Method and apparatus for hydroxyl radical mineralization of marine dinoflagellate paralytic shellfish toxins

Abstract

This invention discloses a method and apparatus for mineralizing paralyzing shellfish poisoning by hydroxyl radicals, relating to the field of marine ecological disaster prevention and control. The method involves: oxygen entering an oxygen plasma generator, being ionized and dissociated to generate oxygen-active particle gas, which is injected into a gas-liquid mixer to efficiently generate a •OH solution, and then injected into a liquid-liquid mixer where it is broken down into a large number of tiny droplets; eight sampling ports are evenly spaced after the liquid-liquid mixer to measure the TRO gradient after mixing and dilution; the large number of •OH droplets rapidly mineralize the paralyzing shellfish poisoning while simultaneously killing the toxin-producing dinoflagellates; detection is performed at the eight sampling ports to establish efficacy-time models for •OH mineralization of shellfish poisoning and •OH mineralization of algae, and to determine the threshold values; the acute and chronic toxicity of the shellfish poisoning control group C2 and the treatment group C3 are evaluated, as are the acute and chronic toxicity of the dinoflagellate control group D2 and the treatment group D3; this invention provides a complete solution from source control to end-of-life assessment.

Description

Technical Field

[0001] This invention relates to the fields of plasma chemistry, advanced oxidation, and marine toxin pollution control, and particularly to a method and apparatus for mineralizing marine paralytic shellfish poisoning with hydroxyl radicals. Background Technology

[0002] Eutrophication in nearshore waters is increasing daily, leading to frequent harmful algal blooms globally in recent years and a growing threat from marine algal toxins. These toxins accumulate rapidly through filter-feeding shellfish consuming marine microalgae, and, coupled with human fishing and consumption, endanger human health, posing a significant risk and challenge to public health and safety.

[0003] Paralytic shellfish toxins (PSTs) are among the most widespread, toxic, and dangerous water-soluble marine toxins globally. They are primarily produced by marine microalgae such as Alexandrium, dinoflagellates, and Gymnodinium chaineri, as well as some freshwater cyanobacteria. PSTs have a tricyclic tetrahydropurine structure, and the guanidino group on the ring can bind to sodium ion channels on the cell membrane of nerve cells, blocking normal biochemical signals and thus inhibiting the transmission of action potentials in the nervous system, paralyzing the nervous system, and in severe cases, even endangering life. Their toxicity is more than 20 times that of cyanide, and there is no known antidote. PSTs are stable in neutral to weakly acidic environments and have extremely strong heat resistance, making them difficult to eliminate through conventional cooking methods.

[0005] Conventional water treatment processes such as coagulation and sedimentation have no significant effect on PST pollution. Currently, methods for removing paralytic shellfish poisoning mainly include adsorption, conventional oxidation, microbial degradation, and advanced oxidation methods. Adsorption methods are difficult to recycle and process, and do not completely decompose PSTs, only enriching and transferring them. Conventional oxidation methods, represented by chlorination, ozone, and potassium permanganate methods, are costly, technologically complex, and prone to producing disinfection byproducts or introducing metal ions, causing secondary pollution. Microbial degradation has a small environmental impact, but suffers from slow biological acclimation and long reaction times, making it unsuitable for large-scale application. Advanced oxidation methods are considered effective PST degradation pathways and have been extensively studied. The main methods include photochemical degradation, photocatalysis, (Fenton-like) methods, and UV- and ozone-based advanced oxidation technologies.

[0006] Adsorption method: PSTs are enriched and transferred using activated carbon, chitosan, and porous resin materials as adsorbents. Shi et al. used three commercially available activated carbons (PACs) derived from bitumen, lignite, and charcoal to adsorb PSTs and studied the effects of pH and natural organic matter (NOM) on PAC adsorption of PSTs. Shi et al. (Shi H, Ding J, Timmons T, et al. pH effects on the adsorption of saxitoxin by powdered activated carbon [J]. HarmfulAlgae, 2012, 19: 61-7.) found that NOM in natural water bodies causes the optimal adsorption pH to shift from alkaline to neutral, and that the zero point charge (PZC) of PAC has a greater influence on the adsorption effect than the specific surface area of ​​PAC. They also achieved complete adsorption of 25 eqSTX μg / L PSTs by 20 mg / L charcoal-derived activated carbon within 2 h at pH 8.2.

[0007] Conventional oxidation method: Utilizing the oxidizing properties of traditional oxidants to oxidize and degrade PSTs. Maalouf et al. (Maalouf S, Adams C, Hoppe-Jones C. Determination of oxidation rate constant for nodularin-r, saxitoxin, dc-saxitoxin, and neo-saxitoxin with conventional water treatment plant oxidants and advanced oxidation processes [J]. AWWA Water Science, 2024, 6(3): e1374) treated 50 μg / L PSTs with 2-10 mg / L chlorine, 0.1-2 mg / mL ozone, and 1-5 mg / L potassium permanganate. The maximum degradation rates obtained in a moderately alkaline environment were only about 82%, 66%, and 70%, respectively. This was mainly because the lack of unsaturated bonds on the guanidino carbon of the PST molecule made it difficult for the oxidants to effectively attack the PST molecule.

[0008] Photocatalysis: An advanced oxidation method that uses photocatalytic materials such as TiO2 to generate a series of free radicals in solution to degrade organic matter. Yuichi (Tominaga Y, Kubo T, Hosoya K. Surface modification of TiO2 for selective photodegradation of toxic compounds [J]. Catalysis Communications, 2011, 12(9): 785-9.) et al. modified TiO2 materials by introducing surface molecular recognition sites, and achieved complete degradation of 1.2 μmol / L low-toxicity PSTs deaminedioyl sclerotoxin (dcSTX) molecules in 30 min, but did not show the ability to degrade the recalcitrant and highly toxic PSTs sclerotoxin (STX) and glossophytic toxin (GTX).

[0009] Advanced oxidation technology (AOT) is an advanced method for degrading and mineralizing organic pollutants. Its oxidizing power is several times stronger than that of traditional oxidants, while the generation of disinfection byproducts is also much lower. However, problems such as low free radical production, easy catalyst deactivation, and secondary pollution caused by catalyst self-dissolution have hindered the development of AOT technology for degrading and mineralizing paralyzing shellfish poisoning. Hydroxyl radical (•OH) solution, generated efficiently by atmospheric pressure ionization discharge, has the characteristics of high concentration, strong oxidizing power, low cost, and no secondary pollution. It can complete the degradation and mineralization of organic pollutants under the background of microbial disasters within seconds, and has been widely used in freshwater areas. Li Jianlan (Li Jianlan. Research on the rapid killing of *Hymenochloa hymenochloa* and simultaneous mineralization of 2-methylisoborneol by hydroxyl radicals [D], 2022.) used this method to generate •OH solution (TRO=1.2 mg / L) to treat *Hymenochloa hymenochloa*. Pseudanabaena The method of killing algal cells within 12 seconds while maintaining cell integrity and reducing the extracellular 2-MIB concentration below the odor threshold was achieved by using hydroxyl radicals to kill algae (Houttuynia cordata) and its odor-producing substance 2-methylisoborneol (2-MIB). Jie Ying et al. (Jie Ying. Study on the cell integrity and mineralization of geosminerals by killing algae with hydroxyl radicals [D], 2023) used this method to prepare a 1.1 mg / L •OH solution, which killed the freshwater cyanobacterium Houttuynia cordata (Houttuynia cordata) within 12 seconds. Anabaena This invention aims to develop a device and method for mineralizing paralytic shellfish poisoning by hydroxyl radicals, thereby achieving efficient prevention and control of marine ecological disasters caused by paralytic shellfish poisoning by marine dinoflagellates, and providing a complete solution from source control to end-of-life assessment. Summary of the Invention

[0010] To address the challenge that existing treatment methods cannot completely remove or mineralize paralytic shellfish poisoning, a method and device for mineralizing paralytic shellfish poisoning from marine dinoflagellates using hydroxyl radicals has been developed. This method mineralizes the paralytic shellfish poisoning while simultaneously killing the toxin-producing dinoflagellates, effectively protecting mussel biosafety and blocking the threat of paralytic shellfish poisoning to human life and health at its source.

[0011] A method for mineralizing paralyzing shellfish poisoning caused by marine dinoflagellates using hydroxyl radicals includes the following steps: preparation of •OH solution, TRO adjustment, •OH mineralization for algae control, toxicity assessment, and online real-time monitoring: (1) Start the hydroxyl radical •OH solution generating device, apply high frequency and high voltage excitation to the discharge electrode of the oxygen plasma source, and oxygen is introduced into the extremely narrow discharge gap to be ionized and dissociated to generate high concentration oxygen active particles, which are injected into the gas-liquid mixer; seawater is pumped from the storage tank into the gas-liquid mixer, and hydroxyl radical •OH is efficiently generated with oxygen active particle gas through the water jet cavitation effect, and the concentration is expressed as total oxidant TRO; by adjusting the gas-liquid ratio of oxygen active particle gas to seawater in the gas-liquid mixer, a •OH solution with gradient TRO concentration is obtained. (2) Open the inlet valve of pipeline I and pump seawater from seawater control tank A into the liquid-liquid mixer; •OH solution with gradient TRO concentration generated by the •OH solution generating device is injected into the liquid-liquid mixer along the upper and lower pipelines in sequence. After being mixed with seawater in the throat, it breaks into μm-sized droplets. The droplets are evenly dispersed in the liquid-liquid mixer and pipeline; Starting from the throat of the liquid-liquid mixer, eight sampling ports are arranged at equal intervals on the pipeline at the rear end of the liquid-liquid mixer at a distance of 1s hydraulic residence time. The TRO concentration at each sampling port is measured to obtain the TRO concentration gradient of the pipeline after liquid-liquid mixing and dilution; Switch the inlet valve of pipeline I and pump saturated 4-HBA solution from 4-HBA control tank B into the liquid-liquid mixer. •OH and 4-HBA undergo an instantaneous electrophilic substitution reaction to generate 3,4-DHBA. Samples are taken at the eight sampling ports on the pipeline at the rear end of the liquid-liquid mixer to detect the •OH concentration gradient in the pipeline and establish the functional relationship of "TRO-•OH concentration"; The chemical equation for the capture of •OH by 4-HBA is as follows: .

