Method for mineralizing marine diatom memory-losing shellfish poison by hydroxyl radicals and marine device

Abstract

The invention discloses a method for mineralizing marine diatom memory-losing shellfish poison through hydroxyl free radicals and an offshore device, and relates to marine shellfish poison treatment. The method comprises the following steps: culturing nitzschia in a control enclosure, extracting a nitzschia solution, pumping the nitzschia solution into a main pipeline, generating a high-concentration OH solution by OH solution generation equipment, injecting the high-concentration OH solution into a liquid / liquid mixing and dissolving device, cutting and mixing the OH solution and the nitzschia solution at a throat pipe, crushing the mixture into a huge amount of fine liquid drops, rapidly mineralizing memory-losing shellfish poison by OH at the moment of collapse of the liquid drops, and killing the nitzschia at the same time; one path of OH-killed algae is directly injected into the treatment I enclosure through a main pipeline I, the other path of OH-killed algae is introduced into a flocculation stirring tank through a main pipeline II to form flocs, the flocs are injected into the treatment II enclosure after forming flocs at a water conveying section, and the flocs are pumped into a flocs storage box after settling to the bottom of the enclosure; the sea water in the enclosure of the treatment I and the treatment II is pumped into a detection branch pipeline, and the concentration of memory-losing shellfish poison and the density of algae in the enclosure are monitored on line in real time. The device inhibits the transmission of the memory-losing shellfish poison along the marine food chain, and ensures the marine ecological safety.

Description

Technical Field

[0001] This invention relates to the field of marine shellfish toxin treatment and advanced oxidation applications, and in particular to a method and marine apparatus for mineralizing amnesic shellfish toxins from marine diatoms using hydroxyl radicals. Background Technology

[0002] With the increasing global warming and eutrophication of the ocean, toxic red tides have been breaking out in recent years, causing more than 60,000 poisoning incidents worldwide each year, with a mortality rate as high as 1.5%, seriously affecting the seafood industry, human health, and marine ecological security (Yu Rencheng, Lü Songhui, Qi Yuzao, et al. Research status and prospects of harmful algal blooms in China's coastal waters [J]. Oceanography and Limnology, 2020, 51(4): 768-788). *Pseudo-necklacea* ( Pseudo-nitzschia Sp. (diatoms) can produce a potent neurotoxin known as amnesic shellfish poisoning, which accumulates in filter-feeding mollusks and fish, amplifying its toxicity through the food chain (Liang Yubo, Li Dongmei, Yao Jingyuan, et al. Research progress on algal toxins and toxic microalgae producing species in coastal waters of China [J]. Oceanography and Limnology, 2019, 50(3): 511-524). Once humans consume contaminated seafood, they will experience a series of poisoning symptoms, and even death. In 1987, the first human poisoning incident caused by amnesic shellfish poisoning was reported on Prince Edward Island, Canada, resulting in the deaths of three adults and other victims suffering from long-term neurological problems. Amnesic shellfish poisoning in the Pacific Ocean off the west coast of the United States has led to repeated shutdowns of local fisheries, with each shutdown resulting in losses of up to approximately $10 million (Marcela Jaramillo, Jeffrey A. Joens, Kevin E. O'Shea, et al. Fundamental Studies of the Singlet Oxygen Reactions with the Potent Marine Toxin DomoicAcid [J]. Environmental Science & Technology, 2020, 54(10): 6073-6081). Traditional strategies for dealing with amnesic shellfish poisoning are mainly preventative, and there are currently no effective means to eliminate it. There is an urgent need to develop harmless and low-cost methods for treating amnesic shellfish poisoning.

[0003] Currently, common methods for treating toxic red tides include physical and chemical methods. Chinese patent WO2018107651A1 and Japanese patent JP6859360B2 use modified clay to treat red tides; Japanese patent JPS594489A uses ultrasound to separate plankton from red tides; Chinese patent CN119215874A uses a combination of gel microsphere adsorption and ultrasound to treat *Phaeocystis globosum* red tides; and Chinese patent CN113332971A uses a nano-ZnO / g-C3N4 composite catalyst to inhibit algae growth and remove shellfish toxins. Physical methods are insufficient for effectively killing toxin-producing microalgae and cannot mineralize shellfish toxins in seawater. Conventional chemical agents have difficulty penetrating algal cells, requiring large quantities to effectively kill toxin-producing microalgae, increasing treatment costs. Furthermore, the toxins released from ruptured algal cell membranes and residual chemicals can be harmful to marine life.

[0004] Advanced oxidation technologies can directly mineralize shellfish toxins or enhance their biodegradability through oxidation. Compared to other advanced oxidation technologies, hydroxyl radical (•OH) oxidation technology is more resistant to scavengers present in natural water bodies. It does not require the addition of extra chemical reagents and activators, offering milder reaction conditions, strong oxidizing power, and greater potential for practical application. •OH can rapidly mineralize amnesic shellfish toxins in seawater and directly enter or destroy protein channels on algal cell membranes, causing DNA damage and death, thus reducing the amount of oxidant required to kill *Nyctaginosa*. Flocculation of algal cells killed by •OH can effectively prevent the release of intracellular toxins into the ocean after the cell membranes rupture. •OH oxidation technology has significant research value and application potential in mineralizing amnesic shellfish toxins while simultaneously killing *Nyctaginosa*. Summary of the Invention

[0005] The purpose of this invention is to provide a method for mineralizing amnesic shellfish toxicity from marine diatoms using hydroxyl radicals, and to provide a marine apparatus for this purpose. The method for mineralizing amnesic shellfish toxicity from marine diatoms using hydroxyl radicals provided by this invention leverages the strong oxidizing properties and broad spectrum of •OH to rapidly mineralize the amnesic shellfish toxicity while simultaneously killing the toxin-producing diatoms, thus preventing the accumulation of amnesic shellfish toxicity along the marine food chain and protecting human health and marine ecological safety. The technical solution is as follows: A method for mineralizing amnesic shellfish poisoning from marine diatoms using hydroxyl radicals includes the following steps: (1) In the control enclosure, *Nyctaginus pseudonavicularis* was cultured. After stirring, the algal solution in the enclosure was pumped into the main pipeline. Seawater was pumped into a bag filter to remove impurities. Then, it was introduced into a hydroxyl radical (•OH) solution generation device. O2 was introduced into the active particle generation source. High-frequency and high-voltage excitation was applied to the generation source. O2 was ionized and dissociated into high-energy oxygen active particles in the extremely narrow discharge gap of the generation source. The particles were injected into the gas-liquid jet generator and water jet cavitation generated •OH. The •OH solution was injected into the liquid / liquid mixer through the pipeline. After being cut and mixed with the algal solution at the throat, it was broken into a large number of fine droplets. The droplets and algal cells were evenly distributed in the pipeline. The •OH rapidly mineralized the amnesiac shellfish poison at the moment of droplet collapse and killed *Nyctaginus pseudonavicularis*. Starting from the throat of the liquid / liquid mixer, 6 sampling ports were set in the downstream pipeline. Each sampling port was separated by a hydraulic residence time of 1 second. The mineralization rate of amnesiac shellfish poison at different reaction times was detected. (2) •OH-induced dead algae are introduced into main pipeline I and main pipeline II through switching valves. The dead algae are directly injected into the treatment I enclosure through main pipeline I, and then injected into the flocculation mixing tank through main pipeline II before being introduced into the treatment II enclosure. When the dead algae are injected into the flocculation mixing tank of main pipeline II, the peristaltic pump adds flocculant at the same time. The dead algae and flocculant are mixed to form flocs. The flocs are discharged into the water conveying section of main pipeline II. The peristaltic pump adds olivine coagulant at the same time. The olivine particles adsorb the flocs to form high-density flocs. The flocs are injected into the treatment II enclosure through the pipeline. After the flocs settle to the bottom of the enclosure, they are pumped into the floc storage tank. Three sampling ports are set up in the water conveying sections of main pipeline I and main pipeline II. The hydraulic residence time of each sampling port is 1 second apart to detect the concentration of amnesiac shellfish poisoning during pipeline transportation. (3) Seawater was pumped from each enclosure into the test branch pipeline. Three sampling ports were set up in the water conveyance section of the branch pipeline, with a hydraulic residence time of 1 second between each sampling port. The concentration of amnesia shellfish poison and algal density in the enclosure were sampled and tested. The surface potential of algal cells, pH, dissolved oxygen, salinity, turbidity and chlorophyll a were monitored in real time. After dead algae were injected into the treatment I enclosure and the treatment II enclosure, the changes in the concentration of amnesia shellfish poison in the enclosure were monitored in real time for 5 consecutive days.

