, such as: multiple units or components can be combined, or integrated into another system, or some features can be ignored or not executed. In addition, the coupling, direct coupling, or communication connection between the various components shown or discussed can be through some interfaces, indirect coupling or communication connection of devices or units, and can be electrical, mechanical, or other forms.

[0052] The units described above as separate components may or may not be physically separate. The components shown as units may or may not be physical units. They may be located in one place or distributed across multiple network units. Some or all of the units may be selected to achieve the purpose of this embodiment according to actual needs.

[0053] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for screening fishery disinfectants based on the analysis of the dehydrated erythromycin reaction process, characterized in that, include: Two reaction systems were set up: one for ultrapure water and the other for aquaculture water. In both reaction systems, the concentration of dehydrated erythromycin was set at 5000 ng / L. Calcium oxide was added to both reaction systems to make the concentration of calcium hydroxide in the reaction system reach 0.01%. Add calcium oxide and react for 8 hours, then add dilute hydrochloric acid to neutralize and bring both reaction systems to pH 7.2; Potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium peroxymonosulfate, and strong chlorine were added to different reaction systems for different reaction analyses, and the reaction concentrations of the above-mentioned fish disinfectants were set at 15 mg / L and 30 mg / L. Sodium thiosulfate solution was added immediately after the reaction in the ultrapure water system for 12 hours and the reaction in the aquaculture water source system for 24 hours. The molar concentration of the sodium thiosulfate solution was 20 times that of the corresponding fish disinfectant. The reaction was stopped by adding sodium thiosulfate solution. The concentrations of dehydrated erythromycin in the two systems after the reaction were determined by UPLC-MS / MS. This also includes: In an ultrapure water reaction system, the concentration changes of dehydrated erythromycin, a fish disinfectant, at 15 mg / L and 30 mg / L were collected. The concentration changes were then analyzed based on the univariate three-parameter attenuation equation y=a*e. -bx +c, fit the concentration change of fish disinfectant in the process of removing dehydrated erythromycin in ultrapure water system, and form the degradation kinetic equation of fish disinfectant on dehydrated erythromycin. From the degradation kinetic equation, screen out the fish disinfectant corresponding to the optimal degradation rate.

2. The method for screening fishery disinfectants based on the analysis of the dehydrated erythromycin reaction process according to claim 1, characterized in that, The fish disinfectant includes potassium permanganate, dibromohydantoin, sodium hypochlorite, potassium peroxymonosulfate, and strong chlorine. The two reaction systems include an ultrapure water system and an aquaculture source water system.

Citation Information

Patent Citations

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