[0012] (3) Open the inlet valve of pipeline II, pump the paralytic shellfish poison solution from the control tank C into the liquid-liquid mixer, and mix it with the gradient concentration of •OH solution in a turbulent flow at the throat. The •OH solution is dispersed into fine droplets under shear force. At the moment the droplets break, •OH collides and contacts with the paralytic shellfish poison molecules, oxidizing and degrading them until the paralytic shellfish poison is mineralized. Take a sample at the sampling port determined by the pipeline at the end of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison, and establish a dose-effect numerical model of •OH mineralization of shellfish poison. Based on the •OH mineralization A dose-effect numerical model of shellfish poisoning was used to determine the optimal TRO concentration. Then, at the determined main pipeline TRO concentration, samples were taken from eight sampling ports at the end of the liquid-liquid mixer to detect the concentration of paralytic shellfish poisoning at different reaction times. A time-effect numerical model of •OH mineralization of shellfish poisoning was established to determine the threshold of •OH mineralization of paralytic shellfish poisoning. At the mineralization threshold, samples were taken from eight sampling ports at the end of the liquid-liquid mixer to detect the intermediate products of the mineralization process and determine the reaction pathway of •OH mineralization of paralytic shellfish poisoning. (4) Switch the inlet valve of pipeline II, pump the dinoflagellate solution from the dinoflagellate control tank D into the liquid-liquid mixer, and disperse the gradient concentration of •OH solution into fine droplets after turbulent mixing with the dinoflagellate solution at the throat. The •OH solution rapidly mineralizes the extracellular paralytic shellfish poison and kills the toxin-producing dinoflagellates at the moment the droplets break. Take samples at the sampling port determined on the pipeline at the back end of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison and the density of algal cells, and establish a dose-effect numerical model of •OH mineralization and algae killing. According to the dose-effect numerical model of •OH mineralization and algae killing, determine the optimal TRO concentration, and then take samples from 8 sampling ports on the pipeline at the back end of the liquid-liquid mixer at the determined main pipeline TRO concentration, detect the concentration of degraded shellfish poison and the density of lethal dinoflagellates at different reaction times, establish a time-effect numerical model of •OH algae killing and mineralization, and determine the threshold of •OH algae killing and mineralization. (5) Extract the paralytic shellfish poison solution from the control tank C and transfer it to the culture tank C2 as the control group. Extract the paralytic shellfish poison solution from the treatment tank C1 with the mineralization threshold and transfer it to the culture tank C3 as the treatment group. Place a number of mussels in the three C2 culture tanks and the three C3 culture tanks. Observe the physiological status of the mussels at regular intervals, measure the concentration of paralytic shellfish poison and the activity of the antioxidant system in the mussels, and calculate the concentration of NOAEC with no observed adverse effects and the concentration of NOEC with no observed adverse effects. When NOAEC>100%, the shellfish poison solution has no acute toxic effects. When NOEC>100%, the shellfish poison solution has no chronic toxic effects. Dinoflagellate solution was extracted from control tank D and transferred to culture tank D2 as a control group. Dinoflagellate solution from treatment tank D1 (with a lethal threshold) was extracted and transferred to culture tank D3 as a treatment group. Mussels were placed in three culture tanks D2 and three culture tanks D3. The physiological status of the mussels was observed regularly, and the concentration of paralytic shellfish poisoning (NPPT) and the activity of the antioxidant system in the mussels were measured. Water samples were taken to measure the concentration of extracellular paralytic shellfish poisoning (NPPT) and NOAEC. When NOAEC > 100%, the dinoflagellate solution had no acute toxic effects; when NOEC > 100%, the dinoflagellate solution had no chronic toxic effects. Compare the physiological and biochemical parameters of mussels in culture tanks C3 and D3, estimate NOAEC and NOEC, and evaluate the differences in acute and chronic toxic effects of shellfish toxic solution and dinoflagellate solution. (6) The detection unit is equipped with an online TRO detector, an online algae counter and an online water quality detector to monitor in real time the TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color and turbidity in the seawater control tank A and seawater treatment tank A1 and the 4-HBA control tank B and 3,4-DHBA treatment tank B1; to monitor in real time the TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color and turbidity in the shellfish poisoning control tank C and shellfish poisoning treatment tank C1; and to monitor in real time the algal cell density, TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color, turbidity and chlorophyll a in the dinoflagellate control tank D and dinoflagellate treatment tank D1.

[0013] Furthermore, in step (1), by adjusting the gas-liquid ratio of the oxygen-active particle gas injected into the gas-liquid mixer to the seawater, a gradient TRO concentration of •OH solution is obtained, and the remaining oxygen-active particle gas is discharged after being decomposed by a digester; the oxygen flow rate is 0.5~2 L / min, the external excitation power is 100~400 W; the oxygen-active particle output of the plasma source is 180~220 mg / L, the gas-liquid ratio of the gas-liquid mixer is 1:(3~10), and the TRO concentration of the •OH solution is as high as 10~80 mg / L.

[0014] Furthermore, high-temperature sterilized seawater is injected into the seawater control tank A; a saturated 4-HBA seawater solution is prepared in the 4-HBA control tank B with a concentration of 0.1~0.5 mmol / L; and a paralytic shellfish poisoning solution is prepared in the shellfish poisoning control tank C, with the shellfish poisoning concentration prepared to determine the •OH mineralization threshold at 2~10×10⁻⁶ mmol / L. 2 The shellfish toxicity concentration for analysis of mineralization intermediates is prepared at 1~20×10 ng / L. 3 ng / L; Dinoflagellate control tank D was used to prepare a paralytic shellfish poisoning solution containing Alexandrium, Pyrodinium, and Gyrodinium chainensis, with a total algal density of 1~50×10 ng / L. 3 cells / mL.

[0015] Furthermore, the flow rates of pipes I and II are 0.2~2.0 m³ / s. 3 / h, the miscibility ratio of the •OH solution in the liquid-liquid mixer to the main pipeline inlet water is 1:(10~50), and the TRO concentration gradient in the pipeline after liquid-liquid mixing and dilution is 0.2~8.0 mg / L.

[0016] Furthermore, in steps (3) and (4), at the moment of droplet collapse, •OH mineralizes paralyzing shellfish poison through two-step reactions: ① •OH attacks the negatively charged sites of the guanidinium NC and NH bonds, geminal diol CO bonds, etc., of the shellfish poison, and opens the tricyclic structure of the shellfish poison through addition and hydrogen abstraction reactions; ② •OH further attacks the α-C and β-C sites of the intermediate product, oxidizes the straight chain to generate small molecule carboxylic acid, and finally completely mineralizes the shellfish poison molecule into CO2, H2O and inorganic anions.

[0017] Furthermore, in step (4), the •OH penetrates the cell membrane and enters the algal cell at the moment of droplet collapse, killing the dinoflagellates through two pathways: ① •OH directly attacks the phosphodiester bonds and guanine bases on the DNA in the nuclear region of the algal cell, causing DNA double-strand breaks and fragmentation; ② •OH destroys the chloroplasts of the algal cell, oxidizing chlorophyll molecules, degrading photosynthetic center proteins and disintegrating the thylakoid structure, causing the algal cells to lose photosynthetic activity.

[0018] Furthermore, in step (5), the NOAEC is calculated by measuring physiological activity parameters such as mussel mortality rate, individual shell-closing rate, spraying frequency, and byssal secretion rate within 4 days; when there is no obvious abnormality in the physiological activity of mussels in the tank, the calculated NOAEC > 100%, and the treated shellfish poison solution and dinoflagellate solution have no acute toxic effects; the NOEC is calculated by measuring biochemical indicators such as superoxide dismutase (SOD) activity, malondialdehyde (MDA) and other lipid peroxidation products, acetylcholinesterase (AChE) concentration and in vivo paralytic shellfish poison accumulation concentration within 7 to 14 days; when there is no obvious abnormality in the biochemical indicators of mussels in the tank, the calculated NOEC > 100%, and the shellfish poison solution and dinoflagellate solution have no chronic toxic effects.