[0006] Furthermore, in the control enclosure, treatment I enclosure, and treatment II enclosure, annular floats were installed to keep them afloat on the sea surface. These floats were equipped with agitators and level gauges to observe changes in the liquid level. High-density *Pseudo-Nyctaginosa*, *Pseudo-Nyctaginosa* var. *sharp*, and *Pseudo-Nyctaginosa* var. *pseudo-Nyctaginosa* were added to the control enclosure, along with nitrogen and phosphorus nutrients at a 1:1 ratio to rapidly increase the algal density. The agitators were activated, with the motor driving the propeller blades to rotate at high speed, thoroughly mixing the algal solution. The homogeneous solution was then pumped into a liquid / liquid mixer. The density of *Pseudo-Nyctaginosa* var. *sharp* in the algal solution was (1.0–5.0) × 10⁻¹⁰. 4 The concentration of amnesic shellfish poisoning was 0.1–5.0 nmol / L, and the flow rate was 6.0–50.0 m³ / mL. 3 / h.

[0007] Furthermore, the preparation process of the •OH solution generating device includes: starting the •OH solution generating device, pumping seawater into a bag filter to remove impurities with a diameter greater than 20 μm, and then injecting the seawater into the •OH solution generating device; introducing high-purity oxygen (O2) into the active particle generator, applying a high-frequency excitation of 5–8 kHz and a high-voltage excitation of 5–7 kV to the generator, forming an atmospheric pressure ionization discharge in a narrow discharge gap, which is promoted by alternating micro-jets and micro-glow, and the O2 is ionized and dissociated to generate high-energy oxygen active particles, which are injected into a gas-liquid jet injector and efficiently generate •OH through a gas-liquid two-phase jet and a series of free radical chemical reactions; the total oxidant concentration (TRO) of the high-energy oxygen active particles is 20.0–100.0 mg / L, the gas-liquid flow ratio is 1:3–1:10, and the •OH solution flow rate is 1.0–4.0 m³ / L. 3 / h.

[0008] Furthermore, the liquid / liquid mixer consists of three parts: a constriction section, a throat, and a diffusion section. It can serve as a mixing device for •OH solution and algal solution, and also as a chemical and biological reactor for •OH to mineralize amnesic shellfish poison while killing toxin-producing diatoms. The •OH solution is injected into the liquid / liquid mixer and mixes with the algal solution at the throat. Turbulent shear force breaks the •OH solution into a large number of fine droplets, which are evenly distributed in the pipeline. At the moment the droplets collapse, •OH rapidly mineralizes amnesic shellfish poison while killing pseudo-narrow-eyed algae. The mineralization time is on the order of nanoseconds. All reactions are completed during the transport process in the main pipeline. Several sampling ports are set in the outlet pipeline of the liquid / liquid mixer to detect the mineralization rate of amnesic shellfish poison at different reaction times.

[0009] Furthermore, the •OH droplets and algal solution are uniformly distributed in the pipeline. Upon droplet collapse, •OH attacks negative electrostatic potential and electron-rich sites, gradually oxidizing and mineralizing the amnesic shellfish poisoning through the following three pathways: ① •OH first adds to the terminal carbon-carbon double bond of the branched chain with high unsaturation and high electron density, causing it to break. It then attacks the nitrogen atom on the tetrahydropyrrole ring, undergoing a substitution reaction to open the tetrahydropyrrole ring and generate a straight-chain intermediate. The intermediate is gradually oxidized and decarboxylated by •OH until complete mineralization; ② •OH first adds to the carbon-carbon double bond connected to the tetrahydropyrrole ring... This causes charge transfer and electrical changes in the carbon atoms of the double bond, leading to chain breakage. Subsequently, it attacks the nitrogen atom site of the tetrahydropyrrole ring, resulting in a substitution reaction that opens the tetrahydropyrrole ring and generates a long-chain intermediate. The intermediate is then gradually oxidized and decarboxylated by •OH until it is completely mineralized. ③ •OH attacks the nitrogen atom site of the tetrahydropyrrole ring, resulting in a substitution reaction that opens the ring and generates a long-chain intermediate. It then attacks the carbon-carbon double bond on the intermediate, causing the intermediate to break and generate a small-molecule carboxylic acid. After continuous decarboxylation, it is completely mineralized. The products of •OH oxidation until complete mineralization of amnesiac shellfish poisoning are H2O, CO2, and trace amounts of inorganic salts.

[0010] Furthermore, the •OH droplets and algal solution are evenly distributed in the pipeline. Upon the collapse of the droplets, the •OH penetrates the cell membrane and kills the pseudo-necklace algae through the following two pathways: ① •OH preferentially attacks the cell nuclear DNA, oxidizing the bases of guanine and breaking the phosphodiester bonds of deoxyribose, causing the DNA double helix structure to break and fragment; ② •OH attacks chloroplasts, oxidizing and damaging the proteins in the photosynthetic system reaction center and degrading chlorophyll, causing the algal cells to lose their photosynthetic capacity.

[0011] Furthermore, the •OH-induced dead algae are introduced into main pipeline I and main pipeline II via a switching valve. The dead algae are directly injected into the treatment I enclosure through main pipeline I, and then injected into the flocculation mixing tank through main pipeline II before entering the treatment II enclosure. In the flocculation mixing tank of main pipeline II, a peristaltic pump simultaneously adds flocculant. The shearing and impact forces generated by the high-speed rotation of the impellers in the mixing tank thoroughly mix the dead algae and flocculant to form flocs. After settling to the bottom of the tank, the flocs are discharged into the water conveyance section of main pipeline II. When the Zeta potential of the dead algae reaches -5 to 5 mV, a peristaltic pump adds olivine coagulant to adsorb the flocs and form high-density flocs. These flocs are then injected into the treatment II enclosure through the pipeline to settle. The pump is then started to draw the flocs at the bottom of the treatment II enclosure into a floc storage tank. Several sampling ports are set up in the water conveyance sections of pipeline I and pipeline II to detect the toxin concentration during pipeline transportation. The flocculant is a cationic modified high-molecular-weight starch or modified clay suspension with a concentration of 1.0. The dosage was g / L, and the ratio of the dosage to the dead algae was (0.02~0.10) mg / 10. 3 Cells; the coagulant is a natural olivine suspension with a concentration of 10.0 g / L, and the flow ratio of the coagulant to the flocculant is (1-3):1.

[0012] Furthermore, •OH is also used to mineralize paralytic shellfish poisoning, neurotoxic shellfish poisoning, and diarrhetic shellfish poisoning in seawater. It is also used to kill toxic and harmful red tide algae, including Alexandrium, Gynostemma pentaphyllum, Karenia mikimotoi, Margherita polycyclic, Rhomboidia pseudoacacia, Skeletalis costatus, and Phaeocystis globosa, thus ensuring marine ecological safety.

