Electrolytic algal removal method and system based on programmed cell death induction threshold

Abstract

This invention provides an electrolytic algae removal method and system based on a programmed cell death induction threshold. The method includes the following steps: S1, real-time detection of algal pollution indicators and Caspase activity values ​​in the water to be treated; S2, based on the data detected in step S1, dynamically calculating the optimal electrolysis treatment time and optimal current density according to a preset programmed cell death induction threshold and a process parameter optimization model; the induction threshold is when the Caspase activity value reaches 150% of its baseline value; S3, controlling the electrolytic algae removal device to operate according to the optimal parameters calculated in step S2, and continuously monitoring the Caspase activity value; S4, stopping the electrolysis treatment when the Caspase activity value reaches the induction threshold and stabilizes. By real-time monitoring of Caspase activity changes and strict control to reach the 150% induction threshold, precise regulation of the programmed cell death process of algae is achieved, avoiding the risks of non-programmed cell rupture and the release of algal toxins and odors caused by strong oxidation in traditional electrolysis technology.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and more specifically, to an electrolytic algae removal method and system based on a programmed cell death induction threshold. Background Technology

[0002] Eutrophication-induced cyanobacterial blooms have become a global challenge for water environment management. Their massive proliferation not only obscures water bodies, consumes dissolved oxygen, and causes the death of aquatic organisms, but also secretes toxic and harmful substances such as algal toxins and foul odors, seriously threatening the safety of drinking water sources and the balance of ecosystems. Current mainstream algae removal technologies can be divided into three main categories: physical, biological, and chemical, and all have significant limitations: Physical algae removal methods (such as mechanical harvesting, membrane filtration, and ultrasonic disruption) require a large investment of equipment and manpower, resulting in a huge workload and high costs for large-scale algal bloom control. They can only remove surface algae and are difficult to eradicate completely. Biological algae removal methods (such as introducing algae-eating microorganisms and planting aquatic plants) depend on specific ecological conditions, have slow algae removal efficiency, and are significantly affected by environmental factors such as temperature and light, making them difficult to cope with sudden algal bloom disasters. Chemical algae removal methods (such as adding copper sulfate, potassium permanganate, and quaternary ammonium salts) can quickly kill algal cells, but chemical agents are prone to remain in the water, destroying the aquatic microbial community structure, causing secondary pollution, and may induce algal cells to release intracellular toxins prematurely, exacerbating water quality deterioration. In contrast, for example, Chinese patent CN120136255A discloses a biomimetic underwater electrolytic algae removal robot system. This system incorporates an anode titanium wire, a cathode titanium wire, a ruthenium-iridium titanium anode, and a titanium cathode for electrolytic algae removal. Chinese patent CN214936219U discloses an ultrasonic-assisted electrolytic algae removal device. The device has an electrolysis assembly fixedly connected to the right outer wall of its treatment tank. The electrolysis assembly includes two electrodes, which are fixedly located on the left and right inner walls of the treatment tank, respectively, for electrolytic algae removal. Electrolytic algae removal technology, with its core advantages such as in-situ reaction, no need for chemical additives, high algae removal efficiency, and no secondary pollution, has become a research hotspot in the field of eutrophication control in recent years. In recent years, electrolytic algae removal technology has developed rapidly both domestically and internationally, with related research and engineering applications emerging continuously. However, how to improve the efficiency of electrolytic algae removal has become an urgent technical problem to be solved. Summary of the Invention

[0003] In view of this, the present invention proposes an electrolytic algae removal method and system based on programmed cell death induction threshold to solve the problems existing in the prior art.

[0004] To achieve the above objectives, this invention proposes an electrolytic algae removal method based on a programmed cell death induction threshold, comprising the following steps: S1. Real-time detection of algal pollution indicators and Caspase enzyme activity values ​​in the water to be treated; S2. Based on the data detected in step S1, and according to the preset programmed cell death induction threshold and process parameter optimization model, dynamically calculate the optimal electrolysis treatment time and optimal current density; the induction threshold is when the Caspase activity value reaches 150% of its baseline value; S3. Control the electrolytic algae removal device to operate according to the optimal parameters calculated in step S2, and continuously monitor the Caspase activity value; S4. Once the Caspase activity value reaches the induction threshold and stabilizes, the electrolysis process is stopped.

[0005] In one embodiment, the processing time calculation formula is as follows:

[0006] Formula for calculating current density:

[0007] in: t represents the processing time, and k is a process coefficient, with a value ranging from 0.5. 2.0; C represents the real-time algal cell density or phycocyanin content, and C0 is its baseline value. E represents the real-time Caspase activity value, and E0 is its baseline value; n is a correction factor, with a value ranging from 0.8. 1.5; J represents the current density, and α is the current density coefficient, with a value ranging from 1.0. 5.0; T, DO, and pH represent real-time water temperature, dissolved oxygen, and pH value, respectively. T0, DO0, and pH0 are the corresponding baseline values.

[0008] In one embodiment, the process coefficient k is taken as 1.5 in open water with high flow. 2.0, and 0.5 in enclosed waters with low flow. 1.0; The correction factor n is set to 1.3 for cyanobacteria with dense cell membrane structures. 1.5, for cyanobacteria with thinner cell membranes, use 0.8. 1.0; The current density coefficient α is used when the algal concentration is higher than 10. 7 When the concentration is 3.0 mg / mL, take 3.0 mg / mL. 5.0, below 10 6 When the concentration is 1.0 μg / mL, take 1.0 μg / mL. 2.0.

[0009] In one embodiment, the Caspase activity baseline value E0 is determined by experimentally measuring the initial activity of the dominant cyanobacteria species in the target water body; The induction threshold is 150% of E0. When the activity value reaches this threshold, the algal cells undergo programmed cell death, and the algal toxin release is less than 1 μg / L.

[0010] In one embodiment, the content of reactive oxygen quenching substances in the water body is monitored in real time; When the content of the active oxygen quenching substance is detected to exceed the set threshold, the current density is dynamically adjusted or the treatment time is extended to ensure that the preset Caspase activity induction effect is achieved.

[0011] In one embodiment, the method is applicable to large bodies of water, including lakes, reservoirs, and rivers, and is adaptable to water temperatures of 5°C. 65℃, pH 6.0 11. Algae concentration 10 4 10 10 Water quality range per mL; The method adapts to different types of algae, including cyanobacteria, diatoms, green algae, and dinoflagellates, by adjusting process parameters.

[0012] This invention also proposes an electrolytic algae-eliminating system based on a programmed cell death induction threshold, comprising: An electrolytic processing unit includes an anode, a cathode, and a modular reactor. The anode includes any one of a ruthenium-iridium-titanium coated electrode, an iridium-tantalum-titanium coated electrode, a platinum-titanium coated electrode, a lead dioxide-titanium coated electrode, a tin-antimony-titanium coated electrode, and a sub-titanium oxide coated electrode. The cathode includes any one of a stainless steel electrode, a titanium electrode, an iron electrode, a nickel electrode, an aluminum electrode, and a copper electrode. The real-time monitoring unit includes sensors for detecting algal contamination indicators, a Caspase activity detection device, and sensors for water temperature, pH, and dissolved oxygen. The intelligent control unit, which is communicatively connected to the electrolysis processing unit and the real-time monitoring unit, is configured to perform the steps of the electrolysis algae removal method based on the programmed cell death induction threshold.

[0013] In one embodiment, the distance between the anode and cathode in the electrolysis unit is 1. 100mm adjustable; The real-time monitoring unit is distributed and covers different areas of the large water surface, with a data acquisition frequency of no less than once every 5 minutes. The intelligent control unit includes a data processing module, a parameter calculation module, and an execution control module, with a response delay of ≤1 minute.

[0014] In one embodiment, the system further includes: The wireless communication unit adopts 5G or LoRa communication protocols to realize remote monitoring and data transmission; The power supply unit, including a solar power module, an energy storage battery pack, and / or a diesel generator, supports off-grid operation of the system.

[0015] In one embodiment, the system is deployed in any of the following forms: shore-based fixed, shipborne mobile, floating platform fixed, or a combination thereof. The combined system includes a pretreatment unit, an electrolysis main treatment unit, and a deep treatment unit, and is suitable for algae removal from wastewater treatment plant effluent or pretreatment of industrial production water.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: By monitoring changes in Caspase activity in real time and strictly controlling it to reach the 150% induction threshold, precise regulation of the programmed cell death process in algae can be achieved, avoiding the non-programmed cell rupture of algae caused by strong oxidation in traditional electrolysis technology.

[0017] It achieves dynamic and precise matching between process parameters and water quality conditions, avoiding the overtreatment and energy waste caused by the one-size-fits-all approach of traditional technologies. While adapting to the complex environment of large water surfaces, energy consumption is only slightly increased, yet large-scale stable operation is achieved, resulting in a better overall cost-performance ratio.

[0018] Through distributed monitoring and dynamic parameter adjustment, it is possible to accurately adapt to the different characteristics of water bodies of different areas: for large enclosed water bodies such as lakes and reservoirs, a floating distributed layout can be adopted to cover the entire water area for monitoring and treatment; for large flowing water bodies such as rivers, fixed treatment units can be set up at key sections, and the treatment time can be dynamically adjusted in combination with the water flow speed.

[0019] Integrating multi-dimensional real-time monitoring, intelligent parameter calculation, and automatic execution control functions, it can achieve 24-hour continuous unattended operation. This significantly reduces the difficulty and cost of operation and maintenance for large-scale water surface management.

[0020] The in-situ electrolysis treatment method eliminates the need for any chemical algaecides, thus avoiding the problems of chemical residues and damage to the aquatic microbial community at the source. Simultaneously, by precisely controlling programmed cell death in algae, it not only reduces the release of algal toxins but also preserves the intact structure of dead algal cells, facilitating subsequent natural settling or assisted separation and preventing secondary pollution of the water body caused by algal cell fragments. Attached Figure Description

[0021] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. In the drawings: Figure 1 This is a flowchart of an electrolytic algae removal method based on a programmed cell death induction threshold, as described in an embodiment of the present invention. Figure 2 This is a schematic diagram of an electrolytic algae-eliminating system based on a programmed cell death induction threshold, as described in an embodiment of the present invention.

[0022] Figure 3 This is a schematic diagram of an electrolytic algae-eliminating system based on a programmed cell death induction threshold, according to another embodiment of the present invention.

[0023] Figure 4 This is a schematic diagram showing the Caspase activity response curves and susceptibility differences of different cyanobacteria in embodiments of the present invention.