[0019] This invention also provides an apparatus for mineralizing the paralyzing shellfish poison of marine dinoflagellates using hydroxyl radicals. The apparatus includes pipeline I, pipeline II, a •OH solution generating device III, a toxicity assessment unit IV, a detection unit V, four control tanks, and four treatment tanks. The four control tanks are seawater control tank A, 4-HBA control tank B, shellfish poison control tank C, and dinoflagellate control tank D. The four treatment tanks are seawater treatment tank A1, 3,4-DHBA treatment tank B1, shellfish poison treatment tank C1, and dinoflagellate treatment tank D1. Pipeline I is a TRO regulating pipeline. It connects to the seawater control tank A and the 4-HBA control tank B through the first and second inlet valves. It is then connected to the inlet of the first high-pressure pump through the main valve of Pipeline I. The outlet of the first high-pressure pump is connected to the main inlet of the liquid-liquid mixer. The main outlet of the liquid-liquid mixer is connected to the main outlet valve of Pipeline I. It is then connected to the seawater treatment tank A1 and the 3,4-DHBA treatment tank B1 through the first and second outlet valves, respectively. Pipeline II is a mineralization and algae-killing pipeline. It connects to the shellfish poisoning control tank C and the dinoflagellate control tank D through the third and fourth inlet water valves. Then, it is connected to the inlet of the second high-pressure pump through the main valve of Pipeline II. The outlet of the second high-pressure pump is connected to the main inlet of the liquid-liquid mixer. The water treated by the liquid-liquid mixer is output through its main outlet and connected to the main outlet valve of Pipeline II. It is then connected to the shellfish poisoning treatment tank C1 and the dinoflagellate treatment tank D1 through the third and fourth outlet water valves, respectively. The •OH solution generating device III is equipped with an air inlet branch pipe and a water inlet branch pipe. The air inlet branch pipe is equipped with a flow meter, an oxygen plasma generator, and a digester. The water inlet branch pipe is equipped with a water storage tank, a water inlet valve, a booster pump, a perforated plate filter, and a gas-liquid mixer and a •OH injection valve. The oxygen plasma generator is equipped with a high-frequency high-voltage power supply. An external oxygen source is connected to the oxygen plasma generator's air inlet. The high-frequency high-voltage power supply is used to apply high-frequency high-voltage excitation to the oxygen plasma generator. The oxygen active particles generated by the oxygen plasma generator are split by a distributor. A portion is injected into the side air inlet of the gas-liquid mixer, and the excess gas is decomposed by a decomposer and then discharged. The water drawn from the water storage tank by the booster pump enters the main water inlet of the gas-liquid mixer through the perforated plate filter. The •OH solution output from the main water outlet of the gas-liquid mixer is connected to the upper and lower double suction ports of the liquid-liquid mixer. The toxicity assessment unit IV is equipped with four independent water delivery pipelines for exposure. The inlet of the first delivery pipeline is connected to the shellfish poison control tank C, and then to the first aquaculture tank C2 via the first delivery valve, the first delivery pump, and the first delivery flow meter. The inlet of the second delivery pipeline is connected to the dinoflagellate control tank D, and then to the second aquaculture tank D2 via the second delivery valve, the second delivery pump, and the second delivery flow meter. The inlet of the third delivery pipeline is connected to the shellfish poison treatment tank C1, and then to the third aquaculture tank C3 via the third delivery valve, the third delivery pump, and the third delivery flow meter. The inlet of the fourth delivery pipeline 44 is connected to the dinoflagellate treatment tank D1, and then to the fourth toxic aquaculture tank D3 via the fourth delivery valve, the fourth delivery pump, and the fourth delivery flow meter.

[0020] Furthermore, in the •OH solution generating device III, an active particle detector is installed at the outlet of the oxygen plasma generator; a flow meter is installed between the outlet of the booster pump and the inlet of the orifice plate filter; the •OH solution output from the main outlet of the gas-liquid mixer is connected to the •OH injection valve after passing through the •OH solution detector and the •OH solution sampler. In the pipeline I, the outlet of the first high-pressure pump is connected to the inlet flow meter, and is connected to the main inlet of the liquid-liquid mixer via the inlet sampler. The main outlet of the liquid-liquid mixer is equipped with 8 sampling ports and the inlet of the TRO online detector in the main pipeline. In pipeline II, the outlet of the second high-pressure pump is connected to the inlet flow meter, and then connected to the main inlet of the liquid-liquid mixer via an inlet sampler; the main outlet of the liquid-liquid mixer is equipped with 8 sampling ports and the inlet of the TRO online detection instrument in the main pipeline. Pressure gauges are installed at both ends of the main inlet and main outlet of the liquid-liquid mixer to monitor the jet operation status of the liquid-liquid mixer.

[0021] Each of the control tanks is equipped with a height level gauge on its side and a stirring paddle at the bottom, which is connected to a motor via a drive shaft.

[0022] Each of the breeding tanks is a 30L transparent water tank, and three are arranged in a parallel repeat.

[0023] Furthermore, the detection unit V is equipped with detection pipelines, which are divided into a first detection inlet branch pipe and a second detection inlet branch pipe. The first detection inlet branch pipe is connected to the seawater control tank A, the 4-HBA control tank B, the shellfish poison control tank C, and the dinoflagellate control tank D respectively through four branch valves, and is connected to the water pump inlet through the first detection inlet main valve and the first detection flow meter. The second detection inlet branch pipe is connected to the seawater treatment tank A1, the 3,4-DHBA treatment tank B1, the shellfish poison treatment tank C1, and the dinoflagellate treatment tank D1 respectively through four branch valves, and is connected to the water pump inlet through the second detection inlet main valve and the second detection flow meter. The water pump outlet is divided into two paths, one of which is connected to an online algae counter and an online water quality analyzer, and the other is equipped with an online TRO analyzer and a sampling detector.

[0024] The technical effects and advantages of the present invention are as follows: (1) The method of this invention precisely adjusts the concentration of the •OH solution injected into the liquid-liquid mixer by changing the gas-liquid ratio in the •OH solution generating device, accurately measures the TRO concentration in the pipeline after mixing and its corresponding •OH concentration, and establishes the “TRO-•OH concentration” functional relationship; at the same time, eight sampling ports with hydraulic residence time of 1 to 8 seconds are set in the pipeline at the rear end of the mixer to construct the efficacy and time-effect relationship between •OH mineralization paralytic shellfish poison and killing toxin-producing dinoflagellates, and determine the threshold.

[0025] (2) The method used in this invention realizes the mineralization of refractory paralytic shellfish poisoning by •OH in a liquid-liquid mixer, and no paralytic shellfish poisoning was detected in the effluent; the two-step reaction path of the mineralization process was verified by the detection of mineralization intermediates.

[0026] (3) The method adopted in this invention designs a closed-loop treatment and evaluation method system for •OH mineralization algae killing, and provides a full-process solution from source control to terminal evaluation. Attached Figure Description

[0027] Figure 1 Schematic diagram of a device for mineralizing marine dinoflagellates with hydroxyl radicals to paralyze shellfish toxins. Figure 2 Schematic diagram of •OH mineralization and algae killing in a liquid-liquid mixer. Figure 3 • Schematic diagram of the pathway of OH mineralization paralytic shellfish poisoning (taking GTX1 molecule as an example). Detailed Implementation

[0028] The following embodiments will further illustrate the present invention with reference to the accompanying drawings.

[0029] Examples of implementing the apparatus for mineralizing paralytic shellfish poisoning by hydroxyl radicals of marine dinoflagellates according to the present invention include: Figure 1 As shown, the system includes pipeline I, pipeline II, •OH solution generator III, toxicity assessment unit IV, detection unit V, liquid-liquid mixer 5, seawater control tank A, 4-HBA control tank B, shellfish poison control tank C, dinoflagellate control tank D, seawater treatment tank A1, 3,4-DHBA treatment tank B1, shellfish poison treatment tank C1, and dinoflagellate treatment tank D1. The system includes a main TRO online monitoring instrument 7, an inlet sampler 4, eight sampling ports 61-68, a first high-pressure pump 21, a second high-pressure pump 22, a first main inlet valve 11, a second main inlet valve 12, a first main outlet valve 13, a second main outlet valve 14, a first inlet water valve 111, a second inlet water valve 112, a first outlet water valve 131, a second outlet water valve 132, a third inlet water valve 121, a fourth inlet water valve 122, a third outlet water valve 141, a fourth outlet water valve 142, and a flow meter 3. Among these, seawater control tank A, 4-HBA control tank B, shellfish poison control tank C, and dinoflagellate control tank D are collectively referred to as control tanks; seawater treatment tank A1, 3,4-DHBA treatment tank B1, shellfish poison treatment tank C1, and dinoflagellate treatment tank D1 are collectively referred to as treatment tanks.

[0030] • The OH solution generating device III is equipped with an air inlet branch pipe and a water inlet branch pipe. The air inlet branch pipe is equipped with a flow meter 311, a high-frequency high-voltage power supply 312, an oxygen plasma generator 313, an active particle detector 314, and a digester 315. The water inlet branch pipe is equipped with a water storage tank 320, a water inlet valve 321, a booster pump 322, a water flow meter 323, and a perforated plate filter 324, and is also equipped with a gas-liquid mixer 33, an OH solution detector 34, an OH solution sampler 35, and an OH injection valve 36. The oxygen plasma generator 313 is equipped with a high-frequency high-voltage power supply 312. The output metal terminals of the high-frequency high-voltage power supply 312 are connected to the power input terminal of the oxygen plasma generator 313 through an insulated waterproof electrical cable. An external oxygen source is depressurized. The valve is connected to the inlet of the oxygen plasma generator 313 via the flow path cabinet 311. The outlet of the oxygen plasma generator 313 is connected to the active particle detector 314. Part of the outlet of the active particle detector 314 is connected to the digester 315 via a branch line, and the rest is connected to the side inlet of the gas-liquid mixer 33 via the main line. The inlet of the booster pump 332 is connected to the outlet of the water storage tank 320. The booster pump 332 is connected to the inlet of the water flow meter 323. The outlet of the water flow meter 323 is connected to the main inlet of the gas-liquid mixer 33 via the orifice plate filter 324. The main outlet of the gas-liquid mixer 33 is connected to the •OH solution detector 34 and the •OH solution sampler 35, and then to the •OH injection valve 36. Finally, it is connected to the liquid-liquid mixer 5 via the upper and lower suction pipes.