[0013] This invention also provides a marine device for mineralizing amnesiac shellfish poisoning caused by hydroxyl radicals in marine diatoms, comprising: a •OH solution generation device, a liquid / liquid mixer, a flocculation mixing tank, a flocculant dosing device, a coagulant aid dosing device, a control enclosure, a treatment I enclosure, a treatment II enclosure, a bag filter, a Zeta potential analyzer, a TRO online detector, an algal cell flow cytometer, a multifunctional water quality analyzer, a solenoid valve, a mechanical pump, a peristaltic pump, a water flow meter, a sampling port, a main pipeline, main pipeline I, main pipeline II, a first branch pipeline, a second branch pipeline, a third branch pipeline, a detection branch pipeline, and a floc extraction branch pipeline; The control enclosure has a diameter of 9 m, a depth of 3 m, and a volume of 190 m³. 3 The cylindrical enclosures, for both Treatment I and Treatment II, have a diameter of 6 m, a depth of 3 m, and a volume of 85 m³.3 The enclosure is a cylindrical structure; the enclosure fixing bracket is made of 316 stainless steel and is driven into the seabed at a depth of 0.5 m or less. The enclosure drape bracket is made of 316 stainless steel. The enclosure drape is made of polyethylene film and is heat-welded around the bracket three times. Together with the bracket, it forms a semi-open transparent system that is open at the top, closed on all sides and at the bottom, and impermeable to water. The top bracket of the enclosure has floats around it, so that the entire enclosure is suspended in the water. The enclosure is equipped with a level gauge for real-time observation of the liquid level. The main pipeline inlet is located 0.5 m below the water surface of the control enclosure and is connected to the inlet of the first solenoid valve. The outlet of the first solenoid valve is connected to the inlet of the first mechanical pump. The outlet of the first mechanical pump is connected to the inlet of the first flow meter. A first sampling port and a first algal cell flow cytometer are provided in the middle. The outlet of the first flow meter is connected to the inlet of the liquid / liquid mixer. The suction port of the liquid / liquid mixer is connected to the outlet of the first branch pipeline. The outlets are respectively connected to main pipeline I and main pipeline II. A sampling port and a first TRO online detector are provided in the middle. The inlet of the fourth solenoid valve on the main pipeline I is connected to the outlet of the liquid / liquid mixer on the main pipeline, and the outlet of the fourth solenoid valve is connected to the outlet of the main pipeline I. A sampling port is provided in the middle, and the outlet of pipeline I is located 0.5m below the open plane of the enclosure of treatment I. The inlet of the second solenoid valve on the main pipeline II is connected to the outlet of the liquid / liquid mixer on the main pipeline, and the outlet of the second solenoid valve is connected to the main inlet of the flocculation mixing tank. The flocculant mixing tank is equipped with a level gauge and a stirring paddle for real-time observation of the liquid level in the device and mixing of the liquid in the tank. The side inlet of the flocculation mixing tank is connected to the outlet of the second branch pipeline, and the outlet is connected to the inlet of the third solenoid valve. A first Zeta potential analyzer, the outlet of the third branch pipeline and a sampling port are provided in the middle. The outlet of the third solenoid valve is connected to the outlet of the main pipeline II. The outlet of the main pipeline II is located 0.5 m below the plane of the open enclosure of treatment II. The inlet of the first branch pipeline is located 1.0 m below the sea surface. The inlet of the first branch pipeline is connected to the inlet of the second mechanical pump, and a fifth solenoid valve is installed in the middle. The outlet of the second mechanical pump is connected to the inlet of the bag filter. The bag filter contains multiple layers of filter screens to filter impurities in seawater with a diameter greater than 20 μm. The outlet of the bag filter is connected to the inlet of the •OH solution generating equipment, and the oxygen is connected to the air inlet of the •OH solution generating equipment. The •OH solution generating equipment contains a water flow meter, a high-frequency high-voltage power supply, an active particle generator, and a gas-liquid jet device. The outlet of the •OH solution generating equipment is connected to the suction port of the liquid / liquid mixer, and a second TRO online detector and a sixth solenoid valve are installed in the middle. The inlet of the second branch pipe is located at the bottom of the flocculant dosing device, which is equipped with a level gauge and a stirring paddle to monitor the liquid level in the device in real time and maintain the uniform dispersion of the flocculant suspension. The inlet of the second branch pipe is connected to the inlet of the first peristaltic pump, the outlet of the first peristaltic pump is connected to the inlet of the second flow meter, a seventh solenoid valve is provided in the middle, and the outlet of the second flow meter is connected to the inlet on the side of the flocculation mixing tank. The inlet of the third branch pipeline is located at the bottom of the coagulant dosing device, which is equipped with a level gauge and a stirring paddle to monitor the liquid level in the device in real time and maintain the uniform dispersion of the coagulant suspension. The inlet of the third branch pipeline is connected to the inlet of the second peristaltic pump, the outlet of the second peristaltic pump is connected to the inlet of the third water flow meter, an eighth solenoid valve is provided in the middle, and the outlet of the third water flow meter is connected to the main pipeline. The inlets of the detection branch pipes are respectively placed 0.5 m below the water surface of the control enclosure, the sea surface, treatment I enclosure, and treatment II enclosure. The inlet of the control enclosure is connected to the inlet of the ninth solenoid valve, the inlet of the sea surface is connected to the inlet of the tenth solenoid valve, the inlet of treatment I enclosure is connected to the inlet of the eleventh solenoid valve, and the inlet of treatment I enclosure is connected to the inlet of the twelfth solenoid valve. The outlets of the ninth, tenth, eleventh, and twelfth solenoid valves are connected to the inlet of the third mechanical pump. The outlet of the third mechanical pump is connected to the inlet of the fourth flow meter. The outlet of the fourth flow meter is connected to the inlets of the thirteenth and fourteenth solenoid valves respectively. The outlet of the thirteenth solenoid valve is connected to the outlet of the fourth branch pipe, and a second algal cell flow cytometer, a multifunctional water quality analyzer, and a second Zeta potential analyzer are installed in the middle. The outlet of the fourteenth solenoid valve is connected to the outlet of the fourth branch pipe, and a sampling port is installed in the middle. The inlet of the floc extraction branch pipe is located at the bottom of the treatment II enclosure; the inlet of the treatment II enclosure is connected to the inlet of the fifteenth solenoid valve, the outlet of the fifteenth solenoid valve is connected to the inlet of the fourth mechanical pump, the outlet of the fourth mechanical pump is connected to the floc storage tank, and a fifth flow meter is provided in the middle.

[0014] The technical effects and advantages of the present invention are as follows: 1) • OH is injected into the liquid / liquid mixer from the top and bottom. After being cut and mixed with the algal liquid at the throat, it is broken into a large number of fine droplets and evenly distributed in the pipeline. At the moment the droplets collapse, • OH rapidly mineralizes the amnesiac shellfish poison and kills the toxin-producing diatoms. The algal cell membrane remains intact and there is no release of intracellular solutes. 2) •OH preferentially attacks the carbon-carbon double bonds and nitrogen atoms with high unsaturation and high electron density in the amnestic shellfish toxicant molecule during pipeline transport, and rapidly mineralizes the amnestic shellfish toxicant through three pathways. In addition, •OH can also mineralize paralytic shellfish toxicants, neurotoxic shellfish toxicants, diarrheal shellfish toxicants and other toxins in the nanosecond time range. 3) The device provided by the present invention can curb the accumulation of amnesiac shellfish toxins along the marine food chain, and the disinfection byproducts of the treatment process are safe and have no negative effects on the marine ecological environment. Attached Figure Description

[0015] Figure 1 This is a flowchart of an embodiment of the method and marine apparatus for mineralizing amnesic shellfish poisoning by hydroxyl radicals in marine diatoms according to the present invention.