[0024] Figure 5 This is a graph showing the relationship between the programmed cell death induction threshold of harmful cyanobacteria and the algae removal effect in an embodiment of the present invention. Detailed Implementation

[0025] Exemplary embodiments of the present disclosure will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present disclosure and to fully convey the scope of the disclosure to those skilled in the art. It should be noted that, unless otherwise specified, the embodiments and features described herein can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0026] It should be noted that electrolytic algae removal mainly involves three technical pathways: electrocoagulation, electroflotation, and electrooxidation. Each pathway exhibits distinct technical characteristics and application scenarios: Electrocoagulation technology generates ferrous or aluminum ions through electrolysis, forming hydroxyl oxide flocs that utilize adsorption and trapping to separate and remove algal cells, making it suitable for water bodies with high turbidity and moderate algal concentration; Electroflotation technology uses microbubbles (such as oxygen) generated by electrolysis to carry algal cells to the surface for separation, offering advantages such as high separation efficiency and low energy consumption, and is often used for algae removal in low-turbidity water bodies; Electrooxidation technology uses strong oxidizing substances (such as hydroxyl radicals) generated at the anode to destroy the cell membrane structure of algal cells, inhibiting their metabolic activity or even directly killing algal cells, resulting in thorough algae removal and simultaneous degradation of some algal toxins. In terms of specific technological innovations, low-energy in-situ copper ionization technology achieves the slow in-situ release of copper ions by precisely controlling the electric field strength. This not only enhances the inactivation effect of copper ions on algal cells but also avoids the problem of excessively high concentrations caused by traditional chemical addition of copper salts, significantly reducing the risk of secondary pollution. Electrolytic filtration technology combines electrolysis and filtration processes, using the catalytic oxidation effect on the electrode surface and the retention effect of the filter media to synergistically remove algae. It can not only efficiently enrich low-concentration algal pollutants but also generate active oxygen to react with toxic pollutants in the water through oxidation-reduction reactions, showing good application prospects in the field of drinking water purification.

[0027] Although existing electrolytic algae removal technologies have made some progress in terms of equipment structure, energy supply, and multi-technology integration, and some technologies have been applied in small-scale water body treatment, analysis of the treatment needs and actual application scenarios for large water bodies reveals that existing technologies still have four core technological bottlenecks, which seriously restrict their large-scale promotion and application in the treatment of cyanobacterial blooms in large water bodies: The optimization of process parameters lacks theoretical guidance: Current electrolytic algae removal process parameters (such as current density, treatment time, and electrode spacing) are mainly determined through empirical summaries from small-scale laboratory tests or simple orthogonal experiments. A precise parameter optimization theoretical system based on water quality parameters and algal characteristics has not yet been established, lacking scientific theoretical support. Existing studies, through orthogonal experiments, have concluded that the factors affecting the electrolytic algae removal effect, in descending order of significance, are: current density > energizing time > settling time > initial pH > electrode spacing. However, this conclusion only applies to specific experimental water bodies and algal species. In actual large-scale water bodies, algal concentration and water quality parameters (pH, dissolved oxygen, temperature, organic matter content, etc.) vary drastically in time and space. Existing empirical parameter determination methods cannot achieve dynamic and precise adjustment of process parameters, leading to large fluctuations in algae removal effects. Insufficient parameters result in incomplete algae removal, while excessively high parameters lead to energy waste and even the risk of algal cell rupture and toxin release.

[0028] The lack of precise control over algal cell death mechanisms is a major obstacle. Traditional electrolytic algae removal technology works by rapidly killing algal cells through strong oxidation or physical disruption (such as adsorption or collision on the electrode surface). This non-programmed cell death process easily triggers cell rupture, releasing large amounts of intracellular algal toxins (such as microcystin-LR, with a median lethal dose of only 50 μg / kg and strong carcinogenicity), exacerbating water pollution risks. Related studies have confirmed significant differences in the response of algal cells at different growth stages to electrolytic treatment: Algal cells in the lag and stationary phases have denser cell membranes, achieving good inactivation (algae removal rate exceeding 70%) after high-voltage, low-flow-rate treatment, but with a cell membrane rupture rate exceeding 60%, leading to a significant increase in dissolved algal toxin concentrations in the water. While algal cells in the logarithmic growth phase have thinner cell membranes and can be inactivated with low voltage, traditional parameter control methods struggle to precisely match the characteristics of algal cells at different growth stages, failing to achieve targeted regulation of algal cell death mechanisms.

[0029] Poor adaptability to large water bodies: Existing electrolytic algae removal technologies and equipment are mostly based on small-scale laboratory water bodies (10-100L) or small-area landscape water bodies (100-1000m²). 2 The design for treating large bodies of water did not fully consider the core characteristics of large water bodies: First, the water is highly mobile, and algae easily spread with the water flow. Traditional fixed equipment is difficult to achieve full coverage treatment, and the problem of "algae quickly replenishing the surrounding area after the treatment area is cleared" is likely to occur. Second, environmental factors vary greatly. Parameters such as temperature, pH, dissolved oxygen, and algae concentration in large bodies of water exhibit significant spatiotemporal heterogeneity, and traditional fixed-parameter equipment cannot adapt to the differences in water quality across the entire area. Third, the treatment scale is large. The volume of large bodies of water is usually millions or even tens of millions of cubic meters. The treatment capacity of traditional small-capacity equipment is insufficient to meet the needs of large-scale treatment, while simply increasing the size of the equipment will lead to a sharp increase in energy consumption and severe electrode polarization. Fourth, construction and operation and maintenance are difficult. Large bodies of water are deep and vast. The installation, commissioning, and subsequent maintenance of traditional equipment require a large number of ships, manpower, and equipment, resulting in high operation and maintenance costs.

[0030] The trade-off between energy consumption and efficiency: There is a significant trade-off between the energy consumption and algae removal efficiency of electrostatic algae removal technology, and existing technologies struggle to achieve a balance between "low energy consumption" and "high efficiency." Although laboratory studies have shown that the optimized electroflotation process can achieve energy consumption as low as 0.18 kWh / m³, this remains a challenge. 3(Corresponding to an algae removal rate of 70%), but this data was obtained under strictly controlled experimental conditions (such as fixed algae concentration, constant temperature and pH, and no water flow interference). In practical applications on large water surfaces, to achieve a higher algae removal rate, it is often necessary to increase the current density or extend the treatment time, leading to a significant increase in energy consumption: relevant engineering cases show that the actual energy consumption of traditional electrolytic algae removal technology in lake management is typically 1.2-2.0 kWh / m³. 3 The energy consumption is 6-10 times higher than that in laboratory settings. Furthermore, the large amounts of organic matter and suspended particles present in large bodies of water can form a passivation film on the electrode surface, leading to electrode polarization, further increasing energy consumption, and reducing algae removal efficiency. How to effectively reduce energy consumption while ensuring algae removal efficiency in large bodies of water is one of the core problems that current technologies urgently need to solve.

[0031] The purpose of this invention is to address the core bottlenecks of existing electrolytic algae removal technologies, such as the lack of theoretical guidance for optimizing process parameters, the inability to precisely control algal cell death mechanisms, poor adaptability to large water bodies, and an imbalance between energy consumption and efficiency. This invention provides a method and system for electrolytic algae removal in large water bodies based on a programmed cell death induction threshold (CCI). By establishing a quantitative correlation model between the CCI and electrolysis process parameters, and using the activity changes of Caspase, a key indicator enzyme of programmed cell death in cyanobacteria, as the core regulatory target, this invention achieves precise targeted treatment of cyanobacterial blooms in large water bodies, synergistic effects of efficient algae removal and low-energy operation, while avoiding the risk of massive release of algal toxins due to algal cell rupture. This provides a scientifically sound and practical technical solution for the treatment of cyanobacterial blooms in large water bodies (lakes, reservoirs, rivers, etc.).

[0032] The core innovation of this invention lies in breaking through the traditional technical paradigm of electrolytic algae removal that relies on empirical parameters. It establishes an optimization system for electrolytic algae removal process parameters, guided by the cyanobacterial programmed cell death induction threshold. The core of this system is the construction of a quantitative calculation formula based on Caspase activity benchmarks and induction thresholds. Research has confirmed that Caspase enzyme is a key regulator of cyanobacterial programmed cell death, and its activity changes directly reflect the cell death mode (programmed / non-programmed death). Using this activity as the core indicator, targeted regulation of the algal cell death process can be achieved. Simultaneously, by incorporating the spatiotemporal dynamic changes of key parameters such as algal concentration, temperature, dissolved oxygen, and pH in large water bodies, these parameters are integrated into the process parameter optimization model. Ultimately, this achieves precise and dynamic control of the electrolytic algae removal process, solving the problems of large fluctuations in algae removal efficiency, high energy consumption, and high risk of algal toxins in traditional technologies applied to large water bodies.

[0033] Reference Figure 1 This embodiment proposes an electrolytic algae removal method based on a programmed cell death induction threshold, comprising the following steps: S1. Real-time detection of algal pollution indicators and Caspase enzyme activity values ​​in the water to be treated; S2. Based on the data detected in step S1, and according to the preset programmed cell death induction threshold and process parameter optimization model, dynamically calculate the optimal electrolysis treatment time and optimal current density; the induction threshold is when the Caspase activity value reaches 150% of its baseline value; S3. Control the electrolytic algae removal device to operate according to the optimal parameters calculated in step S2, and continuously monitor the Caspase activity value; S4. Once the Caspase activity value reaches the induction threshold and stabilizes, stop the electrolysis process.

[0034] In the above embodiments, by real-time monitoring of Caspase activity changes and strict control to reach an induction threshold of 150%, precise regulation of the programmed cell death process in algae is achieved, avoiding the non-programmed cell rupture caused by strong oxidation in traditional electrolysis techniques. Experimental data show that when using this invention to treat Microcystis aeruginosa blooms, the algal cell rupture rate is less than 25%, and the concentration of dissolved microcystin-LR in the water is controlled below 1 μg / L (meeting the limit of GB / T 20466-2006); while the algal cell rupture rate of traditional electrolysis algae removal techniques generally exceeds 60%, and the concentration of dissolved algal toxins can reach 5-10 μg / L. In addition, studies have confirmed that after parameter optimization treatment of logarithmic-phase algal cells according to this invention, the intracellular MC-LR content is reduced by more than 40% compared with that before treatment, further reducing the risk of algal toxin release.

[0035] This embodiment utilizes a parameter optimization method based on the programmed cell death induction threshold to achieve dynamic and precise matching between process parameters and water quality conditions, avoiding the overtreatment and energy waste caused by the one-size-fits-all approach of traditional technologies. Engineering practice data shows that the actual energy consumption of traditional electrolytic algae removal technology in large-scale water surface treatment is 1.2-2.0 kWh / m². 3 In this embodiment, the energy consumption can be controlled within 0.25-0.6 kWh / m³. 3 This reduces energy consumption by 30-50% compared to traditional methods. For example, in an application at a large reservoir, the energy consumption of this invention is 0.25 kWh / m³. 3 Compared to traditional fixed-parameter electrolysis devices (energy consumption 1.5kWh / m³), 3 The energy consumption was reduced by 77%; even compared to the laboratory-optimized electroflotation process (energy consumption 0.18 kWh / m³). 3 Compared to the previous embodiment, this embodiment, while adapting to complex environments on large water surfaces, only slightly increases energy consumption, yet achieves stable operation on a large scale, resulting in a better overall cost-performance ratio.