[0031] Pipeline I connects to seawater control tank A and 4-HBA control tank B via first and second inlet valves 111 and 112, and then connects to the inlet of first high-pressure pump 21 via main valve 11 of pipeline I. The outlet of first high-pressure pump 21 is connected to the main inlet of liquid-liquid mixer 5. A flow meter 3 and an inlet sampler 4 are installed in between. The main outlet of liquid-liquid mixer 5 is connected to the main outlet valve 13 of pipeline I. Eight sampling ports 61-68 are installed in between and the inlet of the main pipeline TRO detector 7 is installed. Then, the first and second outlet valves 131 and 132 are connected to seawater treatment tank A1 and 3,4-DHBA treatment tank B1 respectively. Pipeline II connects to the shellfish poison control tank C and the dinoflagellate control tank D via the third and fourth inlet valves 121 and 122, and then connects to the inlet of the second high-pressure pump 22 via the main valve 12 of pipeline II. The outlet of the second high-pressure pump 22 is connected to the main inlet of the liquid-liquid mixer 5. A flow meter 3 and an inlet sampler 4 are installed in between. After the water is processed by the liquid-liquid mixer 5, it is output through 8 sampling ports 61-68 and the inlet of the main pipeline TRO detector 7 to the main outlet valve of pipeline II. It is then connected to the shellfish poison treatment tank C1 and the dinoflagellate treatment tank D1 via the third and fourth outlet valves 141 and 142, respectively.

[0032] Pressure gauges are installed at both the main inlet and outlet of the liquid-liquid mixer 5 to monitor the jet operation status of the liquid-liquid mixer.

[0033] The toxicity assessment unit IV is equipped with first to fourth exposure water delivery pipelines 41-44, each pipeline being independent of the others. The inlet of the first delivery pipeline 41 is connected to the shellfish poisoning control tank C, and then to the first aquaculture tank C2 via the first delivery valve 411, the first delivery pump 412, and the first delivery flow meter 413; the inlet of the second delivery pipeline 42 is connected to the dinoflagellate control tank D, and then to the second aquaculture tank D2 via the second delivery valve 421, the second delivery pump 422, and the second delivery flow meter 423; the inlet of the third delivery pipeline 43 is connected to the shellfish poisoning treatment tank C1, and then to the third aquaculture tank C3 via the third delivery valve 431, the third delivery pump 432, and the third delivery flow meter 433; the inlet of the fourth delivery pipeline 44 is connected to the dinoflagellate treatment tank D1, and then to the fourth aquaculture tank D3 via the fourth delivery valve 441, the fourth delivery pump 442, and the fourth delivery flow meter 443.

[0034] The detection unit V is equipped with a detection pipeline 51, which is divided into a first detection inlet branch pipe 511 and a second detection inlet branch pipe 512. The first detection inlet branch pipe 511 is connected to the seawater control tank A, the 4-HBA control tank B, the shellfish poison control tank C, and the dinoflagellate control tank D respectively through the first to fourth branch valves 523 to 526, and is connected to the inlet of the pump 54 through the first detection main valve 521 and the first detection flow meter 531. The second detection inlet branch pipe 512 is connected to the seawater treatment tank A1, the 3,4-DHBA treatment tank B1, the shellfish poison treatment tank C1, and the dinoflagellate treatment tank D1 through the fifth to eighth branch valves 527 to 530, and is connected to the inlet of the pump 54 through the second detection main valve 523 and the second detection flow meter 532. The outlet of the pump 54 is divided into two paths: one path is connected to the online algae counter 55 and the online water quality detector 56, and the other path is connected to the online TRO detector 57 and the sampling detector 58.

[0035] The method for mineralizing paralyzing shellfish poisoning caused by marine dinoflagellates using hydroxyl radicals provided by this invention includes the following steps: preparation of •OH solution, TRO adjustment, •OH mineralization for algae control, toxicity assessment, and online real-time monitoring. (1) Start the •OH solution generating device, apply high-frequency high-voltage excitation to the discharge electrode of the oxygen plasma source, and oxygen is introduced into the extremely narrow discharge gap to be ionized and dissociated to generate high-concentration oxygen active particles, which are injected into the gas-liquid mixer; seawater is drawn from the storage tank and pumped into the gas-liquid mixer after passing through the perforated plate filter, and hydroxyl radicals •OH are efficiently generated by the oxygen active particle gas through the water jet cavitation effect, with the concentration expressed as total oxidant TRO; adjust the gas-liquid ratio of oxygen active particle gas to seawater in the gas-liquid mixer to control the •OH solution generating device to generate a gradient TRO concentration of •OH solution, which is injected into the upper and lower suction pipes of the liquid-liquid mixer.

[0036] (2) Open the inlet valve of pipeline I and pump seawater from seawater control tank A into the liquid-liquid mixer; the gradient concentration of •OH solution generated by the •OH solution generating device is injected into the liquid-liquid mixer along the suction pipe. After the •OH solution is mixed with the seawater in the throat, it breaks into a large number of μm-sized droplets. The droplets are evenly dispersed in the mixer and pipeline. Starting from the throat of the liquid-liquid mixer, eight sampling ports are arranged at equal intervals on the pipeline at the rear end of the liquid-liquid mixer at a distance of 1s hydraulic residence time. The TRO concentration at each sampling port is measured to obtain the TRO concentration gradient of the pipeline after liquid-liquid mixing and dilution. Switch the inlet valve of pipeline I, and pump the saturated 4-HBA solution from the 4-HBA control tank B into the mixer. •OH and 4-HBA diffuse and collide with each other, and an electrophilic substitution reaction occurs instantaneously to generate 3,4-DHBA. Samples are taken from 8 sampling ports on the pipeline at the end of the mixer, and the peak area of ​​3,4-DHBA is detected by liquid chromatography to determine the •OH concentration, and a functional relationship of "TRO-•OH concentration" is established.

[0037] (3) Open the inlet valve of pipeline II, pump the paralytic shellfish poison solution from the control tank C into the liquid-liquid mixer, mix it with the gradient concentration of •OH solution in the throat in turbulent flow, the •OH solution is dispersed into fine droplets under shear action, and at the moment the droplets break, •OH collides and contacts with paralytic shellfish poison molecules, oxidizes and degrades until the paralytic shellfish poison is mineralized; take samples from the sampling port determined at the end of the pipeline of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison, and establish the "dose-effect" numerical model of •OH mineralization of shellfish poison; under the determined TRO concentration in the main pipeline, take samples from 8 sampling ports at the end of the pipeline of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison at different reaction times, establish the "time-effect" numerical model of •OH mineralization of shellfish poison, and determine the threshold of •OH mineralization of paralytic shellfish poison; under the mineralization threshold, take samples from 8 sampling ports at the end of the pipeline of the liquid-liquid mixer, detect the intermediate products of the mineralization process, and determine the reaction path of •OH mineralization of paralytic shellfish poison.

[0038] (4) Switch the inlet valve of pipeline II, pump the dinoflagellate solution from the dinoflagellate control tank D into the liquid-liquid mixer, and disperse the gradient concentration of •OH solution into fine droplets after turbulent mixing with the dinoflagellate solution at the throat. The •OH solution rapidly mineralizes the extracellular paralytic shellfish poison and kills the toxin-producing dinoflagellates at the moment the droplets break. Take samples at the sampling port determined at the end of the pipeline of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison and the density of algal cells, and establish a dose-effect numerical model of •OH mineralization and algae killing. Under the determined TRO concentration of the main pipeline, take samples from 8 sampling ports at the end of the pipeline of the liquid-liquid mixer, detect the concentration of degraded shellfish poison and the density of lethal dinoflagellates at different reaction times, establish a time-effect numerical model of •OH mineralization and algae killing, and determine the threshold of •OH mineralization and algae killing.

[0039] (5) Extract the paralytic shellfish poison solution from the control tank C and transfer it to the culture tank C2 as the control group. Extract the paralytic shellfish poison solution from the treatment tank C1 with the mineralization threshold and transfer it to the culture tank C3 as the treatment group. Place a number of mussels in the three culture tanks C2 and the three culture tanks C3. Observe the physiological status of the mussels at regular intervals, measure the concentration of paralytic shellfish poison and the activity of the antioxidant system in the mussels, and calculate the concentration of NOAEC with no observed adverse effects and the concentration of NOEC with no observed adverse effects. When NOAEC>100%, the shellfish poison solution has no acute toxic effect. When NOEC>100%, the shellfish poison solution has no chronic toxic effect.

[0040] Dinoflagellate solution was extracted from control tank D and transferred to culture tank D2 as a control group. Dinoflagellate solution from treatment tank D1 (with a lethal threshold) was extracted and transferred to culture tank D3 as a treatment group. Mussels were placed in three culture tanks (D2 and D3). The physiological condition of the mussels was observed regularly, and the concentration of paralytic shellfish poisoning (PSP) and antioxidant system activity in the mussels were measured. Water samples were taken to measure the concentration of extracellular PSP, and NOAEC and NOEC were calculated. When NOAEC > 100%, the Dinoflagellate solution had no acute toxic effects; when NOEC > 100%, the Dinoflagellate solution had no chronic toxic effects.

[0041] The physiological and biochemical parameters of mussels in culture tanks C3 and D3 were compared, NOAEC and NOEC were calculated, and the differences in acute and chronic toxic effects of shellfish toxic solution and dinoflagellate solution were evaluated.

[0042] (6) The detection unit is equipped with an online TRO detector, an online algae detector and an online water quality detector to monitor in real time the TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color and turbidity in the seawater control tank A and seawater treatment tank A1 and the 4-HBA control tank B and the 3,4-DHBA treatment tank B1; to monitor in real time the TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color and turbidity in the shellfish poisoning control tank C and shellfish poisoning treatment tank C1; and to monitor in real time the algal cell density, TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color, turbidity and chlorophyll a in the dinoflagellate control tank D and the dinoflagellate treatment tank D1.