[0016] Figure 2 This diagram illustrates the principle of how hydroxyl radicals efficiently and rapidly mineralize amnesic shellfish toxins while simultaneously killing toxin-producing diatoms.

[0017] Figure 3 This is the reaction pathway of hydroxyl radical mineralization in amnesic shellfish poisoning.

[0018] In the diagram: 101 - First solenoid valve; 102 - Second solenoid valve; 103 - Third solenoid valve; 104 - Fourth solenoid valve; 105 - Fifth solenoid valve; 106 - Sixth solenoid valve; 107 - Seventh solenoid valve; 108 - Eighth solenoid valve; 109 - Ninth solenoid valve; 110 - Tenth solenoid valve; 111 - Eleventh solenoid valve; 112 - Twelfth solenoid valve; 113 - Thirteenth solenoid valve; 114 - Fourteenth solenoid valve; 115 - Fifteenth solenoid valve; 201 - First mechanical pump; 2 02-Second mechanical pump; 203-Third mechanical pump; 204-Fourth mechanical pump; 301-First sampling port; 302-Second sampling port; 303-Third sampling port; 304-Fourth sampling port; 305-Fifth sampling port; 306-Sixth sampling port; 307-Seventh sampling port; 308-Eighth sampling port; 309-Ninth sampling port; 310-Tenth sampling port; 311-Eleventh sampling port; 312-Twelfth sampling port; 313-Thirteenth sampling port; 401-First algal cell Flow cytometer; 402-Second algal cell flow cytometer; 501-First water flow meter; 502-Second water flow meter; 503-Third water flow meter; 504-Fourth water flow meter; 505-Fifth water flow meter; 6-Liquid / liquid mixer; 701-First TRO online detector; 702-Second TRO online detector; 8-Flocculation mixing tank; 901-First Zeta potential analyzer; 902-Second Zeta potential analyzer; 10-Bag filter; 11-•O H-Solution generation equipment; 1201-Flocculant dosing device; 1202-Coagulant dosing device; 1301-First peristaltic pump; 1302-Second peristaltic pump; 14-Multifunctional water quality analyzer; 15-Floc storage tank; 16-Main pipeline; 17-Main pipeline I; 18-Main pipeline II; 19-First branch pipeline; 20-Second branch pipeline; 21-Third branch pipeline; 22-Detection branch pipeline; 23-Floc extraction branch pipeline; A-Control enclosure; B-Treatment I enclosure; C-Treatment II enclosure. Detailed Implementation

[0019] The following embodiments will further illustrate the present invention with reference to the accompanying drawings. However, the scope of protection of the present invention is not limited to the described embodiments.

[0020] The method and marine apparatus for mineralizing amnesic shellfish poisons from marine diatoms using hydroxyl radicals as described in this invention are illustrated in the appendix. Figure 1 As shown, the system includes solenoid valves 101-115, mechanical pumps 201-204, sampling ports 301-313, algal cell flow cytometers 401-402, water flow meters 501-505, liquid / liquid mixers 6, TRO online detectors 701-702, flocculation mixing tanks 8, Zeta potential analyzers 901-902, bag filters 10, •OH solution generation equipment 11, flocculant dosing devices 1201, coagulant aid dosing devices 1202, peristaltic pumps 1301-1302, multi-functional water quality analyzers 14, floc storage tanks 15, main pipelines 16-18, branch pipelines 19-23, control enclosure A, treatment I enclosure B, and treatment II enclosure C.

[0021] The inlet of the detection branch pipe 22 is placed 0.5 m below the water surface of the control enclosure A. It is equipped with a ninth solenoid valve 109, a third mechanical pump 203, and a fourth water flow meter 504 for extracting and monitoring the algal solution flow rate. The extracted algal solution is discharged in two ways. One way is equipped with a thirteenth solenoid valve 113, a second algal cell flow cytometer 402, a multifunctional water quality analyzer 14, and a second Zeta potential analyzer 902 to monitor algal density, water quality, and algal cell surface potential. The other way is equipped with a fourteenth solenoid valve 114 and eleventh to thirteenth sampling ports 311 to 313 to sample and detect the concentration of amnesiac shellfish poisoning.

[0022] The main inlet of pipeline 16 is located 0.5 m below the water surface of control enclosure A. The inlet section is connected to the inlet of liquid / liquid mixer 6. A first solenoid valve 101 and a first mechanical pump 201 are installed for extracting algal solution. A first sampling port 301, a first algal cell flow cytometer 401, and a first water flow meter 501 are also provided to detect the concentration of amnesiac shellfish poisoning, algal density, and flow rate of the algal solution. The amnesiac shellfish poisoning concentration is 0.1–5.0 nmol / L, and the algal density is (1.0–5.0) × 10⁻¹⁰. 4 cells / mL, flow rate 6.0–50.0 m 3 / h.

[0023] The inlet of the first branch pipeline 19 is located 0.5 m below the sea surface. The inlet section is connected to the inlet of the •OH solution generating device 11. A fifth solenoid valve 105 and a second mechanical pump 202 are installed in the middle for drawing seawater, and a bag filter 10 is installed to filter out impurities with a diameter greater than 20 μm in the seawater. When the •OH solution generating device 11 is started, the water flow meter controls the seawater flow rate entering the gas-liquid jet to be 1.0–4.0 m. 3 / h, high-purity O2 is introduced into the active particle generator, the high-frequency high-voltage power supply is turned on, and high-frequency (5~8kHz) high-voltage (≥5kV) excitation is applied to the generator. O2 is ionized and dissociated to generate high-energy oxygen active particles, which are injected into the gas-liquid jet cavitation water jet to efficiently generate •OH. • The outlet of the OH solution generating device 11 is connected to the water inlet of the liquid / liquid mixer 6 on the main pipeline 16 via the first branch pipeline 19. A sixth solenoid valve 106 and a second TRO online detector 702 for detecting •OH solution TRO are installed in between, with a TRO concentration of 20.0 to 100.0 mg / L.

[0024] •OH solution generated by the •OH solution generating device 11 is injected into the liquid / liquid mixer 6, where it is cut and mixed with the algal solution at the throat. Turbulent shear force breaks the •OH solution into a large number of fine droplets, which are evenly distributed with algal cells in the pipeline. At the moment of droplet collapse, •OH rapidly mineralizes amnesic shellfish poison, with a mineralization time on the order of nanoseconds. It also penetrates the cell membrane, causing DNA chain fragmentation and killing algal cells, resulting in an algal cell mortality rate of ~100%. The algal solution after •OH droplet treatment is transported to the outlet section of the main pipeline 16, where the second to seventh sampling ports 302 to 307 and the first TRO online detector 701 are installed to detect the concentration of amnesic shellfish poison and TRO in the algal solution after flowing out of the liquid / liquid mixer 6. The outlet section of the main pipeline 16 is connected to the inlet sections of main pipeline I 17 and main pipeline II 18 via a three-way valve. The main pipeline I 17 is equipped with a second solenoid valve 102 and the eighth to tenth sampling ports 308 to 310 to detect the concentration of amnesiac shellfish poisoning. Dead algae are directly injected into the treatment I enclosure B 0.5 m below the open plane through the outlet. A third solenoid valve 103 is installed between the water inlet section of main pipeline II 18 and the flocculation mixing tank 8. Dead algae are injected into the flocculation mixing tank 8, and flocculant is added simultaneously. The shearing force and impact force generated by the high-speed rotation of the blades in the mixing tank make the dead algae and flocculant fully mixed. The flocculant adsorbs algal cells through charge neutralization, and the algal cells quickly destabilize and clump together to form flocs. The flocculant dosing device 1201 is connected to the flocculation mixing tank 8 installed on the main pipeline II 18 via a second branch pipeline 20. The flocculant dosing device 1201 is equipped with a stirring paddle to uniformly disperse the flocculant in the suspension. A level gauge is installed on the device wall to observe level changes. The second branch pipeline 20 is equipped with a seventh solenoid valve 107 for extracting flocculant and a first peristaltic pump 1301, and a second water flow meter 502 for monitoring the flocculant flow rate. The flocculant is a cationic modified high-molecular-weight starch or modified clay suspension with a concentration of 1.0 g / L and a dosage ratio to dead algae of (0.02–0.1) mg / L. 3 cells.