[0036] In some embodiments, the processing time calculation formula is as follows:

[0037] Formula for calculating current density:

[0038] in: t represents the treatment time, i.e., the duration required from the start of electrolysis to the point where the caspase activity in the algal cells reaches the induction threshold. k is a process coefficient, ranging from 0.5. 2.0; its value needs to be determined according to the type of water body (such as lakes, reservoirs, rivers) and specific environmental conditions: for open waters with strong flow and rapid algae diffusion, the k value should be 1.5-2.0 to ensure sufficient treatment; for closed waters with weak flow and stable algae concentration, the k value should be 0.5-1.0 to reduce energy consumption.

[0039] C represents the real-time algal cell density or phycocyanin content, and C0 is its baseline value. E represents the real-time Caspase activity value, and E0 is its baseline value. This baseline value needs to be determined based on the historical algae concentration data of the target water body, water quality requirements, and treatment objectives.

[0040] n is a correction factor, with a value ranging from 0.8. 1.5; mainly determined based on the type of cyanobacteria and the aquatic environment: for cyanobacteria with dense cell membrane structures (such as Oscillatoria), the n value is 1.3-1.5 to enhance the sensitivity of the activity response; for cyanobacteria with thinner cell membranes (such as Microcystis aeruginosa), the n value is 0.8-1.0; when the organic matter content in the water is high, the n value can be appropriately increased by 0.2-0.3 to compensate for the effect of reactive oxygen quenching.

[0041] J represents the current density, and α is the current density coefficient, with a value ranging from 1.0. 5.0; Determined based on algae concentration and pollution level in the water: Algae concentration higher than 10 7 When the algae concentration is 10⁶ / mL, α should be 3.0-5.0; when the algae concentration is below 10⁶ / mL, α should be 3.0-5.0. 6 When the number of cells / mL is 1.0-2.0, α is taken as 1.0-2.0.

[0042] T, DO, and pH represent real-time water temperature, dissolved oxygen, and pH value, respectively. T0 is the temperature reference value, which is 25℃. This temperature is the suitable temperature for the growth and metabolism of cyanobacteria, and it is also the temperature at which the activity response is most stable as verified by experiments. Using this as a reference, parameter correction can be achieved under different temperature conditions. DO0 is the dissolved oxygen baseline value, which is 8 mg / L. This is the common value of saturated dissolved oxygen in water under normal temperature and pressure, and is used as the correction baseline for the influence of dissolved oxygen. pH0 is the pH baseline value, which is 7.0 (neutral). Under this pH condition, the oxidation efficiency and activity induction effect of electrolysis of algae are optimal. Based on this, the parameters can be adapted to different pH environments.

[0043] In some embodiments, the process coefficient k is taken as 1.5 in open water with high flow. 2.0, and 0.5 in enclosed waters with low flow. 1.0; the correction factor n is taken as 1.3 for cyanobacteria with dense cell membrane structures. 1.5, for cyanobacteria with thinner cell membranes, use 0.8. 1.0; Current density coefficient α at algal concentrations above 10 7 When the concentration is 3.0 mg / mL, take 3.0 mg / mL. 5.0, below 10 6 When the concentration is 1.0 μg / mL, take 1.0 μg / mL. 2.0.

[0044] In some embodiments, the Caspase activity baseline value E0 is determined by experimentally measuring the initial activity of the dominant cyanobacterial species in the target water body; the induction threshold is 150% of E0, and when the activity value reaches this threshold, the algal cells undergo programmed cell death, and the intracellular algal toxin release is less than 1 μg / L.

[0045] In some embodiments, the content of reactive oxygen quenching substances in the water is monitored in real time; when the content of reactive oxygen quenching substances exceeds a set threshold, the current density is dynamically adjusted or the treatment time is extended to ensure that the preset Caspase activity induction effect is achieved.

[0046] In some embodiments, the method is applicable to large bodies of water, including lakes, reservoirs, and rivers, and can be adapted to water temperatures of 5°C. 65℃, pH 6.0 11. Algae concentration 10 4 10 10 The water quality range was measured by adjusting process parameters to suit different types of algae, including cyanobacteria, diatoms, green algae, and dinoflagellates.

[0047] Reference Figure 2 and Figure 3 This invention also proposes an electrolytic algae removal system based on a programmed cell death induction threshold, comprising: an electrolytic treatment unit including an anode, a cathode, and a modular reactor; the anode using any one of the following: ruthenium-iridium-titanium coated electrode, iridium-tantalum-titanium coated electrode, platinum-titanium coated electrode, lead dioxide-titanium coated electrode, tin-antimony-titanium coated electrode, and titanium suboxide coated electrode; and the cathode using any one of the following: stainless steel electrode, or titanium electrode, iron electrode, nickel electrode, aluminum electrode, and copper electrode. It should be noted that other materials may also be used besides those listed above.

[0048] Specifically, the core of the electrolysis treatment unit consists of an anode, a cathode, and a modular reactor. The anode uses a ruthenium-titanium coated electrode, which boasts high catalytic activity, corrosion resistance, and a long service life (continuous operation exceeding 5000 hours), efficiently generating active oxidizing substances (hydroxyl radicals, hypochlorous acid, etc.). The cathode uses stainless steel or titanium electrodes to ensure electrode stability and reduce costs. The electrode spacing is adjustable from 1-100mm, dynamically adjusted by an intelligent control unit based on water turbidity and algae concentration (widening the spacing to prevent clogging when turbidity is high, and narrowing it to improve oxidation efficiency when turbidity is low). The core function of this unit is to induce programmed cell death in algae under the precise current density output controlled by the intelligent control unit, while avoiding excessive oxidation that could lead to cell rupture.

[0049] The real-time monitoring unit includes sensors for detecting algal contamination indicators, a Caspase activity detection device, and sensors for water temperature, pH, and dissolved oxygen.

[0050] Specifically, the real-time monitoring unit adopts a multi-sensor integrated design, including algae density / phycocyanin detection sensors (with a detection accuracy of up to 10). 4 The system includes a Caspase activity detection device (using fluorescence spectrophotometry with a detection limit of 10 relative activity units), a high-precision pH sensor (measurement range 4.0-10.0, accuracy ±0.01), a dissolved oxygen sensor (measurement range 0-20 mg / L, accuracy ±0.05 mg / L), and a temperature sensor (measurement range 0-40℃, accuracy ±0.1℃). These sensors are distributed to cover different areas of a large water surface for water quality monitoring. Data is collected once every 5 minutes to ensure real-time capture of dynamic changes in water quality and algae characteristics.

[0051] The intelligent control unit, which is communicatively connected to the electrolysis processing unit and the real-time monitoring unit, is configured to perform the steps of the electrolysis algae removal method based on the programmed cell death induction threshold.

[0052] Specifically, the intelligent control unit, as the "core brain" of the system, integrates a data processing module, a parameter calculation module, and an execution control module. The data processing module filters, calibrates, and integrates the multi-dimensional data collected by the real-time monitoring unit; the parameter calculation module embeds the processing time and current density calculation formulas of this invention, and automatically calculates the optimal process parameters based on the integrated real-time data; the execution control module regulates the current output, processing time, and electrode spacing of the electrolysis processing unit through signal transmission, while simultaneously coordinating the operation of auxiliary units to achieve full automation of the monitoring, calculation, and control process, with a response delay of ≤1 minute.

[0053] Reference Figure 4 and Figure 5The above embodiments, through distributed monitoring and dynamic parameter adjustment, can accurately adapt to the different characteristics of various large water bodies: for enclosed large water bodies such as lakes and reservoirs, a floating distributed deployment can be used to cover the entire water area for monitoring and treatment; for flowing large water bodies such as rivers, fixed treatment units can be set up at key sections, and the treatment time can be dynamically adjusted in conjunction with the water flow velocity. Simultaneously, by adjusting coefficients such as k, n, and α in the formula, it can adapt to the characteristics of different types of cyanobacteria (Microcystis, Anabaena, Longsporium, Spirophyllum, Cylindrica, etc.), and can even be extended to the treatment of eukaryotic algae such as diatoms, green algae, and dinoflagellates. Experimental verification shows that this invention is effective at water temperatures of 5-65℃, pH of 6.0-11, and algae concentrations of 10... 4 -10 10 It can achieve an algae removal rate of over 80% across a wide range of algae / mL, making it far more adaptable than traditional fixed-parameter technologies.

[0054] The above embodiments integrate multi-dimensional real-time monitoring, intelligent parameter calculation, and automatic execution control functions, enabling 24-hour continuous unattended operation. The intelligent control unit has data storage, fault diagnosis, and remote early warning functions, automatically recording historical monitoring data and processing parameters for later process optimization. When sensor malfunction, electrode polarization, or sudden changes in water quality are detected, emergency procedures (such as switching to a backup sensor, initiating electrode cleaning, and adjusting process parameters) can be automatically initiated, and alarm information can be sent to the remote control center. Compared with traditional technologies that require frequent manual inspections and parameter adjustments, this invention can reduce the need for manual intervention by more than 80%, significantly reducing the operation and maintenance difficulty and cost of large-scale water surface management.

[0055] The system in this embodiment employs in-situ electrolysis, eliminating the need for any chemical algaecides and preventing the problems of chemical residues and damage to the aquatic microbial community from the source. Simultaneously, by precisely controlling programmed cell death in algae, it not only reduces the release of algal toxins but also preserves the intact structure of dead algal cells, facilitating subsequent natural settling or assisted separation and preventing secondary pollution of the water body caused by algal cell fragments. Furthermore, the system's electrode materials (iridium-tantalum titanium, lead-titanium dioxide, stainless steel, aluminum, copper, etc.) are all environmentally friendly materials with a long service life and no harmful substances leaching out. The cleaning wastewater from the auxiliary unit can be recycled back into the water body after simple treatment, with no additional pollutant discharge, fully meeting the environmental protection requirements for large-scale water surface ecological management.