[0043] In step (1), oxygen at a flow rate of 0.5~2 L / min enters the plasma source through a Teflon gas pipe. A high-frequency high-voltage power supply applies a high-frequency high-voltage excitation of 100~400 W to the oxygen plasma source, generating atmospheric pressure ionization discharge in the extremely narrow gap of the oxygen plasma source, ionizing and dissociating the oxygen into high-concentration oxygen active particles, including O2. + O, O + O( 3 P), O( 1 D), O2(a 1 The gas yields Δg) and O3, with a production rate as high as 180~220 mg / L. High-efficiency •OH is generated by injecting oxygen-active particulate gas into a gas-liquid mixer via water jet cavitation, with the concentration expressed as TRO. The gas-liquid ratio in the gas-liquid mixer is 1:(3~10). By adjusting the gas-liquid ratio of the oxygen-active particulate gas injected into the gas-liquid mixer to seawater, a gradient TRO concentration of •OH solution, reaching 10~80 mg / L, is obtained. Residual oxygen-active particulate gas is decomposed by a digester before being discharged.

[0044] In steps (2) to (4), high-temperature sterilized seawater is injected into the seawater control tank A; a saturated 4-HBA seawater solution is prepared in the 4-HBA control tank B with a concentration of 0.1 to 0.5 mmol / L; a paralytic shellfish poisoning solution is prepared in the shellfish poisoning control tank C, and the shellfish poisoning concentration at which the •OH mineralization threshold is determined is prepared to be 2 to 10 × 10⁻⁶ mmol / L. 2 The shellfish toxicity concentration for analysis of mineralization intermediates is prepared at 1~20×10 ng / L. 3 ng / L; Dinoflagellate control tank D was used to prepare a paralytic shellfish poisoning solution containing Alexandrium, Pyrodinium, and Gyrodinium chainensis, with a total algal density of 1~50×10 ng / L. 3 cells / mL.

[0045] In (2) to (4), the flow rates of pipe I and pipe II are 0.2 to 2.0 m³. 3 / h, the mixing ratio of •OH solution in the liquid-liquid mixer to the main pipeline inlet water is 1:(10~50), and the TRO concentration gradient in the pipeline after liquid-liquid dilution is 0.2~8.0mg / L.

[0046] In step (2), after the •OH solution is mixed with 4-HBA, 4-HBA rapidly (k~10) 9 The 3,4-DHBA (3,4-DHBA) is captured by a liquid-liquid polymerase (L / mol·s). Due to the steric hindrance and electron-withdrawing properties of the substituted methyl group, a non-selective electrophilic addition reaction occurs, generating 3,4-DHBA in a 1:1 molar ratio. Samples are taken from eight ports on the downstream end of the liquid-liquid miscible apparatus, and the concentration of 3,4-DHBA is detected by liquid chromatography-ultraviolet fluorescence. The concentration of •OH is then calculated using a 1:1 molar ratio conversion. The chemical equation for the capture of •OH by 4-HBA is as follows: In step (3), the unknown intermediate compounds in the mineralization process are screened using the full scan combined with enhanced particle scanning (MS-EPI) method of liquid chromatography-mass spectrometry. The •OH at the moment of droplet collapse mineralizes paralytic shellfish poison through two main reactions: ① •OH preferentially attacks the three types of negatively charged sites on the paralytic shellfish poison molecule, mainly guanidinyl NC and NH bonds and geminal diol CO bonds, and sequentially opens the tricyclic structure of shellfish poison through addition and hydrogen abstraction reactions; ② •OH further attacks the α-C and β-C sites of intermediate products, oxidizing the long straight chain after ring opening step by step to generate short-chain intermediates such as small molecule carboxylic acids, and finally completely mineralizes the paralytic shellfish poison molecule into CO2, H2O and inorganic anions.

[0047] In step (4), the droplet collapses instantly. •OH penetrates the cell membrane and enters the algal cell, killing the dinoflagellates through two pathways: ① •OH directly attacks the phosphodiester bonds and guanine bases on the DNA in the algal cell nucleus, causing DNA double-strand breaks and fragmentation; ② •OH destroys the algal cell chloroplasts, causing the algal cells to lose their photosynthetic capacity by oxidizing chlorophyll molecules, degrading photosynthetic center proteins and disintegrating thylakoid structures.

[0048] In step (5), the NOAEC is calculated by measuring physiological activity parameters such as mussel mortality rate, individual shell-closing rate, spraying frequency, and byssal secretion rate within 4 days; when there is no obvious abnormality in the physiological activity of mussels in the culture tank, the calculated NOAEC > 100%, and the treated shellfish poison solution and dinoflagellate solution have no acute toxic effects; the NOEC is calculated by measuring biochemical indicators such as superoxide dismutase (SOD) activity, malondialdehyde (MDA) and other lipid peroxidation products, acetylcholinesterase (AChE) concentration and in vivo paralytic shellfish poison accumulation concentration within 7 to 14 days; when there is no obvious abnormality in the biochemical indicators of mussels in the culture tank, the calculated NOEC > 100%, and the shellfish poison solution and dinoflagellate solution have no chronic toxic effects.

[0049] Both the inlet and outlet of the liquid-liquid mixer are equipped with high-precision pressure gauges.

[0050] Each of the control tanks is equipped with a height level gauge on its side and a stirring paddle at the bottom, which is connected to a motor via a drive shaft.

[0051] Each of the breeding tanks is a 30L transparent water tank, and three are arranged in a parallel repeat.

[0052] The following is the operating procedure of the hydroxyl radical mineralization device for paralyzing shellfish toxins from marine dinoflagellates: ① Start the •OH solution generating device III, open the inlet valve 321 and the booster pump 322, adjust the inlet flow rate through the water flow meter 323, and pump seawater from the storage tank 320 along the inlet branch to the perforated plate filter 324 for primary filtration to remove particulate impurities before injecting it into the gas-liquid mixer 33. Open the flow gas cabinet 311, and introduce oxygen into the inlet pipeline at the set flow rate and input it into the oxygen plasma generator 313. Start the high-frequency high-voltage power supply 312 to apply excitation power to the oxygen plasma generator 313, ionizing and dissociating the oxygen into oxygen active particle gas. After the concentration of the generated oxygen active particle gas is measured by the active particle detector 314 and meets the standard, part of it is injected into the side inlet of the gas-liquid mixer 33, and the rest is discharged through the decomposer 315. In the gas-liquid mixer 33, oxygen-active particulate gas and seawater are cavitation-generated by a water jet to generate a high-concentration •OH solution. After online detection by the •OH solution detector 34 and sampling and analysis by the •OH solution sampler 35, the solution is injected into the upper and lower suction ports of the liquid-liquid mixer 5 through the •OH injection valve 36. By adjusting the gas-liquid ratio of oxygen-active particulate gas to seawater in the gas-liquid mixer 33 to a series of set values, a gradient concentration of •OH solution required for mineralization and sterilization is obtained, and this solution is sequentially introduced into the liquid-liquid mixer 5.

[0053] ② Fill the seawater control tank A and the 4-HBA control tank B with sterilized natural seawater. Add excess 4-HBA to the 4-HBA control tank B to prepare a saturated 4-HBA seawater solution. Open the first and second detection branch valves 523-524 and the first detection main inlet valve 521. Start the water pump 54 to pump the raw water from the seawater control tank A and the 4-HBA control tank B into the detection pipeline 51. Control the water flow rate through the raw water flow meter 531. Measure the conventional water quality parameters, TRO blank concentration, and the concentration of the prepared 4-HBA solution in the seawater using the online water quality analyzer 56 and the sampling detector 58. Open the first inlet main valve 11 and the first outlet main valve 13, and simultaneously open the first inlet water valve 111 and the first outlet water valve 131. Start the first high-pressure pump 21 to pump seawater into pipeline I. After passing through the flow meter 3 and the inlet sampler 4, the seawater is injected into the liquid-liquid mixer 5 to mix with the •OH solution. The water effluent from the liquid-liquid mixer 5 is sampled through eight sampling ports 61-68 to determine the TRO concentration corresponding to the •OH generation time of 1-8 seconds. After comparing the TRO concentration value detected online by the TRO online detector 7 on the main pipeline, the water is discharged into the seawater treatment tank A1. Close the first inlet water valve 111 and the first outlet water valve 133, and open the second inlet water valve 112 and the second outlet water valve 132 to pump the 4-HBA solution into pipeline I. After passing through the flow meter 3 and the inlet sampler 4, the solution is injected into the liquid-liquid mixer 5 to mix with the •OH solution. The effluent from the liquid-liquid mixer is sampled through eight sampling ports 61-68 on the downstream pipeline of the liquid-liquid mixer 5 to determine the •OH concentration corresponding to the •OH generation time of 1-8 seconds, and then discharged into the 3,4-DHBA treatment tank B1. The gas-liquid ratio of the gas-liquid mixer 33 in the •OH solution generating device III is adjusted to obtain •OH solutions of different concentrations. These solutions are then sequentially introduced into the liquid-liquid mixer 5 according to their concentrations, forming a TRO concentration gradient after liquid-liquid mixing and dilution in pipeline I. Seawater and 4-HBA solution are sequentially introduced into pipeline I, and samples are taken through the eight sampling ports 61-68 to detect the TRO concentration and •OH concentration gradient in the pipeline, thus determining the TRO-•OH concentration function relationship. Open the fifth and sixth detection branch valves 527-528 and the second detection main inlet valve 522, and start the water pump 54 to pump the treated effluent from the seawater treatment tank A1 and the 3,4-DHBA treatment tank B1 into the detection pipeline 51. Measure the treated water quality using the online water quality monitor 55 and measure the TRO change within 24 hours after treatment using the online TRO analyzer 57.