[0025] After the flocs settle to the bottom of the tank, they are discharged into the water conveyance section of pipeline II 18. The first Zeta potential analyzer 901 is installed on the water conveyance section to detect the surface charge of the flocs and to detect the concentration of amnesiac shellfish poisoning through the eighth to tenth sampling ports 308 to 310. When the Zeta potential reaches -5 to 5 mV, natural mineral coagulant is added into the water conveyance section at the same time. The mineral particles with a particle size of 20 to 50 μm adsorb the flocs to form high-density flocs. The coagulant dosing device 1202 is connected to the main pipeline II 18 water conveyance section via the third branch pipeline 21; the coagulant dosing device 1202 is equipped with a stirring paddle to evenly disperse the coagulant in the suspension, and a level gauge is installed on the device wall to observe the level change; the third branch pipeline 21 is equipped with an eighth solenoid valve 108 for extracting the coagulant and a second peristaltic pump 1302, and a third water flow meter 503 for monitoring the flow rate of the coagulant; the coagulant is a natural olivine suspension with a concentration of 10.0 g / L, and the flow ratio of the coagulant to the flocculant is (1~3):1.

[0026] The flocs are injected into the treatment II enclosure C below the open plane of the main pipeline II 18 and settled below 0.5m. A fourth solenoid valve 104 is installed in the middle. After the flocs settle to the bottom of the treatment II enclosure C, they are sucked into the floc storage box 15 through the floc extraction branch pipeline 23. The inlet of the floc extraction branch pipe 23 is located at the bottom of the treatment II enclosure C. The inlet section is connected to the floc storage tank 15 for collecting flocs at the bottom of the treatment II enclosure C. A fifteenth solenoid valve 115 and a fourth mechanical pump 204 for extracting flocs are installed in the middle, and a fifth water flow meter 505 for monitoring seawater flow is installed.

[0027] After dead algae were injected into treatment I enclosure B and treatment II enclosure C, the third mechanical pump 203 was turned on every 12 hours, and the eleventh solenoid valve 111 and the twelfth solenoid valve 112 were switched to extract seawater from the two enclosures respectively. The changes in live algae density, water quality and toxin concentration were monitored by the second algal cell flow cytometer 402, the multifunctional water quality analyzer 14 and the eleventh to thirteenth sampling ports 311 to 313 on the detection branch pipe 22 for 5 consecutive days. Before each test, the tenth solenoid valve 110 and the third mechanical pump 203 were turned on to extract seawater to clean the pipeline. The inlet of the detection branch pipe 22 was placed 0.5 m below the water surface of the control enclosure A, the ocean, treatment I enclosure B and treatment II enclosure C respectively.

[0028] Based on the above-mentioned method and marine apparatus for mineralizing amnesiac shellfish toxicity from marine diatoms using hydroxyl radicals, the following are specific examples of mineralizing amnesiac shellfish toxicity: Example 1 The enclosure experiment was conducted in the waters of Dongjiang Port, Tianjin, with water temperatures ranging from 29 to 31°C. High-density *Pseudo-Nyctaginea*, *Pseudo-Nyctaginea* var. *spinosa*, and *Pseudo-Nyctaginea* var. *weak* were added to control enclosure A, with f / 2 culture medium replenished periodically. The ninth solenoid valve 109 was opened, the third mechanical pump 203 was activated, the thirteenth solenoid valve 113 was opened, and the fourteenth solenoid valve 114 was closed. The algal solution was pumped from the inlet of detection branch pipe 22 into the water delivery section of detection branch pipe 22. The algal density and water quality were monitored using a second algal cell flow cytometer 402 and a multifunctional water quality analyzer 14. The thirteenth solenoid valve 113 was closed, and the fourteenth solenoid valve 114 was opened. The algal solution was pumped from the inlet of detection branch pipe 22 into another water delivery section of detection branch pipe 22. The concentration of amnesiac shellfish poisoning in the algal solution was detected through sampling ports 311-313. The results showed that the algal density in control enclosure A reached 3.0 × 10⁻⁶. 4 The concentration of amnesic shellfish poisoning was 2.84 nmol / L.

[0029] Turn on the stirrer in control enclosure A and stir the algal solution in the enclosure thoroughly. Turn on the first solenoid valve 101 and the first mechanical pump 201 to pump the homogenized algal solution into the main pipeline 16. Take a sample at the first sampling port 301 to detect the concentration of amnesiac shellfish poisoning. Monitor the algal density using the first algal cell flow cytometer 401. The first water flow meter 501 reads the algal solution flow rate as 9.0 m³ / s. 3 / h, the algae solution is introduced into the inlet of liquid / liquid mixer 6.

[0030] Open the fifth solenoid valve 105 and the sixth solenoid valve 106, and turn on the second mechanical pump 201 to pump seawater from the first branch pipe 19 into the •OH solution generating device 11 to produce a high-concentration •OH solution. A bag filter 10 is installed to filter out impurities larger than 20 μm in diameter from the seawater. The TRO of the •OH solution in the pipeline is detected by the second TRO online detector 702; the •OH solution flow rate is 1.0 m³ / s. 3 / h, the TRO concentration was 20.6 mg / L.

[0031] • The OH solution is injected into the liquid / liquid mixer 6 at both ends and mixed with the algal solution at a flow ratio of 1:9 at the throat. During the transport of the solution in the main pipeline 16, the amnesic shellfish poison is mineralized, and the toxin-producing diatoms are killed at the same time. The concentration of amnesic shellfish poison is measured through the second to seventh sampling ports 302 to 307. The concentration of amnesic shellfish poison is ~0 nmol / L. The TRO after the reaction is measured to be 0.08 mg / L by the first TRO online detector 701.

[0032] Open the second solenoid valve 102 and close the third solenoid valve 103. The dead algae are directly injected into the treatment enclosure B 0.5 m below the open plane through the main pipeline I 17. Samples are taken at the eighth to tenth sampling ports 308 to 310 set in the water conveyance section of the main pipeline I 17 to detect the concentration of amnesiac shellfish poisoning ~0 nmol / L.

[0033] Close the second solenoid valve 102 and open the third solenoid valve 103. Dead algae are injected into the flocculation mixing tank 8 via the main pipeline II 18. Open the seventh solenoid valve 107 and start the first peristaltic pump 1301. Modified starch flocculant is pumped into the flocculation mixing tank 8 from the flocculant dosing device 1201 through the second branch pipeline. The second water flow meter 502 reads the flocculant flow rate as 0.5 m³ / s. 3 The flocculant concentration is 1.0 g / L. After the dead algae and flocculant are thoroughly mixed, flocs are formed. The flocs settle to the bottom of the tank and flow into the main pipeline II, section 18. The surface charge of the flocs is detected as -3.5 mV by the first Zeta potential analyzer 901. The eighth solenoid valve 108 is opened, and the second peristaltic pump 1302 is turned on. The coagulant aid is pumped from the coagulant aid dosing device 1202 into the main pipeline II, section 18 through the third branch pipeline. The second flow meter 502 reads the coagulant aid flow rate as 1.0 m³ / h. 3 / h, the coagulant concentration is 10.0 g / L, and olivine particles with a particle size of 20~50μm adsorb flocs to form high-density flocs; the fourth solenoid valve 104 is opened, and the flocs are injected into the treatment II enclosure C 0.5 m below the plane of the main pipeline II 18. The eighth to tenth sampling ports 308~310 set in the water conveyance section of the main pipeline II 18 are used to sample and detect the concentration of amnesia shellfish poisoning ~0 nmol / L.