[0056] In some embodiments, the system further includes an auxiliary unit, which may specifically include an intelligent water inlet / outlet system, an electrode self-cleaning system, and an emergency backup system. The water inlet / outlet system employs a flow-adjustable pump body, dynamically adjusting the water flow rate (adjustment range 0.5-5m) according to the real-time load of the processing unit. 3The system ensures full contact between algae and electrodes; the electrode self-cleaning system uses pneumatic wiping, and automatically starts the cleaning program when electrode polarization causes a decrease in current efficiency of more than 10%, avoiding the formation of a passivation film on the electrode surface and ensuring stable processing efficiency; the emergency support system integrates a backup power supply and a fault alarm module to ensure the safe operation of the system in extreme weather or equipment failure, while also providing timely feedback on fault information.

[0057] In some embodiments, the distance between the anode and cathode in the electrolysis unit is 1. 100mm adjustable; the real-time monitoring unit adopts a distributed layout, covering different areas of the large water surface, and the data acquisition frequency is no less than once every 5 minutes; the intelligent control unit includes a data processing module, a parameter calculation module and an execution control module, with a response delay of ≤1 minute.

[0058] In some embodiments, the system further includes: a wireless communication unit that uses 5G or LoRa communication protocols to enable remote monitoring and data transmission; and a power supply unit that includes a solar power module, an energy storage battery pack, and / or a diesel generator to support off-grid operation of the system.

[0059] In some embodiments, the system is deployed in any of the following forms: shore-based fixed type, shipborne mobile type, floating platform fixed type, or combination type; the combination system includes a pretreatment unit, an electrolysis main treatment unit, and an advanced treatment unit, and is suitable for algae removal from wastewater treatment plant effluent or pretreatment of industrial production water.

[0060] Example 1: Small-scale water body verification experiment.

[0061] Experimental objective: To verify the accuracy of the electrolytic algae removal process parameter optimization model based on the Caspase activity induction threshold, to clarify the algae removal effect and algal toxin control capability of this method on Microcystis in a controlled small water body environment, and to provide basic experimental data support for subsequent large water surface engineering applications.

[0062] Experimental conditions: Water treatment: 10L of laboratory-pure cultured Microcystis aeruginosa (FACHB-1196) was cultured in BG11 medium to the mid-logarithmic growth phase to ensure uniform algal cell activity.

[0063] Initial algal density: 3.0 × 10⁻⁶ 6 The number of cells / mL was determined by counting with a hemocytometer. Each group was counted in triplicate, and the average value was taken.

[0064] Water temperature: 25±1℃, temperature is controlled by a constant temperature water bath, and the temperature fluctuation error is ≤0.5℃.

[0065] pH: 7.0±0.2, adjusted by 0.1mol / L HCl or NaOH solution, and monitored in real time using a precision pH meter.

[0066] Dissolved oxygen: 8.0±0.5mg / L. After adjusting to saturated dissolved oxygen using an aeration device, let stand for 2 hours to ensure uniform distribution of dissolved oxygen.

[0067] Experimental apparatus: 500mL beaker (as a small electrolytic reactor), ruthenium-titanium coated anode (50cm² area) 2 Titanium cathode (50cm²) 2 DC regulated power supply (output accuracy 0.01mA), high-speed refrigerated centrifuge (speed range 0-15000r / min), fluorescence spectrophotometer (excitation wavelength 488nm, emission wavelength 525nm), precision pH meter (accuracy ±0.01), dissolved oxygen meter (accuracy ±0.05mg / L).

[0068] Experimental steps: Caspase activity baseline (E0) determination: The core objective of this step is to determine the initial activity level of the *Microcystis* used in the experiment, providing a benchmark for subsequent induction threshold determination. The determination is performed using fluorescence spectrophotometry based on the specific substrate hydrolysis reaction. The specific procedures are as follows: Take 100 mL of the logarithmic growth phase algal solution and place it in a centrifuge tube. Centrifuge at 4℃ and 8000 r / min for 10 min, discard the supernatant, and collect the algal cell precipitate at the bottom.

[0069] Add 2 mL of phosphate buffer (PBS, pH 7.4, concentration 0.05 mol / L) to the algal cell pellet, and use an ultrasonic cell disruptor (power 200W, working time 3s, interval 5s, total time 5min) to disrupt the cells in an ice bath to obtain cell homogenate; then centrifuge at 4℃ and 12000r / min for 15min, and take the supernatant as crude enzyme solution.

[0070] Mix 100 μL of crude enzyme solution with 100 μL of specific substrate (Z-RR-AMC; Sigma-Aldrich, USA, concentration 100 μmol / L) and incubate in a 37℃ water bath for 30 min. Use a fluorescence spectrophotometer to measure the fluorescence intensity of the reaction system, with the excitation wavelength set at 488 nm and the emission wavelength set at 525 nm.

[0071] Meanwhile, a blank control group (using PBS buffer instead of crude enzyme solution) and a negative control group (inactivated crude enzyme solution) were set up. After subtracting the background fluorescence value, the initial Caspase activity was calculated according to the activity standard curve, and finally, E0=100 relative activity units (RU) were obtained.

[0072] Electrolysis treatment parameter calculation: Based on the process parameter optimization formula constructed in this invention, and combined with the controlled conditions of this small water body experiment, the values ​​of each parameter were determined and the calculations were completed. The specific process is as follows: The formula for calculating processing time is: t = k × (C / C0) × (E / E0) n ; Parameter values ​​were chosen based on the following: This experiment involved a closed, small water body with stable algae concentration; therefore, the process coefficient k was set to 1.0. The target algae density was consistent with the initial algae density (C = C0 = 3.0 × 10⁻⁶). 6 (cells / mL); initial activity E=E0=100R.U.; Microcystis cell membrane is relatively thin, so the correction factor n is set to 1.0.

[0073] Calculation process: t = 1.0 × (3.0 × 10) 6 / 3.0×10 6 )×(100 / 100) 1 =1.0 × 1.0 × 1.0 = 1.0 hour; The formula for calculating current density is: J = α × (C / C0) × (T / T0) × (DO / DO0) × (pH / pH0); Parameter values ​​are based on: initial algal density of 3.0 × 10⁻⁶. 6 The concentration was low to medium, so the current density coefficient α was set to 2.0. The experimental water temperature, dissolved oxygen, and pH were all controlled under the baseline conditions (T=T0=25℃, DO=DO0=8mg / L, pH=pH0=7.0), and no additional correction was required.

[0074] Calculation process: J = 2.0 × 1.0 × 1.0 × 1.0 × 1.0 = 2.0 mA / cm 2 .

[0075] Parameter validation: Based on preliminary experimental data, the calculated parameters can ensure that the activity of algal cells gradually increases to the induction threshold (150 R.U.), while avoiding excessive oxidation that could lead to cell rupture, thus balancing algae removal efficiency with low energy consumption.

[0076] Electrolysis process: Electrolysis was carried out strictly according to the calculated parameters, and the state of the reaction system was monitored throughout the process to ensure process stability. The specific operation is as follows: Electrode pretreatment: The ruthenium-titanium coated anode and titanium cathode were soaked in 1 mol / L HCl solution for 30 min (to remove the surface oxide layer) and ultrasonically cleaned with deionized water for 10 min. After drying, they were installed in a 500 mL beaker reactor. The electrode spacing was adjusted to 10 mm to ensure that the two electrodes were parallel and aligned.

[0077] Reactor setup: Add 10L of the prepared algal solution to the reactor, and place a magnetic stir bar (200r / min) to ensure that the algal solution is mixed evenly and to avoid local concentration differences; place the reactor in a constant temperature water bath and maintain the water temperature at 25±1℃.

[0078] Electrolysis start-up and monitoring: Connect a DC regulated power supply and set the current density to 2.0 mA / cm². 2 Electrolysis was initiated; samples were taken at a frequency of 15 minutes per sample, with each sample being 5 mL. Caspase activity was measured using the aforementioned fluorescence spectrophotometric method. When the activity reached 150 R.U. (i.e., E / E0 = 1.5, reaching the programmed cell death induction threshold), the current parameters were maintained for 30 minutes before electrolysis was stopped to ensure that the algal cells fully entered the programmed cell death process.

[0079] Effectiveness evaluation: After treatment, the effectiveness was evaluated using national standard methods and professional testing techniques, focusing on two core dimensions: algae removal efficiency and algal toxin control. Specific indicators and testing methods are as follows: Algae removal efficiency test: Take the treated algae solution and use the hemocytometer to determine the density of remaining algae cells (count 5 times in parallel for each group). At the same time, determine the chlorophyll a content according to GB / T7494-1987 "Determination of total nitrogen in water quality by alkaline potassium persulfate digestion ultraviolet spectrophotometry". Calculate the algae cell removal rate and chlorophyll a removal rate.

[0080] The results showed that the algal cell removal rate was 75.2%±1.3%, the chlorophyll a removal rate was 78.4%±0.8%, and the relative standard deviation (RSD) of parallel experiments was less than 2%, indicating that the algae removal effect was stable.

[0081] Algal toxin control effect detection: The content of intracellular microcystin-LR (MC-LR) in the algal solution before and after treatment was determined by high performance liquid chromatography (HPLC). Chromatographic conditions: C18 column (4.6 mm × 250 mm, 5 μm), mobile phase: methanol:water = 60:40 (containing 0.1% trifluoroacetic acid), flow rate 1.0 mL / min, detection wavelength 238 nm, column temperature 30 ℃.

[0082] The results showed that the intracellular microcystin-LR content decreased by 40% ± 3.2% compared with that before treatment, and the concentration of dissolved MC-LR in the water after treatment was 0.8 μg / L, which was lower than the limit of GB / T 20466-2006 (1 μg / L), effectively avoiding the risk of algal toxin release.

[0083] Experimental Conclusion: This embodiment, through strict control of experimental conditions in a small water body, verified the scientific validity and effectiveness of the electrolytic algae removal method based on the Caspase activity induction threshold. Experimental results show that by accurately calculating and controlling the treatment time (1.0 h) and current density (2.0 mA / cm²), the method can effectively remove algae. 2 This method successfully induced the Caspase activity of Microcystis aeruginosa to a programmed cell death threshold of 150 R.U., achieving a high algae removal efficiency of over 95%. Simultaneously, the intracellular algal toxin content was significantly reduced, and the dissolved algal toxin concentration met national standards, achieving the dual goals of "highly efficient algae removal + low algal toxin risk." Furthermore, the parameters obtained in this experiment showed a 98% fit with the computational model, demonstrating the accuracy of the process parameter optimization system of this invention and laying a solid experimental foundation for subsequent dynamic parameter adjustment and system application in complex environments on large water surfaces.

[0084] Example 2: Application in large-scale water surface engineering (verification of large-scale treatment).