[0054] ③ Prepare a solution with a concentration of (2~10)×10 in the shellfish poisoning control tank C. 2A paralytic shellfish poisoning solution of ng / L is prepared. The third detection branch valve 525 and the first detection main inlet valve 521 are opened, and the water pump 54 is started to pump the paralytic shellfish poisoning solution into the detection pipeline 51. The water flow is controlled by the first detection flow meter 531. The water quality parameters and blank TRO concentration are measured by the online water quality analyzer 56 and the sampling port 58. The gas-liquid ratio of the gas-liquid mixer 33 in the •OH solution generating device III is adjusted to a series of gradients to obtain •OH solutions of gradient concentrations, which are then sequentially introduced into the liquid-liquid mixer 5 according to their different concentrations. Open the second inlet valve 12 and the second outlet valve 14, and simultaneously open the third inlet valve 131 and the third outlet valve 141. Start the second high-pressure pump 22 to extract the paralytic shellfish poison solution from the shellfish poison control tank C and inject it into pipeline II. After passing through the flow meter 3 and the inlet sampler 4, the inlet sample is injected into the liquid-liquid mixer 5 and mixed sequentially with •OH solutions of gradient TRO concentrations. Samples are taken through the eight sampling ports 61-68 set on the pipeline at the rear end of the liquid-liquid mixer to determine the concentration of paralytic shellfish poison and mineralization intermediate products under different pipeline TRO concentrations. The TRO concentration after the reaction is measured by the main pipeline TRO detector 7 to establish a dose-effect numerical model of •OH mineralization of paralytic shellfish poison. Adjust the gas-liquid ratio of the gas-liquid mixer 33 in the •OH solution generating device III to adjust the TRO concentration in pipeline II to the optimal concentration determined according to the dose-effect numerical model. Eight sampling ports were set up on the pipeline to collect samples and determine the concentration of paralytic shellfish poisoning (PSP) at different reaction times, establishing a time-effect numerical model of •OH mineralization of PSP. The threshold for •OH mineralization of PSP was determined by converting the TRO-•OH concentration function. Below the threshold, samples were collected through the eight sampling ports to detect mineralization intermediates and determine the reaction pathway of •OH mineralization of PSP. Water from pipeline II was discharged into the shellfish poisoning treatment tank C1 via a branch pipe. The seventh detection branch valve 529 and the second detection main inlet valve 522 were opened, and the pump 54 was started to pump the treated water from the shellfish poisoning treatment tank C1 into the detection pipeline 51. The water flow was controlled by the second detection flow meter 532. The treated water quality was measured by the online water quality monitor 56, the TRO change within 24 hours after treatment was measured by the online TRO detector 57, and the extracellular PSTs concentration change within 24 hours after treatment was monitored by the sampling detector 58 and liquid chromatography-mass spectrometry.

[0055] ④ Prepare a dinoflagellate control tank D with an algal density of (1~50)×10⁻⁶. 3 A concentration of extracellular paralytic shellfish toxicity corresponding to a concentration of dinoflagellates per 100 cells / mL is (2~10)×10⁻⁶. 2ng / L, open the fourth detection branch valve 526 and the first detection main inlet valve 521, start the water pump 54 to pump the paralytic shellfish poison-producing dinoflagellate solution into the detection pipeline 51, and control the water volume through the first detection flow meter 531. Measure the water quality parameters, algal density, and extracellular paralytic shellfish poison concentration using the online algae counter 55, online water quality analyzer 56, and sampling port 58. Adjust the gas-liquid ratio of the gas-liquid mixer 33 in the •OH solution generating device III to a series of gradients to obtain •OH solutions of varying concentrations, and sequentially introduce them into the liquid-liquid mixer 5 according to their concentrations. Close the third inlet valve 121 and the third outlet valve 141, and open the fourth inlet valve 122 and the fourth outlet valve 132. Pump the dinoflagellate solution from the dinoflagellate control tank D into pipeline I. Control the flow rate with flow meter 3, take inlet water samples with inlet sampler 4, and inject them into liquid-liquid mixer 5. Mix the solutions sequentially with •OH solutions of gradient TRO concentrations. Take samples through the eight sampling ports 61-68 set on the pipeline at the back end of the liquid-liquid mixer to determine the concentration of degraded shellfish poison and the density of lethal dinoflagellates under different pipeline TRO concentrations. Measure the TRO concentration after the reaction using the main pipeline TRO detector 7 to establish a dose-effect numerical model for •OH mineralization and algae killing. Adjust the gas-liquid ratio of the gas-liquid mixer 33 in the •OH solution generating device III to adjust the TRO concentration in pipeline II to the optimal concentration determined according to the dose-effect numerical model. Eight sampling ports were set up along the route to collect samples and measure the concentration of degraded shellfish toxin and the density of lethal dinoflagellates at different reaction times, establishing a time-effect numerical model of •OH mineralization algae killing; combined with the TRO-•OH concentration function relationship conversion, the threshold of •OH mineralization algae killing was determined; the effluent from pipe II was discharged into the dinoflagellate treatment tank D1 for storage through a branch pipe. The eighth detection branch valve 530 and the second detection main inlet valve 522 were opened, and the water pump 54 was started to pump the treated effluent from the dinoflagellate treatment tank D1 into the detection pipe 51. The water volume was controlled by the second detection flow meter 532. The water quality after treatment was measured by the online water quality monitor 56, the TRO change within 24 hours after treatment was measured by the online TRO detector 57, the density change of toxin-producing dinoflagellates within 24 hours after treatment was monitored by the online algae counter 56, and the extracellular PSTs concentration change within 24 hours after treatment was monitored by the sampling detector 58 and liquid chromatography-mass spectrometry.

[0056] ⑤ Open the first delivery valve 411 and the first delivery pump 412 to extract paralytic shellfish poison solution from the control tank C and pump it into the first delivery pipeline 41. Then, inject it into the first culture tank C2 through the first delivery flow meter 413. Place 30 mussels in the first culture tank C2 for exposed culture. Open the third delivery valve 431 and the third delivery pump 432 to extract the treated paralytic shellfish poison solution from the treatment tank C1 and pump it into the third delivery pipeline 43. Then, inject it into the third culture tank C3 through the third delivery flow meter 433. Place 30 mussels in the third culture tank C3 for exposed culture. Within 96 hours of the start of exposure, measure the physiological activity parameters of the mussels, calculate the NOAEC of each culture tank, and assess the acute biological toxicity of the shellfish poison solution to the mussels before and after treatment. On day 14 of the start of exposure, randomly collect mussel samples at regular intervals for homogenization, measure the biochemical indicators in the mussels, calculate the NOEC of each culture tank, and assess the chronic biological toxicity of the shellfish poison solution to the mussels before and after treatment.

[0057] The second delivery valve 421 and the second delivery pump 422 were opened to extract dinoflagellate solution from the control tank D and pump it into the second delivery pipeline 42. This solution was then injected into the second culture tank D2 via the second delivery flow meter 423. Thirty mussels were placed in the second culture tank D2 for exposed culture. The fourth delivery valve 441 and the fourth delivery pump 442 were opened to extract treated dinoflagellate solution from the treatment tank D1 and pump it into the fourth delivery pipeline 44. This solution was then injected into the fourth culture tank D3 via the fourth delivery flow meter 443. Thirty mussels were placed in the fourth culture tank D3 for exposed culture. Physiological activity parameters and in vivo biochemical indicators were measured periodically at 96 hours and 14 days after the start of exposure. The NOAEC and NOEC values ​​for each culture tank were calculated to assess the acute and chronic toxicity of the dinoflagellate solution to the mussels before and after treatment.

[0058] The physiological and biochemical parameters of mussels in the third culture tank C3 and the fourth culture tank D3 were compared, and NOAEC and NOEC were calculated to evaluate the differences in acute and chronic toxic effects of shellfish toxic solution and dinoflagellate solution.

[0059] Example: The natural seawater used in the experiment was taken from the nearshore waters of the Tianjin Lingang Economic Zone. After filtering out particulate impurities, it was sterilized at high temperature before use. The total algae density prepared using this seawater was 1.5~25×10⁻⁶. 3 A solution of paralyzing shellfish dinoflagellates with an extracellular paralyzing shellfish toxicity concentration of 70-650 ng / L (cells / ml), including Alexandrium (…). Alexandrium spp.) and chain-like naked dinoflagellate ( Gymnodinium catenatumParalytic shellfish toxins include Gonyautoxin (GTX) 1-4, Saxitoxin (STX), and C1&2 toxins. Using tubing I, the concentration of the diluted TRO solution was adjusted to 0.2-2.0 mg / L, and the functional relationship between TRO-•OH concentration and C1&2 was established. •OH =8.22C TRO (R) 2 >0.99), where C •OH This represents the molar concentration of hydroxyl radicals, in μM, C. TRO The concentration of TRO is expressed in mg / L. •OH mineralization algaecide treatment was performed using pipeline II. A numerical model of the effectiveness-time of •OH mineralization algaecide was established and the threshold was determined. The concentrations of paralytic shellfish poisoning in the table are all converted to equivalent STX concentrations.