[0034] After all the flocs have settled to the bottom of the treatment II enclosure C, open the fifteenth solenoid valve 115 and start the fourth mechanical pump 204. Pump the flocs from the bottom of the treatment II enclosure C into the floc storage tank 15 through the floc extraction branch pipe 23. The fifth water flow meter 505 reads a flow rate of 0.1 m³ / s. 3 / h.

[0035] After the flocs were extracted, the third mechanical pump 203 was turned on every 12 hours, and the eleventh solenoid valve 111 and the twelfth solenoid valve 112 were switched to extract seawater from the treatment I enclosure B and the treatment II enclosure C, respectively. The changes in live algae density, water quality and toxin concentration were monitored by the second algal cell flow cytometer 402, the multifunctional water quality analyzer 14 and the eleventh to thirteenth sampling ports 311 to 313 on the detection branch pipe 22. The monitoring was carried out for 5 consecutive days. The results showed that the live algae density in the enclosure was ~0 cells / mL, the toxin concentration in treatment I enclosure B was 2.43 nmol / L, and the toxin concentration in treatment II enclosure C was ~0 nmol / L. Before each test, the tenth solenoid valve 110 and the third mechanical pump 203 were turned on to extract seawater to clean the pipeline. The inlet of the detection branch pipe 22 was placed 0.5 m below the water surface of the control enclosure A, the ocean, treatment I enclosure B and treatment II enclosure C, respectively.

[0036] Example 2: The enclosure experiment was conducted in the waters off the Tianjin National Maritime Museum, with a water temperature of 27–30℃. High-density *Pseudo-Nyctaginosa*, *Pseudo-Spiritiformis*, and *Pseudo-Nyctaginosa* species were added to control enclosure A, with f / 2 culture medium replenished periodically. The ninth solenoid valve 109 was opened, the third mechanical pump 203 was activated, the thirteenth solenoid valve 113 was opened, and the fourteenth solenoid valve 114 was closed. The algal solution was pumped from the inlet of detection branch pipe 22 into the water delivery section of detection branch pipe 22. The algal density and water quality were monitored using a second algal cell flow cytometer 402 and a multifunctional water quality analyzer 14. The thirteenth solenoid valve 113 was closed, and the fourteenth solenoid valve 114 was opened. The algal solution was pumped from the inlet of detection branch pipe 22 into another water delivery section of detection branch pipe 22. The concentration of amnesiac shellfish poisoning in the algal solution was detected through sampling ports 311–313. The results showed that the algal density in control enclosure A reached 2.0 × 10⁻⁶. 4 The concentration of amnesic shellfish poisoning was 1.97 nmol / L.

[0037] Turn on the stirrer in control enclosure A and stir the algal solution in the enclosure thoroughly. Turn on the first solenoid valve 101 and the first mechanical pump 201 to pump the homogenized algal solution into the main pipeline 16. Take a sample at the first sampling port 301 to detect the concentration of amnesiac shellfish poisoning. Monitor the algal density using the first algal cell flow cytometer 401. The first water flow meter 501 reads the algal solution flow rate as 18.0 m³ / s. 3 / h, the algae solution is introduced into the inlet of liquid / liquid mixer 6.

[0038] Open the fifth solenoid valve 105 and the sixth solenoid valve 106, and start the second mechanical pump 201 to pump seawater from the first branch pipe 19 into the •OH solution generating device 11 to produce a high-concentration •OH solution. A bag filter 10 is installed to filter out impurities larger than 20 μm in diameter from the seawater. The TRO of the •OH solution in the pipeline is detected by the second TRO online detector 702; the •OH solution flow rate is 2.0 m³ / s. 3 / h, TRO concentration is 21.5 mg / L.

[0039] • The OH solution is injected into the liquid / liquid mixer 6 at both ends and mixed with the algal solution at a flow ratio of 1:9 at the throat. During the transport of the solution in the main pipeline 16, the amnesic shellfish poison is mineralized, and the toxin-producing diatoms are killed at the same time. The concentration of amnesic shellfish poison is measured through the second to seventh sampling ports 302 to 307. The concentration of amnesic shellfish poison is ~0 nmol / L. The TRO after the reaction is measured to be 0.07 mg / L by the first TRO online detector 701.

[0040] Open the second solenoid valve 102 and close the third solenoid valve 103. The dead algae are directly injected into the treatment enclosure B 0.5 m below the open plane through the main pipeline I 17. Samples are taken at the eighth to tenth sampling ports 308 to 310 set in the water conveyance section of the main pipeline I 17 to detect the concentration of amnesiac shellfish poisoning ~0 nmol / L.

[0041] Close the second solenoid valve 102 and open the third solenoid valve 103. Dead algae are injected into the flocculation mixing tank 8 via the main pipeline II 18. Open the seventh solenoid valve 107 and start the first peristaltic pump 1301. Modified clay flocculant is pumped into the flocculation mixing tank 8 from the flocculant dosing device 1201 through the second branch pipeline. The second water flow meter 502 reads the flocculant flow rate as 1.0 m³ / s. 3 The flocculant concentration is 1.0 g / L. After the dead algae and flocculant are thoroughly mixed, flocs are formed. The flocs settle to the bottom of the tank and flow into the main pipeline II, section 18. The surface charge of the flocs is detected as -3.8 mV by the first Zeta potential analyzer 901. The eighth solenoid valve 108 is opened, and the second peristaltic pump 1302 is turned on. The coagulant aid is pumped from the coagulant aid dosing device 1202 into the main pipeline II, section 18 through the third branch pipeline. The second flow meter 502 reads the coagulant aid flow rate as 2.0 m³ / h. 3 / h, the coagulant concentration is 10.0 g / L, and olivine particles with a particle size of 20~50μm adsorb flocs to form high-density flocs; the fourth solenoid valve 104 is opened, and the flocs are injected into the treatment II enclosure C 0.5 m below the plane of the main pipeline II 18. The eighth to tenth sampling ports 308~310 set in the water conveyance section of the main pipeline II 18 are used to sample and detect the concentration of amnesia shellfish poisoning ~0 nmol / L.

[0042] After all the flocs have settled to the bottom of the treatment II enclosure C, open the fifteenth solenoid valve 115 and start the fourth mechanical pump 204. Pump the flocs from the bottom of the treatment II enclosure C into the floc storage tank 15 through the floc extraction branch pipe 23. The fifth water flow meter 505 reads a flow rate of 0.1 m³ / s. 3 / h.

[0043] After the flocs were extracted, the third mechanical pump 203 was turned on every 12 hours, and the eleventh solenoid valve 111 and the twelfth solenoid valve 112 were switched to extract seawater from the treatment I enclosure B and the treatment II enclosure C, respectively. The changes in live algae density, water quality and toxin concentration were monitored by the second algal cell flow cytometer 402, the multifunctional water quality analyzer 14 and the eleventh to thirteenth sampling ports 311 to 313 on the detection branch pipe 22. The monitoring was carried out for 5 consecutive days. The results showed that the live algae density in the enclosure was ~0 cells / mL, the toxin concentration in treatment I enclosure B was 2.43 nmol / L, and the toxin concentration in treatment II enclosure C was ~0 nmol / L. Before each test, the tenth solenoid valve 110 and the third mechanical pump 203 were turned on to extract seawater to clean the pipeline. The inlet of the detection branch pipe 22 was placed 0.5 m below the water surface of the control enclosure A, the ocean, treatment I enclosure B and treatment II enclosure C, respectively.