[0085] Project Background: A large drinking water source reservoir (drainage area 50 km²) 2 The reservoir area is approximately 10 km². 2 The average water depth is 15 meters, and the total reservoir capacity is 150 million cubic meters. 3 A large-scale cyanobacterial bloom occurred during the summer, with monitoring showing that the dominant species was Microcystis (accounting for more than 85% of the total algae), and the average algal density in the central area of ​​the reservoir reached 5.0 × 10⁻⁶. 7 The algal density at the edge region was 2.0 × 10⁶ cells / mL. 7 -3.5×10 7 With a concentration of microcystins per mL and a water transparency of only 30 cm, the concentration of dissolved microcystin-LR reached 6.2 μg / L, far exceeding the limit of GB / T 20466-2006 (1 μg / L), seriously threatening the drinking water safety of nearly 2 million people in three surrounding cities. There is an urgent need to carry out efficient and safe large-scale algae removal and treatment.

[0086] System design scheme: Equipment Layout: Based on reservoir flow field simulation results (calculated using the MIKE21 hydrodynamic model) and combined with data from algae distribution hotspot investigations, a distributed layout strategy of "dense in the core area + interception at key sections" is adopted. Electrolytic algae removal units are arranged at three key sections of the reservoir: the inlet (to intercept algae from upstream and reduce the load on subsequent treatment), the central pollution core area (where algae concentration is highest and treatment is intensified), and the outlet (to ensure that the effluent quality meets the standards). Among them, nine units are arranged in the central area, and three units are arranged at the inlet and outlet. Each unit is configured with a processing capacity of 1000m. 3The modular electrolysis reactor has a capacity of / h and is installed on a floating platform (hull size 6m×4m×1.5m). It is equipped with an anchoring device that can withstand level 3 winds and waves and is adaptable to changes in reservoir water depth (suitable for water depths of 5-25m). The electrode spacing is preset to 10mm and can be dynamically adjusted according to the turbidity of the water. A total of 15 processing units are deployed, with a total processing capacity of 15,000 m³. 3 / h, calculated based on the average daily water exchange cycle of the reservoir, can achieve full circulation treatment of the reservoir water in 3 days, ensuring that the treatment coverage is comprehensive and without dead ends.

[0087] Electrolytic algae removal units are installed at the reservoir's inlet, central area, and outlet; each unit has a treatment capacity of 1000 m³ / h. 3 An electrolytic reactor with a capacity of 15000 m³ / h; 15 processing units are arranged in total, with a total processing capacity of 15000 m³ / h. 3 / h.

[0088] Real-time monitoring system: Constructing a three-tiered monitoring network of "unit-level monitoring + regional-level monitoring + central-level control": Each processing unit is equipped with an integrated algae density / phycocyanin detection sensor (detection range 10). 4 -10 9 (Size: per mL, accuracy: ±5%, response time: ≤30 seconds)); Caspase activity detection device (using fluorescence spectrophotometry, detection limit: 10 relative activity units, detection frequency: once every 15 minutes); Multi-parameter water quality monitor (simultaneously monitors pH, dissolved oxygen, and temperature, with measurement ranges of 4.0-10.0, 0-20 mg / L, and 0-40℃, respectively, and accuracies of ±0.01, ±0.05 mg / L, and ±0.1℃, respectively). Monitoring data is transmitted in real time to the central control center on the shore via a LoRa wireless communication module (transmission distance ≥3km, strong anti-interference capability). The center is equipped with a data storage server (capable of storing one year of historical data) and a visualization monitoring platform, enabling 24-hour continuous monitoring, real-time display of data curves, and alarms for abnormal thresholds (such as algae density exceeding 10). 8 Automatic alarm will sound when the number of cells / mL or the activity deviates from the threshold by ±20%.

[0089] Each treatment unit is equipped with an algae density sensor, a Caspase activity detection device, and a multi-parameter water quality monitor.

[0090] The data is transmitted wirelessly to the central control center, enabling continuous 24-hour monitoring.

[0091] Process parameter calculation and optimization: Combining on-site water quality monitoring data from the reservoir with the core formula of this invention, initial parameters were calculated, and a dynamic optimization mechanism was established. Initial parameter calculation: The initial algal density in the reservoir area, measured on-site, was C = 5.0 × 10⁻⁶.7 Therefore, the baseline value C0 is set to 5.0 × 10⁻⁶ cells / mL. 7 Caspase activity per mL was measured by on-site sampling; the initial Caspase activity of the dominant species Microcystis was E0 = 80 relative activity units, and the target induction threshold was 120 relative activity units (1.5 × E0). Calculation of treatment time: Considering the reservoir is an open water body with strong flow, the process coefficient k is taken as 1.5; initial activity E = 80 relative activity units, target activity E = 100 relative activity units (transitional value during the start-up phase), and the Microcystis correction coefficient n is taken as 1.2; substituting into the formula t = 1.5 × (5.0 × 10 7 / 5.0×10 7 )×(100 / 80) 1 · 2 =1.5×1×(1.25) 1 · 2 ≈1.875 hours; Calculated current density: The initial algal density was relatively high (5.0 × 10⁻⁶). 7 (Cells / mL), current density coefficient α is taken as 3.0; the actual measured water temperature T=28℃ (reference value T0=25℃), dissolved oxygen DO=6mg / L (reference value DO0=8mg / L), pH=7.5 (reference value pH0=7.0); substituting into the formula J=3.0×1.0×(28 / 25)×(6 / 8)×(7.5 / 7.0)=3.0×1.0×1.12×0.75×1.07≈2.81mA / cm 2 ; Dynamic adjustment: The system is set to automatically update parameters every hour. When any of the following conditions are detected, the optimal parameters will be recalculated immediately: ① Algae density fluctuation exceeds 20%; ② Caspase activity deviates from the target threshold by ±15%; ③ Any parameter such as water temperature, pH, or dissolved oxygen changes by more than 10%. During the adjustment process, the change in current density will be ensured to be no more than 0.5 mA / cm². 2 To avoid shock oxidation that could cause algal cell rupture.

[0092] Initial parameter calculation: C0 = 5.0 × 10 7 Cells / mL, E0=80 relative activity units (as determined on-site); Calculate the processing time: t = 1.5 × (5.0 × 10⁻⁶) 7 / 5.0×10 7 )×(100 / 80) 1 · 2 =1.875 hours; Calculate the current density: J = 3.0 × 1.0 × (28 / 25) × (6 / 8) × (7.5 / 7.0) = 3.0 × 1.0 × 1.12 × 0.75 × 1.07 = 2.81 mA / cm² 2 .

[0093] Dynamic adjustment: The system automatically updates parameters every hour based on real-time monitoring data.

[0094] Operational Results: The system operated continuously and stably for 30 days. The effectiveness of the treatment was evaluated through multi-point sampling and monitoring (12 monitoring points were set up in the reservoir area). Specific data are as follows: Algae control effect: The overall algae density of the reservoir decreased from the initial 5.0 × 10⁻⁶. 7 The number of cells / mL decreased to 3.2 × 10⁻⁶. 6 CFU / mL (far below the drinking water source control standard of 5.0×10⁻⁶) 6 (number of algae / mL), with the algal density in the central treatment area decreasing to 1.8 × 10⁻⁶. 6 The algae removal rate was 76.4%; the chlorophyll a content decreased from the initial 85 μg / L to 12 μg / L, with a removal rate of 85.9%. Energy consumption and cost advantages: The average energy consumption of the system is 0.25 kWh / m³. 3 Compared to traditional fixed-parameter electrolytic algae removal technology (engineering measured energy consumption 1.2-2.0 kWh / m³), this technology offers significant advantages. 3 The water volume was reduced by 79%-87%, based on a daily treatment capacity of 360,000 m³. 3 Calculations show that the average daily energy consumption is only 9,000 kWh, saving 32,400 to 58,500 kWh of energy per day compared to traditional technologies; Comprehensive water quality improvement: Water transparency increased from 30cm to 85cm, dissolved microcystin-LR concentration was stably controlled below 0.8μg / L (meeting national standards), pH was stable between 7.2 and 7.8, dissolved oxygen content increased to 7.5-8.2mg / L, water odor was completely eliminated, and water quality reached GB3838-2002 Class II standard, meeting the requirements for drinking water source supply.

[0095] After 30 days of continuous operation, the overall algae density in the reservoir decreased from 5.0 × 10⁻⁶. 7 The number of cells / mL decreased to 5.0 × 10⁻⁶. 6 The number of cells / mL is below 0.25; the average energy consumption is 0.25 kWh / m³. 3 Compared with traditional methods, it reduces water quality by about 40%; water transparency increases from 30cm to 80cm, and water quality is significantly improved.

[0096] Engineering Features: This embodiment fully verifies the core technological advantages and engineering feasibility of the present invention in complex environments on large water surfaces: Through floating distributed layout and water flow field adaptation design, it solves the problem of insufficient full-water coverage and easy occurrence of "blind spots" in traditional fixed equipment; the dynamic parameter optimization mechanism based on Caspase activity threshold effectively adapts to the characteristics of strong spatiotemporal heterogeneity of water quality on large water surfaces, ensuring stable algae removal effect and no risk of secondary release of algal toxins; the integrated intelligent system of "monitoring-computation-control" significantly reduces the operation and maintenance difficulty of large water surface treatment, requiring no manual intervention throughout the process, and the equipment failure rate is less than 3%; the low energy consumption advantage significantly reduces the operating cost of large-scale treatment, providing a replicable and scalable engineering technology solution for the treatment of cyanobacterial blooms in drinking water sources such as large lakes and reservoirs.

[0097] Example 3: Specific treatments for different types of cyanobacteria blooms.

[0098] Experimental Objective: Addressing the diversity of dominant cyanobacterial bloom species in natural water bodies (significant differences in cell structure, physiological characteristics, and toxicity among different algal species), and the difficulty of adapting traditional electrolytic algae removal techniques to the treatment needs of various algal species due to fixed parameters, this embodiment aims to verify the specific adaptability and treatment effect of the parameter optimization system based on the Caspase activity induction threshold of this invention on different typical cyanobacterial blooms. Through targeted treatment of three common high-risk cyanobacterial blooms—Microcystis, Longiflora, and Cylindrica pseudocystis—the experiment clarifies the corresponding process parameter adjustment strategies for different algal species, verifying the core advantage of this invention—"one system, multiple adaptability"—in complex algal bloom water bodies, and providing parameter basis and technical support for the actual treatment of mixed algal blooms in large water bodies.

[0099] Experimental Design: 1. Algal strain preparation and pretreatment: Three typical cyanobacteria blooming algae were selected as experimental subjects, all isolated from a eutrophic lake in southern my country (the actual area where the algal bloom occurred). After purification and culture, they were used in the experiment to ensure the representativeness and authenticity of the algal strains. Microcystis: The most widely distributed and frequently occurring cyanobacterial bloom algae globally, capable of producing potent carcinogenic microcystin toxins. Its cell membrane is relatively thin, but the colony easily forms a gel-like sheath. In experimental culture, the initial algal density was controlled at 3.0 × 10⁻⁶ during the mid-logarithmic growth phase. 6 Cells / mL were cultured in BG11 medium at 25°C, with a light intensity of 3000 lux and a light-dark ratio of 12h:12h.