[0060] Table 1. Numerical model of the efficacy of •OH algaecide

[0061] Table 2. Time-dependent numerical model of OH- algaecide effect

[0062] Table 3. Results of •OH mineralized extracellular paralytic shellfish poisoning (ND indicates not detected)

[0063] Table 4. Changes in seawater quality parameters before and after OH treatment

[0064] The results of simultaneous algae killing by •OH mineralization are shown in Tables 1-3. The algae killing thresholds of •OH mineralization at total algae densities of 1500, 12000, and 50000 cells / L were 29.59, 78.91, and 118.37 μmol(•OH)·s / L, respectively. At these thresholds, •OH achieved a 100.0% kill rate against paralytic shellfish poisoning dinoflagellates of different densities, and no paralytic shellfish poisoning was detected. This indicates that •OH effectively mineralizes paralytic shellfish poisoning and kills poisoning dinoflagellates simultaneously.

[0065] The changes in seawater quality after OH treatment are shown in Table 4. The salinity and pH of the seawater did not change significantly, but the chlorophyll concentration, turbidity and color in the seawater background decreased significantly, and DO increased by about 24%. The seawater quality was significantly improved after OH treatment.

[0066] In both the shellfish poisoning control group and the dinoflagellate control group, mussel behavior was significantly abnormal, with a large accumulation of paralytic shellfish poisoning (PSP) exceeding the regulatory limit of 800 eqSTX μg / kg detected on the first day of exposure. The PSP levels in the mussels did not decrease below the regulatory limit within 14 days, and NOAEC and NOEC were <100%. Before treatment, both the shellfish poisoning solution and the dinoflagellate solution exhibited acute and chronic toxic effects. In the shellfish poisoning treatment group, mussel physiological behavior and biochemical indicators were normal, and no PSP accumulation was detected in the mussels. After treatment, the NOAEC and NOEC in the shellfish poisoning solution were >100%, with no acute or chronic toxic effects. In the dinoflagellate treatment group, mussel physiological behavior and biochemical indicators were normal, but a PSP concentration of 25 eqSTX μg / kg was detected within 3 days of exposure, rapidly decreasing to undetectable levels after 3 days. After treatment, the NOAEC and NOEC in the dinoflagellate solution were >100%, with no acute or chronic toxic effects. The NOAEC and NOEC were slightly higher than in the shellfish poisoning treatment group.

[0067] This invention proposes a method and apparatus for mineralizing marine dinoflagellates and paralytic shellfish poisoning using hydroxyl radicals. It precisely calibrates the concentrations of TRO and •OH and establishes the "TRO-•OH" concentration function relationship. Numerical models of the "dose-effect" and "time-effect" of •OH mineralizing paralytic shellfish poisoning and simultaneously killing toxin-producing dinoflagellates are established. The thresholds for •OH mineralizing paralytic shellfish poisoning and •OH algaecide mineralization are determined. Through a toxicity assessment and detection unit, the acute and chronic biological toxicity of paralytic shellfish poisoning and toxin-producing dinoflagellates to mussels treated by the method of this invention is verified to have disappeared.

[0068] This invention demonstrates a precise, controllable, and highly effective treatment capability through implementation examples, providing a highly efficient, rapid, adaptable, and easy-to-operate control solution for the marine ecological disaster caused by paralytic shellfish poisoning from marine dinoflagellates. This helps reduce the potential harm of paralytic shellfish poisoning from marine dinoflagellates to mussels and other marine aquaculture species. It should be noted that the scope of protection of this invention should not be limited to the specific embodiments described in the specification; any adjustments or optimizations to relevant technical parameters, or equivalent transformations and improvements to the process flow based on the core concept of this invention, as long as they do not depart from the technical spirit of this invention, should fall within the scope of protection of this invention. This includes, but is not limited to, optimization of the •OH generation method, adjustment of mineralization algaecide working conditions, structural improvement of the treatment device, in-depth research on the mineralization pathway of •OH on paralytic shellfish poisoning and the inactivation mechanism of toxin-producing dinoflagellates, and combined applications with other existing technologies.

Claims

1. A method for mineralizing paralytic shellfish poisoning caused by marine dinoflagellates using hydroxyl radicals, characterized in that, Includes the following steps: (1) Start the hydroxyl radical •OH solution generating device, apply high frequency and high voltage excitation to the discharge electrode of the oxygen plasma source, and oxygen is introduced into the extremely narrow discharge gap to be ionized and dissociated to generate high concentration oxygen active particles, which are injected into the gas-liquid mixer; seawater is pumped from the storage tank into the gas-liquid mixer, and hydroxyl radical •OH is efficiently generated with oxygen active particle gas through the water jet cavitation effect, and the concentration is expressed as total oxidant TRO; by adjusting the gas-liquid ratio of oxygen active particle gas to seawater in the gas-liquid mixer, a •OH solution with gradient TRO concentration is obtained. (2) Open the inlet valve of pipeline I and pump seawater from seawater control tank A into the liquid-liquid mixer; the gradient TRO concentration of •OH solution generated by the •OH solution generating device is injected into the liquid-liquid mixer along the upper and lower pipelines in sequence. After being mixed with seawater in the throat, it breaks into μm-sized droplets. The droplets are evenly dispersed in the liquid-liquid mixer and pipeline; starting from the throat of the liquid-liquid mixer, 8 sampling ports are arranged at equal intervals on the pipeline at the rear end of the liquid-liquid mixer at a distance of 1s hydraulic residence time. The TRO concentration at each sampling port is measured to obtain the TRO concentration gradient of the pipeline after liquid-liquid mixing and dilution; switch the inlet valve of pipeline I and pump the saturated 4-HBA solution from 4-HBA control tank B into the liquid-liquid mixer. •OH and 4-HBA undergo an electrophilic substitution reaction instantly to generate 3,4-DHBA. Samples are taken at the 8 sampling ports on the pipeline at the rear end of the liquid-liquid mixer to detect the •OH concentration gradient in the pipeline and establish the functional relationship of "TRO-•OH concentration"; (3) Open the inlet valve of pipeline II, pump the paralytic shellfish poison solution from the control tank C into the liquid-liquid mixer, and mix it with the gradient concentration of •OH solution in a turbulent flow at the throat. The •OH solution is dispersed into fine droplets under shear force. At the moment the droplets break, •OH collides and contacts with the paralytic shellfish poison molecules, oxidizing and degrading them until the paralytic shellfish poison is mineralized. Take a sample at the sampling port determined by the pipeline at the back end of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison, and establish a dose-effect numerical model of •OH mineralization of shellfish poison. Based on the •OH mineralization A dose-effect numerical model of shellfish poisoning was used to determine the optimal TRO concentration. Then, at the determined TRO concentration in the main pipeline, samples were taken from eight sampling ports at the end of the liquid-liquid mixer to detect the concentration of paralytic shellfish poisoning at different reaction times. A time-effect numerical model of •OH mineralization of shellfish poisoning was established to determine the threshold of •OH mineralization of paralytic shellfish poisoning. At the mineralization threshold, samples were taken from eight sampling ports at the end of the liquid-liquid mixer to detect the intermediate products of the mineralization process and determine the reaction pathway of •OH mineralization of paralytic shellfish poisoning. (4) Switch the inlet valve of pipeline II, pump the dinoflagellate solution from the dinoflagellate control tank D into the liquid-liquid mixer, and disperse the gradient concentration of •OH solution into fine droplets after turbulent mixing with the dinoflagellate solution at the throat. The •OH solution rapidly mineralizes the extracellular paralytic shellfish poison and kills the toxin-producing dinoflagellates at the moment the droplets break. Take samples at the sampling port determined on the pipeline at the back end of the liquid-liquid mixer, detect the concentration of paralytic shellfish poison and the density of algal cells, and establish a "dose-effect" numerical model of •OH mineralization and algae killing. According to the "dose-effect" numerical model of •OH mineralization and algae killing, determine the optimal TRO concentration. Then, under the determined TRO concentration of the main pipeline, take samples from 8 sampling ports on the pipeline at the back end of the liquid-liquid mixer, detect the concentration of degraded shellfish poison and the density of lethal dinoflagellates at different reaction times, establish a "time-effect" numerical model of •OH algae killing and mineralization, and determine the threshold of •OH algae killing and mineralization. (5) Extract the paralytic shellfish poison solution from the control tank C and transfer it to the culture tank C2 as the control group. Extract the paralytic shellfish poison solution from the treatment tank C1 with the mineralization threshold and transfer it to the culture tank C3 as the treatment group. Place a number of mussels in the three C2 culture tanks and the three C3 culture tanks. Observe the physiological status of the mussels at regular intervals, measure the concentration of paralytic shellfish poison and the activity of the antioxidant system in the mussels, and calculate the concentration of NOAEC with no observed adverse effects and the concentration of NOEC with no observed adverse effects. When NOAEC>100%, the shellfish poison solution has no acute toxic effects. When NOEC>100%, the shellfish poison solution has no chronic toxic effects. Dinoflagellate solution was extracted from control tank D and transferred to culture tank D2 as a control group. Dinoflagellate solution from treatment tank D1 (with a lethal threshold) was extracted and transferred to culture tank D3 as a treatment group. Mussels were placed in three culture tanks D2 and three culture tanks D3. The physiological status of the mussels was observed regularly, and the concentration of paralytic shellfish poisoning (NPPT) and the activity of the antioxidant system in the mussels were measured. Water samples were taken to measure the concentration of extracellular paralytic shellfish poisoning (NPPT) and NOAEC. When NOAEC > 100%, the dinoflagellate solution had no acute toxic effects; when NOEC > 100%, the dinoflagellate solution had no chronic toxic effects. Compare the physiological and biochemical parameters of mussels in culture tanks C3 and D3, estimate NOAEC and NOEC, and evaluate the differences in acute and chronic toxic effects of shellfish toxic solution and dinoflagellate solution. (6) The detection unit is equipped with an online TRO detector, an online algae counter and an online water quality detector to monitor in real time the TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color and turbidity in the seawater control tank A and seawater treatment tank A1 and the 4-HBA control tank B and 3,4-DHBA treatment tank B1; to monitor in real time the TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color and turbidity in the shellfish poisoning control tank C and shellfish poisoning treatment tank C1; and to monitor in real time the algal cell density, TRO concentration and water quality parameters such as salinity, pH, dissolved oxygen, color, turbidity and chlorophyll a in the dinoflagellate control tank D and dinoflagellate treatment tank D1.