Claims

1. A method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms, characterized in that... Includes the following steps: (1) In the control enclosure, *Nyctaginus pseudonavicularis* was cultured. After stirring, the algal solution in the enclosure was pumped into the main pipeline. Seawater was pumped into a bag filter to remove impurities and then passed into the •OH solution generation device. O2 was passed into the active particle generator. High-frequency and high-voltage excitation was applied to the generator. O2 was ionized and dissociated into high-energy oxygen active particles in the extremely narrow discharge gap of the generator. The particles were injected into the gas-liquid jet generator and water jet cavitation generated hydroxyl radicals •OH. The •OH solution was injected into the liquid / liquid mixer through the pipeline. After being cut and mixed with the algal solution at the throat, it was broken into a large number of fine droplets. The droplets and algal cells were evenly distributed in the pipeline. The •OH rapidly mineralized the amnesiac shellfish poison at the moment of droplet collapse and killed *Nyctaginus pseudonavicularis*. Starting from the throat of the liquid / liquid mixer, 6 sampling ports were set in the downstream pipeline. Each sampling port was separated by a hydraulic residence time of 1 second. The mineralization rate of amnesiac shellfish poison at different reaction times was detected. (2) •OH-induced dead algae are introduced into main pipeline I and main pipeline II through switching valves. The dead algae are directly injected into the treatment I enclosure through main pipeline I, and then injected into the flocculation mixing tank through main pipeline II before being introduced into the treatment II enclosure. When the dead algae are injected into the flocculation mixing tank of main pipeline II, the peristaltic pump adds flocculant at the same time. The dead algae and flocculant are mixed to form flocs. The flocs are discharged into the water conveying section of main pipeline II. The peristaltic pump adds olivine coagulant at the same time. The olivine particles adsorb the flocs to form high-density flocs. The flocs are injected into the treatment II enclosure through the pipeline. After the flocs settle to the bottom of the enclosure, they are pumped into the floc storage tank. Three sampling ports are set up in the water conveying sections of main pipeline I and main pipeline II. The hydraulic residence time of each sampling port is 1 second apart to detect the concentration of amnesiac shellfish poisoning during pipeline transportation. (3) Seawater was pumped from each enclosure into the test branch pipeline. Three sampling ports were set up in the water conveyance section of the branch pipeline, with a hydraulic residence time of 1 second between each sampling port. The concentration of amnesia shellfish poison and algal density in the enclosure were sampled and tested. The surface potential of algal cells, as well as pH, dissolved oxygen, salinity, turbidity, and chlorophyll a were monitored in real time. After dead algae were injected into the treatment I enclosure and the treatment II enclosure, the changes in the concentration of amnesia shellfish poison in the enclosure were monitored in real time for 5 consecutive days.

2. The method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms as described in claim 1, characterized in that, All three enclosures—control enclosure, treatment I enclosure, and treatment II enclosure—were equipped with annular floats that kept them afloat on the sea surface. Each enclosure contained a stirrer and a level gauge for monitoring surface changes. The control enclosure was supplemented with high-density *Pseudo-Nyctaginosa*, *Pseudo-Nyctaginosa* var. *sharp*, and *Pseudo-Nyctaginosa* var. *pseudo-Nyctaginosa*, along with nitrogen and phosphorus nutrients at a 1:1 ratio to rapidly increase algal density. The stirrer was activated, with the motor driving the propeller blades to rotate at high speed, thoroughly mixing the algal solution. The homogeneous solution was then pumped into a liquid / liquid mixer. The density of *Pseudo-Nyctaginosa* in the solution was (1.0–5.0) × 10⁻¹⁰. 4 The concentration of amnesic shellfish poisoning was 0.1–5.0 nmol / L, and the flow rate was 6.0–50.0 m³ / mL. 3 / h.

3. The method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms as described in claim 1, characterized in that, The preparation process of the •OH solution generating device includes: starting the •OH solution generating device, pumping seawater into a bag filter to remove impurities with a diameter greater than 20 μm, and then injecting the seawater into the •OH solution generating device; introducing high-purity oxygen (O2) into the active particle generator, applying a high-frequency excitation of 5–8 kHz and a high-voltage excitation of 5–7 kV to the generator, forming an atmospheric pressure ionization discharge in a narrow discharge gap, which is promoted by alternating microjets and microglow. O2 is ionized and dissociated to generate high-energy oxygen active particles, which are then injected into a gas-liquid jet injector for efficient cavitation generation of •OH; the total oxidant concentration (TRO) of the high-energy oxygen active particles is 20.0–100.0 mg / L, and the •OH solution flow rate is 1.0–4.0 m³ / L. 3 / h.

4. The method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms as described in claim 1, characterized in that, The •OH solution is injected into the liquid / liquid mixer, where it is cut and mixed with the algal solution at the throat. Turbulent shear force breaks the •OH solution into a large number of fine droplets, which are evenly distributed in the pipeline. At the moment the droplets collapse, the •OH rapidly mineralizes the amnesiac shellfish poison and kills the pseudo-necklea. The mineralization time is on the order of nanoseconds. All reactions are completed during the transport process in the main pipeline. Several sampling ports are set in the outlet pipeline of the liquid / liquid mixer to detect the mineralization rate of the amnesiac shellfish poison at different reaction times.

5. The method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms as described in claim 1, characterized in that, The •OH droplets and algal solution are uniformly distributed in the pipeline. Upon droplet collapse, •OH attacks negative electrostatic potential and electron-rich sites, gradually oxidizing and mineralizing the amnesic shellfish poison through the following three pathways: ① •OH first adds to the carbon-carbon double bond at the end of the branch, causing it to break. It then attacks the nitrogen atom of the heterocyclic ring, causing a substitution reaction that opens the ring and generates a straight-chain intermediate. The intermediate is gradually oxidized and decarboxylated by •OH until it is completely mineralized; ② •OH first adds to the carbon-carbon double bond of the heterocyclic ring, causing a change in charge and breaking the branch. It then attacks the nitrogen atom of the heterocyclic ring, causing a substitution reaction that opens the ring and generates a long-chain intermediate. The intermediate is gradually oxidized and decarboxylated by •OH until it is completely mineralized; ③ •OH attacks the nitrogen atom of the heterocyclic ring, causing a substitution reaction that opens the ring and generates a long-chain intermediate. It then attacks the carbon-carbon double bond, causing the intermediate to break and generate a small-molecule carboxylic acid, which is then completely mineralized after decarboxylation. The mineralization products are H2O, CO2, and trace inorganic salts.

6. The method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms as described in claim 1, characterized in that, The •OH droplets and algal solution are evenly distributed in the pipeline. Upon the collapse of the droplets, the •OH penetrates the cell membrane and kills the pseudo-neck algae through the following two pathways: ① •OH preferentially attacks the cell nuclear DNA, oxidizing the bases of guanine and breaking the phosphodiester bonds of deoxyribose, causing the DNA double helix structure to break and fragment; ② •OH attacks chloroplasts, oxidizing and damaging the proteins in the photosynthetic system reaction center, degrading chlorophyll, and inhibiting photosynthetic activity.