[0100] Long-spored algae: a common filamentous cyanobacterium that easily forms network colonies. Its cell membrane is relatively thick and rich in cellulose, exhibiting strong tolerance to oxidative stress. It can produce anthocyanin; the initial algal density at the early stationary phase is 2.5 × 10⁻⁶. 6The cells / mL were cultured under the same conditions as Microcystis aeruginosa, with an additional 0.1 g / L NaHCO3 added to suit its carbon fixation characteristics.

[0101] *Cyclops*: an invasive cyanobacterium with a wide range of environmental adaptability. It produces cyclopsin (a hepatotoxic and neurotoxic agent). Its cells are elongated cylindrical with dense cell walls. When cultured to the late logarithmic growth phase, the initial algal density is 2.0 × 10⁻⁶. 6 The cell / mL culture temperature was adjusted to 28℃ (to match its optimal growth temperature), and the light intensity was 2500 lux.

[0102] 2. Caspase activity baseline determination: The determination was performed using fluorescence spectrophotometry combined with a specific substrate (Z-RR-AMC, concentration 100 μmol / L) to ensure the comparability of activity data across different algal species. The specific procedure is as follows: Take 100 mL of algal culture in the logarithmic growth phase of each algal species, centrifuge at 4℃ and 8000 r / min for 10 min, and collect the algal cell pellet. Add 2 mL of phosphate buffer (PBS, 0.05 mol / L) at pH 7.4, and obtain cell homogenate using an ultrasonic cell disruptor (power 200W, 3 s operation, 5 s interval, ice bath disruption for 5 min). Centrifuge again (4℃, 12000 r / min, 15 min), and collect the supernatant as crude enzyme solution. Mix 100 μL of crude enzyme solution with 100 μL of specific substrate, incubate at 37℃ for 30 min, and measure the fluorescence intensity using a fluorescence spectrophotometer (excitation wavelength 488 nm, emission wavelength 525 nm). Subtract the background fluorescence values ​​of the blank control group (PBS buffer instead of crude enzyme solution) and the inactivated control group (crude enzyme solution boiled at 100℃ for 10 min), and calculate the baseline activity value according to the activity standard curve. Set up 3 parallel samples for each experiment, and control the relative standard deviation (RSD) within 5%. The final measurement results are as follows: Microcystis: E0=120 relative activity units (RU), which is consistent with the initial activity range of Microcystis reported in most literature, verifying the reliability of the data; Longsporium: E0=85 relative activity units (RU), lower than Microcystis, which is presumably related to its filamentous cell structure and strong environmental tolerance; Cylindrica pseudocystis: E0=95 relative activity units (RU), which is between the former two, matching its cell wall density and metabolic activity.

[0103] 3. Calculation and Determination of Processing Parameters: Based on the process parameter optimization formula of this invention, and combined with the cell characteristics (cell membrane thickness, sensitivity to oxidative stress) and initial culture conditions of the three algal species, the process parameters (k, n, α values) for each algal species are determined respectively. The specific calculation process is as follows (microcystis aeruginosa is used as an example for detailed explanation; the other two algal species are derived using the same logic): (1) Calculation of Microcystis parameters: k value determination: k is a process coefficient, which is related to the water type and algal species sensitivity. Microcystis cell membranes are relatively thin and highly sensitive to reactive oxygen species (such as hydroxyl radicals) generated by electrolytic oxidation. The activity can be induced to reach the threshold without a long treatment time. Therefore, referring to the low energy consumption range of closed water bodies, k=0.8 was determined. The value of n was determined as follows: n is a correction factor, which is related to the algal species and cell membrane structure. Microcystis cells have thin membranes, but the colonies easily form gel sheaths, which slightly hinders the contact between oxidized substances and intracellular enzymes. Therefore, the correction factor needs to be appropriately increased to enhance the sensitivity of the activity response; n = 1.2 was determined. Induction threshold setting: uniformly adopt 150% of E0, that is, target activity E = 1.5 × 120 = 180 R.U.; Processing time calculation: t = k × (C / C0) × (E / E0) n Where C represents the initial algal density of 3.0 × 10⁻⁶. 6 C0 was selected as the baseline value consistent with the initial algal density (3.0 × 102). 6 (number of cells / mL), therefore C / C0 = 1.0. Substituting the values, we get: t = 0.8 × 1.0 × (180 / 120) 1 · 2 =0.8×1.0×1.5 1 · 2 ≈0.8 × 1.58 = 1.13 hours; Current density calculation: J = α × (C / C0) × (T / T0) × (DO / DO0) × (pH / pH0). The initial algal density of Microcystis was 3.0 × 10⁻⁶. 6 The concentration of dissolved oxygen (DO) was determined to be 2.5 mg / mL (medium to low concentration); the experimental temperature was T = 25℃ (consistent with the baseline T0 = 25℃); dissolved oxygen (DO) was 8 mg / L (consistent with the baseline DO0 = 8 mg / L); and pH was 7.0 (consistent with the baseline pH0 = 7.0). Therefore, the environmental factor correction term was 1.0 for all parameters. Substituting the values ​​into the calculation: J = 2.5 × 1.0 × 1.0 × 1.0 × 1.0 = 2.5 mA / cm² 2 .

[0104] (2) Calculation of parameters for *Leptospora*: k value determined: Longsporium is a filamentous alga with a dense cell structure and strong tolerance to oxidative stress. The treatment time needs to be extended to ensure sufficient activity induction. Therefore, k=1.2 (a value with high adaptability to closed water bodies). The value of n was determined as follows: the cell wall is rich in cellulose, making it difficult for oxidative substances to penetrate. Therefore, the correction coefficient needs to be increased to enhance the activity response, and n=1.4 was determined. Target activity E = 1.5 × 85 = 127.5 RU, initial algal density C = 2.5 × 10 6 cells / mL, C0 = 2.5 × 10 6 cells / mL (C / C0=1.0); Processing time t = 1.2 × 1.0 × (127.5 / 85) 1 · 4 =1.2×1.5 1 · 4 ≈1.2 × 1.74 = 1.50 hours; Current density α value: 2.5 × 10⁻⁶ for filamentous algae concentration 6 The oxidation intensity needs to be increased by increasing the current density to achieve a concentration of 1 / mL, thus α = 3.0. Since all environmental factors are baseline values, J = 3.0 × 1.0 × 1.0 × 1.0 × 1.0 = 3.0 mA / cm². 2 .

[0105] (3) Calculation of parameters for Cyclospora pseudocytozoa: k value determined: Cylindrica pseudocystis is highly adaptable and has a moderate degree of cell membrane density, so k=1.0 (intermediate value). n value determined: Due to the dense cell wall, the correction factor needs to be appropriately increased, and n is determined to be 1.3; Target activity E = 1.5 × 95 = 142.5 RU, initial algal density C = 2.0 × 10⁻⁶ 6 cells / mL, C0 = 2.0 × 10⁻⁶ 6 cells / mL (C / C0=1.0); Processing time t = 1.0 × 1.0 × (142.5 / 95) 1 · 3 =1.0×1.5 1 · 3 ≈1.0 × 1.35 = 1.35 hours; Current density α value: Algae density 2.0 × 10 6 The concentration of particles per mL was determined, and α was set at 2.8. Since all environmental factors were baseline values, J = 2.8 × 1.0 × 1.0 × 1.0 × 1.0 = 2.8 mA / cm³. 2 .

[0106] 4. Electrolysis Treatment and Effect Testing: The same small modular electrolysis reactor as in Example 1 was used (anode: ruthenium-titanium coated electrode, area 50 cm²). 2 Cathode: Titanium electrode, area 50 cm² 2Electrolysis was performed on three different algal solutions using an electrode spacing of 10 mm. Samples were taken every 15 minutes during treatment to monitor Caspase activity. Treatment was continued for 30 minutes after the activity reached the target threshold (1.5E0). After treatment, the core performance indicators were measured using the following methods: Algae removal rate: The average value was calculated using the hemocytometer counting method (5 parallel counts per group) combined with the chlorophyll a content determination (GB / T7494-1987). Activity induction fold: The ratio of the final activity value after treatment to the initial baseline value (E0); Intracellular toxin changes: Intracellular microcystin-LR (Microcystis), anabain (Lycopodium), and columnocystin (Pseudococcus) were determined by high performance liquid chromatography (HPLC). Chromatographic conditions: C18 column (4.6 mm × 250 mm, 5 μm), mobile phase methanol:water = 60:40 (containing 0.1% trifluoroacetic acid), flow rate 1.0 mL / min, detection wavelength 238 nm, column temperature 30 ℃.

[0107] Comparison of treatment effects: After targeted parameter treatment, all three types of cyanobacteria achieved the expected algae removal effect and activity induction target. Specific data are shown in the table below:

[0108] Results analysis: 1. Inherent differences exist in the baseline values ​​of Caspase activity among different cyanobacteria, necessitating the establishment of a species-specific baseline database: Experimental results show significant differences in the initial baseline values ​​of three typical cyanobacteria blooming in algae. This difference stems from the evolutionary characteristics and cellular structure differences of the algal species—Microcystis aeruginosa exhibits high cellular metabolic activity and strong enzyme synthesis capacity; while the filamentous structure of Longsporium leads to relatively dispersed intracellular enzyme distribution and lower apparent activity. This result indicates that using a uniform baseline value in actual large-scale water surface management will lead to parameter calculation deviations. The strategy proposed in this invention of "first determining the E0 of the target algal species, then determining the induction threshold" is necessary. Further efforts are needed to establish a database of Caspase activity baseline values ​​for common cyanobacteria blooming in algae to improve the efficiency of field application.

[0109] 2. By adjusting the values ​​of k and n, specific adaptations to different cyanobacteria can be achieved, verifying the universality of the parameter optimization system: For the high tolerance of *Lycopodium*, increasing the k value (1.2) extends the treatment time, and increasing the α value (3.0) enhances the current density, ensuring that the oxidative intensity penetrates the filamentous structure; for the high sensitivity of *Microcystis*, a lower k value (0.8) is used to reduce energy consumption; for the moderately dense cell wall of *Cyclopyralid*, an intermediate parameter value is selected. Ultimately, all three algal species achieved a 1.5-fold increase in activity induction target, and the algae removal rate exceeded 75%, proving that the parameter optimization system of this invention can flexibly adjust coefficients to adapt to the differences in characteristics of different cyanobacteria, solving the core pain point of traditional fixed parameter technology where "one parameter is difficult to adapt to multiple algal species".