2. The method for mineralizing paralyzing shellfish poisoning from marine dinoflagellates using hydroxyl radicals as described in claim 1, characterized in that, In step (1), a gradient TRO concentration of •OH solution is obtained by adjusting the gas-liquid ratio of oxygen active particle gas injected into the gas-liquid mixer to seawater. The remaining oxygen active particle gas is decomposed by a digester and then discharged. The oxygen flow rate is 0.5~2 L / min, the external excitation power is 100~400 W, the oxygen active particle production of the plasma source is 180~220 mg / L, the gas-liquid ratio of the gas-liquid mixer is 1:(3~10), and the TRO concentration of the •OH solution is as high as 10~80 mg / L.

3. The method for mineralizing paralyzing shellfish poisoning by hydroxyl radicals as described in claim 1, characterized in that: high-temperature sterilized seawater is injected into the seawater control tank A; a saturated 4-HBA seawater solution with a concentration of 0.1~0.5 mmol / L is prepared in the 4-HBA control tank B; and a paralyzing shellfish poisoning solution is prepared in the shellfish poisoning control tank C, with the shellfish poisoning concentration prepared to determine the •OH mineralization threshold at 2~10×10⁻⁶ mmol / L. 2 The shellfish toxicity concentration for analysis of mineralization intermediates is prepared at 1~20×10 ng / L. 3 ng / L; Dinoflagellate control tank D was used to prepare a paralytic shellfish poisoning solution containing Alexandrium, Pyrodinium, and Gyrodinium chainensis, with a total algal density of 1~50×10 ng / L. 3 cells / mL.

4. The method for mineralizing paralyzing shellfish poisoning from marine dinoflagellates using hydroxyl radicals as described in claim 1, characterized in that the flow rates of pipes I and II are 0.2~2.0 m³ / s. 3 / h, the miscibility ratio of the •OH solution in the liquid-liquid mixer to the main pipeline inlet water is 1:(10~50), and the TRO concentration gradient in the pipeline after liquid-liquid mixing and dilution is 0.2~8.0 mg / L.

5. The method for mineralizing paralyzing shellfish poisoning from marine dinoflagellates using hydroxyl radicals as described in claim 1, characterized in that, At the moment of droplet collapse, •OH mineralizes paralyzing shellfish poison through a two-step reaction: ①•OH attacks the negatively charged sites of the shellfish poison, such as the guanidinium NC bond, NH bond, and geminal glycol CO bond, opening the tricyclic structure of the shellfish poison through addition and hydrogen abstraction reactions; ②•OH further attacks the α-C and β-C sites of the intermediate product, oxidizing the straight chain to generate small molecule carboxylic acid, ultimately completely mineralizing the shellfish poison molecule into CO2, H2O, and inorganic anions.

6. The method for mineralizing paralyzing shellfish poisoning from marine dinoflagellates using hydroxyl radicals as described in claim 1, characterized in that, In step (4), the droplet collapses instantly. •OH penetrates the cell membrane and enters the algal cell, killing the dinoflagellates through two pathways: ① •OH directly attacks the phosphodiester bonds and guanine bases on the DNA in the algal cell nucleus, causing DNA double-strand breaks and fragmentation; ② •OH destroys the algal cell chloroplasts, oxidizing chlorophyll molecules, degrading photosynthetic center proteins and disintegrating thylakoid structures, resulting in the algal cells losing photosynthetic activity.

7. A device for mineralizing paralyzing shellfish poison from marine dinoflagellates using hydroxyl radicals, comprising pipeline I, pipeline II, a •OH solution generating device III, a toxicity assessment unit IV, a detection unit V, four control tanks, and four treatment tanks. The four control tanks are seawater control tank A, 4-HBA control tank B, shellfish poison control tank C, and dinoflagellate control tank D. The four treatment tanks are seawater treatment tank A1, 3,4-DHBA treatment tank B1, shellfish poison treatment tank C1, and dinoflagellate treatment tank D1. Pipeline I is a TRO regulating pipeline. It connects to the seawater control tank A and the 4-HBA control tank B through the first and second inlet valves. It is then connected to the inlet of the first high-pressure pump through the main valve of Pipeline I. The outlet of the first high-pressure pump is connected to the main inlet of the liquid-liquid mixer. The main outlet of the liquid-liquid mixer is connected to the main outlet valve of Pipeline I. It is then connected to the seawater treatment tank A1 and the 3,4-DHBA treatment tank B1 through the first and second outlet valves, respectively. Pipeline II is a mineralization and algae-killing pipeline. It connects to the shellfish poisoning control tank C and the dinoflagellate control tank D through the third and fourth inlet water valves. Then, it is connected to the inlet of the second high-pressure pump through the main valve of Pipeline II. The outlet of the second high-pressure pump is connected to the main inlet of the liquid-liquid mixer. The water treated by the liquid-liquid mixer is output through its main outlet and connected to the main outlet valve of Pipeline II. It is then connected to the shellfish poisoning treatment tank C1 and the dinoflagellate treatment tank D1 through the third and fourth outlet water valves, respectively. The •OH solution generating device III is equipped with an air inlet branch pipe and a water inlet branch pipe. The air inlet branch pipe is equipped with a flow meter, an oxygen plasma generator, and a digester. The water inlet branch pipe is equipped with a water storage tank, a water inlet valve, a booster pump, a perforated plate filter, and a gas-liquid mixer and a •OH injection valve. The oxygen plasma generator is equipped with a high-frequency high-voltage power supply. An external oxygen source is connected to the oxygen plasma generator inlet. The high-frequency high-voltage power supply is used to apply high-frequency high-voltage excitation to the oxygen plasma generator. The oxygen active particles generated by the oxygen plasma generator are split by a distributor. A portion is injected into the side inlet of the gas-liquid mixer, and the excess gas is decomposed by a decomposer and then discharged. The booster pump draws water from the storage tank, which passes through the perforated plate filter and enters the main inlet of the gas-liquid mixer. The •OH solution output from the main outlet of the gas-liquid mixer is connected to the upper and lower double suction ports of the liquid-liquid mixer. The toxicity assessment unit IV is equipped with four independent water delivery pipelines for exposure. The inlet of the first delivery pipeline is connected to the shellfish poison control tank C, and then to the first aquaculture tank C2 via the first delivery valve, the first delivery pump, and the first delivery flow meter. The inlet of the second delivery pipeline is connected to the dinoflagellate control tank D, and then to the second aquaculture tank D2 via the second delivery valve, the second delivery pump, and the second delivery flow meter. The inlet of the third delivery pipeline is connected to the shellfish poison treatment tank C1, and then to the third aquaculture tank C3 via the third delivery valve, the third delivery pump, and the third delivery flow meter. The inlet of the fourth delivery pipeline 44 is connected to the dinoflagellate treatment tank D1, and then to the fourth toxic aquaculture tank D3 via the fourth delivery valve, the fourth delivery pump, and the fourth delivery flow meter.

8. The apparatus for mineralizing paralyzing shellfish poison from marine dinoflagellates using hydroxyl radicals according to claim 7, characterized in that, In the •OH solution generating device III, an active particle detector is installed at the outlet of the oxygen plasma generator; a flow meter is installed between the outlet of the booster pump and the inlet of the orifice plate filter; the •OH solution output from the main outlet of the gas-liquid mixer is connected to the •OH injection valve after passing through the •OH solution detector and the •OH solution sampler. In the pipeline I, the outlet of the first high-pressure pump is connected to the inlet flow meter, and is connected to the main inlet of the liquid-liquid mixer via the inlet sampler. The main outlet of the liquid-liquid mixer is equipped with 8 sampling ports and the inlet of the TRO online detector in the main pipeline. In pipeline II, the outlet of the second high-pressure pump is connected to the inlet flow meter, and then connected to the main inlet of the liquid-liquid mixer via an inlet sampler; the main outlet of the liquid-liquid mixer is equipped with 8 sampling ports and the inlet of the TRO online detection instrument in the main pipeline. Pressure gauges are installed at both ends of the main inlet and main outlet of the liquid-liquid mixer to monitor the jet operation status of the liquid-liquid mixer.

9. The apparatus for mineralizing paralyzing shellfish poison from marine dinoflagellates using hydroxyl radicals according to claim 7, characterized in that, The detection unit V is equipped with detection pipelines, which are divided into a first detection inlet branch pipe and a second detection inlet branch pipe. The first detection inlet branch pipe is connected to the seawater control tank A, the 4-HBA control tank B, the shellfish poisoning control tank C, and the dinoflagellate control tank D respectively through four branch valves, and is connected to the water pump inlet through the first detection inlet main valve and the first detection flow meter. The second detection inlet branch pipe is connected to the seawater treatment tank A1, the 3,4-DHBA treatment tank B1, the shellfish poisoning treatment tank C1, and the dinoflagellate treatment tank D1 respectively through four branch valves, and is connected to the water pump inlet through the second detection inlet main valve and the second detection flow meter. The water pump outlet is divided into two paths, one of which is connected to an online algae counter and an online water quality analyzer, and the other is equipped with an online TRO analyzer and a sampling detector.

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