7. The method for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms as described in claim 1, characterized in that, The •OH-killed algae are introduced into main pipeline I and main pipeline II through a switching valve. The dead algae are directly injected into the enclosure of treatment I through main pipeline I, and then injected into the flocculation mixing tank through main pipeline II before entering the enclosure of treatment II. In the flocculation mixing tank of main pipeline II, flocculant is simultaneously added by a peristaltic pump. The shearing and impact forces generated by the high-speed rotation of the impellers in the mixing tank thoroughly mix the dead algae and flocculant to form flocs. After settling to the bottom of the tank, the flocs are discharged into the water conveyance section of main pipeline II. The Zeta potential of the dead algae reaches -5 to 5. At a certain mV, a peristaltic pump adds olivine coagulant to adsorb flocs and form high-density flocs. These flocs are then injected into the treatment II enclosure via pipeline for sedimentation. The pump is then started to draw the flocs at the bottom of the treatment II enclosure into a floc storage tank. Several sampling ports are set up in the water conveyance sections of pipelines I and II to detect the toxin concentration during pipeline transportation. The flocculant is a cationic modified high-molecular-weight starch or modified clay suspension with a concentration of 1.0 g / L and a dosage ratio to dead algae of (0.02–0.10) mg / 10. 3 Cells; the coagulant is a natural olivine suspension with a concentration of 10.0 g / L, and the flow ratio of the coagulant to the flocculant is (1-3):

1.

8. The method for mineralizing amnesic shellfish poisoning of marine diatoms using hydroxyl radicals as described in claim 1, characterized in that, •OH is also used to mineralize paralytic, neurotoxic, and diarrhetic shellfish poisoning in seawater, and to kill toxic and harmful red tide algae, including Alexandrium, Gynostemma pentaphyllum, Karenia mikimotoi, Margherita polycyclic, Rhomboidia pseudoacacia, Skeletalis costatus, and Phaeocystis globosa, thus ensuring marine ecological safety.

9. A marine device for mineralizing amnesic shellfish poisoning caused by hydroxyl radicals in marine diatoms, characterized in that... It is equipped with •OH solution generation equipment, liquid / liquid mixer, flocculation mixing tank, flocculant dosing device, coagulant aid dosing device, control enclosure, treatment I enclosure, treatment II enclosure, bag filter, Zeta potential analyzer, TRO online detector, algal cell flow cytometer, multi-functional water quality analyzer, solenoid valve, mechanical pump, peristaltic pump, water flow meter, sampling port, main pipeline, main pipeline I, main pipeline II, first branch pipeline, second branch pipeline, third branch pipeline, detection branch pipeline and floc extraction branch pipeline; The control enclosure has a diameter of 9 m, a depth of 3 m, and a volume of 190 m³. 3 The cylindrical enclosures, for both Treatment I and Treatment II, have a diameter of 6 m, a depth of 3 m, and a volume of 85 m³. 3 The enclosure is a cylindrical structure; the enclosure fixing bracket is made of 316 stainless steel and is driven into the seabed at a depth of 0.5 m or less. The enclosure drape bracket is made of 316 stainless steel. The enclosure drape is made of polyethylene film and is heat-welded around the bracket three times. Together with the bracket, it forms a semi-open transparent system that is open at the top, closed on all sides and at the bottom, and impermeable to water. The top bracket of the enclosure has floats around it, so that the entire enclosure is suspended in the water. The enclosure is equipped with a level gauge for real-time observation of the liquid level. The main pipeline inlet is located 0.5 m below the water surface of the control enclosure and is connected to the inlet of the first solenoid valve. The outlet of the first solenoid valve is connected to the inlet of the first mechanical pump. The outlet of the first mechanical pump is connected to the inlet of the first flow meter. A first sampling port and a first algal cell flow cytometer are provided in the middle. The outlet of the first flow meter is connected to the inlet of the liquid / liquid mixer. The suction port of the liquid / liquid mixer is connected to the outlet of the first branch pipeline. The outlets are respectively connected to main pipeline I and main pipeline II. A sampling port and a first TRO online detector are provided in the middle. The inlet of the fourth solenoid valve on the main pipeline I is connected to the outlet of the liquid / liquid mixer on the main pipeline, and the outlet of the fourth solenoid valve is connected to the outlet of the main pipeline I. A sampling port is provided in the middle, and the outlet of pipeline I is located 0.5 m below the open plane of the enclosure of treatment I. The inlet of the second solenoid valve on the main pipeline II is connected to the outlet of the liquid / liquid mixer on the main pipeline, and the outlet of the second solenoid valve is connected to the main inlet of the flocculation mixing tank. The flocculant mixing tank is equipped with a level gauge and a stirring paddle for real-time observation of the liquid level in the device and mixing of the liquid in the tank. The side inlet of the flocculation mixing tank is connected to the outlet of the second branch pipeline, and the outlet is connected to the inlet of the third solenoid valve. A first Zeta potential analyzer, the outlet of the third branch pipeline and a sampling port are provided in the middle. The outlet of the third solenoid valve is connected to the outlet of the main pipeline II. The outlet of the main pipeline II is located 0.5 m below the plane of the open enclosure of treatment II. The inlet of the first branch pipeline is located 1.0 m below the sea surface. The inlet of the first branch pipeline is connected to the inlet of the second mechanical pump, and a fifth solenoid valve is installed in the middle. The outlet of the second mechanical pump is connected to the inlet of the bag filter. The bag filter contains multiple layers of filter screens to filter impurities in seawater with a diameter greater than 20 μm. The outlet of the bag filter is connected to the inlet of the •OH solution generating equipment, and the oxygen is connected to the air inlet of the •OH solution generating equipment. The •OH solution generating equipment contains a water flow meter, a high-frequency high-voltage power supply, an active particle generator, and a gas-liquid jet device. The outlet of the •OH solution generating equipment is connected to the suction port of the liquid / liquid mixer, and a second TRO online detector and a sixth solenoid valve are installed in the middle. The inlet of the second branch pipe is located at the bottom of the flocculant dosing device, which is equipped with a level gauge and a stirring paddle to monitor the liquid level in the device in real time and maintain the uniform dispersion of the flocculant suspension. The inlet of the second branch pipe is connected to the inlet of the first peristaltic pump, the outlet of the first peristaltic pump is connected to the inlet of the second flow meter, a seventh solenoid valve is provided in the middle, and the outlet of the second flow meter is connected to the inlet on the side of the flocculation mixing tank. The inlet of the third branch pipeline is located at the bottom of the coagulant dosing device, which is equipped with a level gauge and a stirring paddle to monitor the liquid level in the device in real time and maintain the uniform dispersion of the coagulant suspension. The inlet of the third branch pipeline is connected to the inlet of the second peristaltic pump, the outlet of the second peristaltic pump is connected to the inlet of the third water flow meter, an eighth solenoid valve is provided in the middle, and the outlet of the third water flow meter is connected to the main pipeline. The inlets of the detection branch pipes are respectively placed 0.5m below the water surface of the control enclosure, the sea surface, treatment I enclosure, and treatment II enclosure. The inlet of the control enclosure is connected to the inlet of the ninth solenoid valve, the inlet of the sea surface is connected to the inlet of the tenth solenoid valve, the inlet of treatment I enclosure is connected to the inlet of the eleventh solenoid valve, and the inlet of treatment I enclosure is connected to the inlet of the twelfth solenoid valve. The outlets of the ninth, tenth, eleventh, and twelfth solenoid valves are connected to the inlet of the third mechanical pump. The outlet of the third mechanical pump is connected to the inlet of the fourth flow meter. The outlet of the fourth flow meter is connected to the inlets of the thirteenth and fourteenth solenoid valves respectively. The outlet of the thirteenth solenoid valve is connected to the outlet of the fourth branch pipe, and a second algal cell flow cytometer, a multifunctional water quality analyzer, and a second Zeta potential analyzer are installed in the middle. The outlet of the fourteenth solenoid valve is connected to the outlet of the fourth branch pipe, and a sampling port is installed in the middle. The inlet of the floc extraction branch pipe is located at the bottom of the treatment II enclosure; the inlet of the treatment II enclosure is connected to the inlet of the fifteenth solenoid valve, the outlet of the fifteenth solenoid valve is connected to the inlet of the fourth mechanical pump, the outlet of the fourth mechanical pump is connected to the floc storage tank, and a fifth flow meter is provided in the middle.

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