[0110] 3. Specific treatment achieves a synergistic effect of "highly efficient algae removal + low toxin risk," meeting the requirements of ecological governance: After treatment, the intracellular toxin content of the three types of cyanobacteria was significantly reduced (by 28%-35%), and the concentration of dissolved toxins was lower than the limit for drinking water in my country (1 μg / L). This result verifies that the present invention, through precise induction of programmed cell death, can avoid the problems of algal cell rupture and large-scale toxin release caused by traditional strong oxidation, and can still achieve effective control of toxin risk even for cyanobacteria with different toxicities.

[0111] 4. Provide technical support for the treatment of mixed algal blooms: Cyanobacterial blooms in natural water bodies are mostly mixed algal blooms. The parameter adjustment logic of this embodiment can be extended to mixed algal species scenarios. By monitoring the dominant species and corresponding activity benchmark values ​​in the mixed algal bloom in real time, and adopting the parameter calculation strategy of "weighted average" or "dominant species dominance", the efficient treatment of mixed algal blooms can be achieved, further expanding the practical application scenarios of this invention.

[0112] Example 4: Treatment of non-cyanobacterial blooms (eukaryotic algal blooms).

[0113] The electrolytic algae removal method of this invention is not only applicable to the treatment of cyanobacterial blooms, but can also be extended to the treatment of non-cyanobacterial blooms such as diatoms, green algae, and dinoflagellates by targeted adjustment of process parameters. Non-cyanobacteria and cyanobacteria differ significantly in cell structure (such as cell wall composition and cell membrane permeability), physiological characteristics (such as metabolic rate and sensitivity to oxidative stress), and growth environment requirements. Traditional algae removal technologies often suffer from low treatment efficiency or secondary pollution due to poor parameter adaptability. This embodiment achieves precise algae removal by optimizing key coefficients in the process parameter formula, combining the characteristics of non-cyanobacteria with the features of the aquatic environment, thus verifying the wide applicability of this invention.

[0114] Example 5.1: Diatom bloom treatment.

[0115] Diatoms are a common dominant species in freshwater algal blooms. Their cell walls are mainly composed of silica (SiO2·nH2O), which is hard and dense. Compared to cyanobacteria cell walls, they are more resistant to electrolytic oxidation, and conventional electrolytic parameters are insufficient to penetrate the cell wall and induce cell death, leading to incomplete algae removal. This embodiment addresses the unique characteristics of diatom cell walls by optimizing process parameters to achieve efficient algae removal.

[0116] 1. Target of treatment: A reservoir attached to a drinking water source (total capacity 2 million m³) 3 In spring, diatom blooms occurred in the area (average water depth 8m), with monitoring showing that the dominant species was Cyclotellasp., with a cell density reaching 4.0 × 10⁻⁶. 6 The algae count is only 25 cm, and the chlorophyll a content is 32 μg / L, which seriously affects the water quality and urgently requires efficient algae removal treatment.

[0117] 2. Parameter adjustment strategy: Diatoms have thicker cell walls and contain a silica layer, making them significantly more resistant to electrolytic oxidation than cyanobacteria. Therefore, it is necessary to increase the current density to enhance the oxidation intensity and ensure that active oxidants penetrate the cell wall and act on the cell interior, thereby inducing caspase activity to rise to the programmed cell death threshold.

[0118] Parameter adjustment: Based on the characteristics of Cyclocarya paliurus and the reservoir water environment (moderate flow, water temperature 18℃, pH 7.5), the core coefficient values ​​were determined as follows: α=3.5 (current density coefficient, which is 1.5-2.0 higher than that of cyanobacteria treatment to match the high oxidation requirements of siliceous cell walls); k=1.2 (process coefficient, the reservoir is a semi-enclosed water body with a moderate algal diffusion rate, and the value is between that of enclosed and open water); n=1.3 (correction coefficient, the permeability of diatom cell membranes is low, and the coefficient needs to be increased to enhance the sensitivity of the activity response).

[0119] The calculated value is: J = 3.5 mA / cm 2 t=1.5 hours; at the same time, considering the water temperature is lower than the benchmark value (25℃), the current density formula is used for correction to ensure that programmed mortality can still be stably induced in low-temperature environments.

[0120] Processing effect: The algae removal rate reached 83.5%, and simultaneous monitoring showed that the chlorophyll a removal rate reached 81.2%, with the remaining algal cell density decreasing to 2.6 × 10⁻⁶. 5 The algae count / mL meets the algae control requirements for drinking water sources; Microscopic observation revealed that diatom cells exhibited obvious characteristics of programmed cell death: cell shrinkage, uniform chlorophyll degradation, no cell membrane rupture, and intact intracellular silica shell, thus avoiding secondary water pollution caused by the release of intracellular organic matter. After treatment, the water transparency increased by 60%, from 25cm to 40cm, the turbidity decreased from 8.5NTU to 3.2NTU, and the dissolved oxygen concentration increased from 6.8mg / L to 7.9mg / L, significantly enhancing the water's self-purification capacity. Energy consumption monitoring shows that the energy consumption for this treatment was 0.45 kWh / m³. 3 Compared to traditional electrolytic algae removal technology for treating diatom blooms (energy consumption 1.0-1.5 kWh / m³), 3 The energy consumption was reduced by more than 50%, demonstrating the energy-saving advantages of parameter optimization. The algae removal rate reached 83.5%; diatom cells showed obvious programmed cell death characteristics; and the water transparency increased by 60% after treatment.

[0121] Example 5.2: Treatment of green algal blooms.

[0122] Green algae are common algal blooms in landscape water bodies (such as park lakes and artificial wetlands), with Chlamydomonas and Scenedesmus being the dominant species. Landscape water bodies have special requirements such as high pedestrian traffic, low disturbance during treatment, and the need to ensure aesthetic appeal (no odor, no visible equipment marks). Traditional fixed algae removal equipment can easily damage the landscape, while chemical algae removal can produce odors. This embodiment uses a floating electrolytic algae removal device, combined with a low-disturbance parameter design, to achieve efficient and low-impact treatment of green algal blooms in landscape water bodies.

[0123] 1. Subject of treatment: A landscape lake in a city center park (water area 8000m²) 2 (Average water depth 2.5m) Green algal blooms occur in summer, with Chlamydomonas sp. as the dominant species, reaching a cell density of 6.5 × 10⁻⁶. 6 The water concentration is low (crystals / mL), the water is dark green, and the transparency is only 15cm. Some areas have a slight fishy odor, which seriously affects the landscape and the visitor experience. The scenic lake has no fixed power supply and is surrounded by pedestrian walkways, making large-scale civil engineering construction impossible.

[0124] 2. System type: The floating electrolytic algae removal device is adopted, which is suitable for landscape water bodies with no power supply, low disturbance, and the core needs of ensuring the landscape.

[0125] The boat measures 5m x 3m x 1.2m and is made of lightweight fiberglass. The surface of the boat is coated with a water-colored paint to blend into the landscape and avoid disrupting the visual effect. The boat is equipped with anti-collision rubber strips to prevent collisions with the lake shore or other boats.

[0126] Processing capacity: 500m 3 / h, a single unit can cover 500-800m 2 Water area, targeting 8000m 2 The scenic lake utilizes 16 distributed devices to achieve full water coverage.

[0127] Equipped with a solar power generation system (5kW): It uses monocrystalline silicon solar panels and a matching energy storage battery pack (20kWh capacity), which can achieve continuous operation for 24 hours on cloudy days; the power generation system is integrated into the top of the hull, with the height controlled below 1.2m to avoid obstructing the view; it is also equipped with a small wind-assisted power generation device to improve the stability of energy supply and completely eliminate dependence on the power grid.

[0128] Processing parameters: Considering the special requirements of landscape water bodies (low disturbance, no odor, and avoidance of algal cell rupture releasing a fishy smell), a mild treatment strategy of "low current density + long treatment time" was adopted, with the current density set at 1.5 mA / cm³. 2 (2.0-3.0 mA / cm² lower than the conventional value for cyanobacteria treatment) 2 This reduces cell rupture and the release of odor-causing substances caused by strong oxidation.

[0129] Extending the treatment time to 2.5 hours and verifying it through formula calculation: Considering the characteristics of Chlamydomonas cell membrane being relatively thin (moderately sensitive to oxidation) and the stable algae concentration in the landscape lake (C / C0=1.3), setting k=0.8 (process coefficient of enclosed water area) and n=0.9 (green algae correction coefficient), it was calculated that a treatment time of 2.5 hours can ensure that caspase activity reaches the induction threshold and achieve programmed cell death.

[0130] Phased treatment plan: The landscape lake is divided into 4 treatment zones, with 2 zones treated per batch, rotating every 12 hours to avoid water flow disturbance caused by multiple devices operating simultaneously; the influent / effluent flow rate is controlled at 0.8 m³ / h during treatment. 3 / h, ensuring that there are no obvious water flow marks on the water surface and that it does not affect citizens' visits.

[0131] Considering the special requirements of landscape water features, a lower current density (1.5 mA / cm²) was adopted. 2 ); extend the processing time to 2.5 hours; process in batches to avoid impacting the landscape.

[0132] Running result: After a week of continuous treatment, the green algae density increased from 6.5 × 10⁻⁶. 6 The number of cells / mL decreased to 9.75 × 10⁻⁶. 5 The number of cells / mL decreased by 85%; the water color changed from dark green to light yellow, and the transparency increased from 15cm to 45cm, meeting the requirements for landscape water transparency (≥40cm).

[0133] Energy consumption is 0.32 kWh / m 3 Compared to traditional grid-connected fixed units (energy consumption 0.6-0.8 kWh / m³), 3The energy consumption of solar power systems is reduced by more than 50%; the daily power generation of the solar power system is 12kWh, which fully meets the operation requirements of the equipment, achieves zero-carbon governance, and meets the ecological and environmental protection requirements of landscape water bodies.

[0134] Convenience of operation and maintenance: The system adopts intelligent control, which can remotely monitor the operation status. Only one manual inspection is required per week, reducing the operation and maintenance cost by 70% compared with traditional technology, and is suitable for the long-term operation and maintenance needs of landscape water bodies.

[0135] After a week of continuous treatment, the algae density decreased by 85%, the water remained clear, and no odor was produced. The energy consumption was 0.32 kWh / m³. 3 .

[0136] Example 5.3: Treatment of dinoflagellate blooms.

[0137] Dinoflagellates are common harmful algal blooms in coastal areas, estuaries, and aquaculture zones, with Alexandrium and Gymnodinium being the dominant species. They produce highly toxic paralytic and diaphoretic shellfish toxins, which can cause the death of farmed organisms and even harm human health through the food chain. Coastal aquaculture areas are characterized by high salinity, strong water flow, and significant spatial and temporal variations in water quality parameters. Traditional algae removal technologies are easily affected by salinity, leading to electrode polarization, and are difficult to achieve precise coverage of flowing water. This embodiment optimizes process parameters and system design based on the characteristics of dinoflagellates and the marine environment to achieve efficient algae removal and toxin control.

[0138] 1. Subject of Treatment: A dinoflagellate bloom occurred in the autumn in the waters adjacent to a nearshore shellfish aquaculture area (aquaculture area of ​​500 mu, average water depth of 5m), with the dominant species being Alexandrium sp., and the algal cell density reaching 3.5 × 10⁻⁶. 6 The concentration of paralytic shellfish toxin in the water was found to be 8.6 μg / L, resulting in a small number of deaths among farmed Manila clams. If not addressed promptly, this could lead to large-scale losses in aquaculture and pollute the surrounding marine environment. The salinity of this area is 32‰, the water flow velocity is 0.3 m / s, and the diurnal temperature range is 5℃, indicating significant fluctuations in water quality parameters.

[0139] 2. Parameter adjustment strategy: Dinoflagellate cells contain cellulose cell walls and are moderately sensitive to oxidative stress. Excessive oxidation can easily lead to cell membrane rupture and release large amounts of paralytic shellfish toxins, while insufficient oxidation cannot achieve efficient algae removal. Therefore, a balanced strategy of "medium current density + moderately extended treatment time" is adopted to ensure algae removal efficiency while strictly controlling toxin release.

[0140] Parameter adjustment: Considering the characteristics of dinoflagellates and the high mobility of the seawater, the core coefficients are set as follows: α=2.8 (current density coefficient, matching the oxidation requirements of cellulose cell walls, between cyanobacteria and diatoms); k=1.8 (process coefficient, due to the high mobility of the seawater and the rapid diffusion of algae, the coefficient needs to be increased to ensure sufficient treatment); n=1.2 (correction coefficient, dinoflagellates have moderate sensitivity to caspase activity induction, and the value is chosen to balance induction efficiency and energy consumption).

[0141] The calculated value is: J = 2.8 mA / cm 2 t=2.0 hours; For the special environment of high salinity (32‰) in the sea area, a salinity correction mechanism is added: In high-salinity environments, chloride ions easily generate chlorine gas on the electrode surface, leading to electrode polarization and increasing the risk of toxin generation. Therefore, an electrode spacing fine-tuning mechanism is activated, adjusting the spacing from the conventional 10mm to 12mm to reduce the current density gradient on the electrode surface and reduce chlorine gas generation; Simultaneously, a salinity sensor is added to the intelligent control unit to monitor salinity changes in real time. When salinity fluctuations exceed ±3‰, the current density is automatically fine-tuned (fluctuation range ±0.2mA / cm²). 2 This ensures processing stability.

[0142] Processing effect: The algae removal rate reached 84.2%. Microscopic observation showed that the dinoflagellate cells were morphologically intact without obvious rupture, and activity testing confirmed that programmed cell death had been achieved, with no large-scale release of intracellular toxins; the density of remaining algal cells decreased to 2.03 × 10⁻⁶. 5 The algae count / mL meets the requirements for algae control in aquaculture areas.

[0143] After treatment, the water transparency increased by 70%, from 20cm to 54cm; the dissolved oxygen concentration increased from 5.2mg / L to 7.8mg / L; through phytoplankton community monitoring, the structure of the marine phytoplankton community gradually recovered and stabilized after treatment, and the proportion of beneficial algae such as diatoms and green algae increased from 35% before treatment to 68%, providing sufficient food for aquaculture organisms.

[0144] The system's continuous operation energy consumption remains stable at 0.38 kWh / m³. 3 Compared to traditional electrolytic algae removal technology for treating dinoflagellate blooms in the sea (energy consumption 1.2-1.8 kWh / m³), 3 The efficiency is reduced by more than 67%; the electrode can operate continuously for 720 hours in a high-salt environment without obvious polarization, and its service life meets the requirements of engineering applications, making it suitable for large-scale and long-term marine treatment needs.

[0145] Example 6: Different applications of electrolytic algae removal systems.

[0146] The electrolytic algae removal system of this invention can flexibly adopt four core application forms—shore-based, ship-mounted, floating platform, and combined—depending on water type, treatment needs, and site conditions, to adapt to large-scale algae removal requirements in different scenarios. Specific implementation examples of each form are as follows: Example 6.1: Shore-based electrolytic algae removal system.

[0147] Application scenario: A city landscape lake (water area 8000m²) 2 The average water depth is 2.5m, and the total volume is 20,000 m³. 3 It is a closed, small to medium-sized water body, dominated by green algae, with an algal density reaching 5.2 × 10⁻⁶ in summer. 6 With algae counts per mL decreasing and water transparency dropping to 15 cm, routine algae control is necessary. The site has a fixed location on the shore, suitable for constructing a fixed shore-based treatment system.

[0148] System design: The system adopts a shore-based fixed installation mode, with the main equipment arranged on the hardened lake shore. It is connected to the landscape lake through inlet and outlet water pipes to form a closed-loop system of "water intake-treatment-return".

[0149] Core Unit: Two modular electrolysis processing units are installed (each unit has a processing capacity of 500m³). 3 / h), the anode uses a ruthenium-titanium coated electrode, the cathode uses a stainless steel electrode, and the electrode spacing can be adjusted from 8-15mm; Pretreatment unit: Equipped with a mechanical bar screen (1mm aperture) + sedimentation tank to remove large impurities such as fallen leaves and suspended particles from the water, and to prevent clogging of the electrodes; Auxiliary unit: integrates intelligent control cabinet, online monitoring system (real-time monitoring of algae density, pH, and temperature) and grid power supply module (10kW power) to achieve automated operation.

[0150] Processing parameters: Based on the characteristics of Chlamydomonas, the current density was set to 1.8 mA / cm². 2 The processing time is 1.5 hours; the intelligent control unit monitors data, and when the algae density is below 10... 5 When the count / mL reaches a certain level, it will automatically switch to intermittent operation mode (run for 2 hours, then stop for 4 hours).

[0151] Operational results: After one week of continuous system operation, the algae density decreased to 8.5 × 10⁻⁶. 4 The algae removal rate reached 83.7%; water transparency improved to 45cm, meeting the water quality requirements for landscape water bodies; and operating energy consumption remained stable at 0.38kWh / m³. 3 With an average daily operating cost of approximately 91.2 yuan, it is suitable for routine treatment of small and medium-sized enclosed water bodies.

[0152] Example 6.2: Shipborne electrolytic algae removal system.

[0153] Application scenario: A large lake (water area 50km²) 2 (Average water depth 8m), cyanobacterial blooms occur regionally in summer, with algae density reaching 6.8×10⁻⁶ in the core polluted area. 7 The algae density in the surrounding waters varies greatly, requiring flexible relocation to the polluted area for targeted treatment. Furthermore, the available space along the lake shore is limited.

[0154] System design: Based on the modification of a 50-ton motorboat, it adopts a shipborne mobile design to achieve precise treatment wherever algae are found.

[0155] Core Unit: Three shipborne liftable electrolysis processing modules (each module has a processing capacity of 1000m³). 3 / h), the module can adjust the immersion depth according to the water depth (adapted to water depth of 3-15m), and the electrode adopts ruthenium titanium-titanium alloy combined electrode, which has strong resistance to water flow impact; Power and power supply: The hull is equipped with a diesel engine (120kW) and an integrated solar auxiliary power supply system (8kW) to ensure stable energy supply during mobile operations; Monitoring and control: Equipped with a portable multi-parameter monitor (real-time detection of algae density, Caspase activity, and dissolved oxygen), the data is wirelessly transmitted to the shipboard control cabinet, and the processing parameters can be adjusted manually or automatically.

[0156] Processing parameters: For areas with high algae density, the current density is set to 3.2 mA / cm². 2 The treatment time is 2.0 hours; it adopts a combination of "fixed-point treatment + slow-speed cruise treatment" mode, with fixed-point treatment of the core pollution area and cruise speed controlled at 5km / h to treat the surrounding diffusion area.

[0157] Operational results: A single vessel can complete 20,000 m of work in 8 hours of continuous operation. 3 Water treatment reduced algae density in the core polluted area to 3.1 × 10⁻⁶. 6 The algae removal rate reached 85.4%; the concentration of dissolved microcystins in the water decreased from 5.8 μg / L to 0.9 μg / L, meeting the surface water environmental quality standards; the energy consumption for mobile operation was 0.52 kWh / m³. 3 It is suitable for emergency management of algal blooms in large water areas.

[0158] Example 6.3: Floating platform electrolytic algae removal system.

[0159] Application scenario: A large reservoir (total capacity 120 million m³) 3 The reservoir has an average water depth of 18m. The central area of ​​the reservoir is a high-incidence area for algae, and the shore is far from the core treatment area, making shore-based installation unsuitable. In addition, long-term stable treatment is required, and frequent relocation of equipment is unnecessary.

[0160] System Design: The system adopts a floating platform design, which is fixed to the central area of ​​the reservoir by anchor chains. The fixed position can be finely adjusted according to the distribution of algae to achieve long-term fixed-point treatment.

[0161] Core Unit: The floating platform is equipped with four large-scale electrolytic processing units (total processing capacity 4000m³). 3 / h), with an adjustable electrode spacing of 10-20mm, and equipped with a self-cleaning system to prevent suspended particles in the water from adhering to the electrodes; Energy supply: It adopts a complementary power supply system of "solar power + wind power" (solar power 15kW, wind power 5kW), and is equipped with an energy storage battery pack (capacity 50kWh), which can achieve long-term continuous operation without grid coverage; Monitoring and Communication: An integrated distributed monitoring network covers a 500m water area. Monitoring data is remotely transmitted to the shore control center via 5G, enabling remote monitoring and parameter adjustment.

[0162] Processing parameters: Based on the water flow rate of the reservoir, the current density is set at 2.5 mA / cm². 2 The processing time is 1.8 hours; through the intelligent control unit linked to water flow velocity monitoring data, when the water flow velocity exceeds 0.3 m / s, the current density is automatically increased to 2.8 mA / cm². 2 This ensures effective algae removal.

[0163] Operational results: The system ran stably for one month, and the algae density in the treated area remained stable at 2.5 × 10⁻⁶. 5 The algae removal rate remains above 82% with a density of less than 100 cells / mL; energy consumption is stable at 0.40 kWh / m³. 3 Compared with traditional shore-based systems, it saves more than 60% of the power grid supply cost and is suitable for long-term fixed-point management of large open water areas.

[0164] Example 6.4: Combined electrolytic algae removal system.

[0165] Application scenario: Wastewater discharge outlet of a wastewater treatment plant (daily discharge volume 10,000 m³) 3 / d), the effluent still contains a small amount of algae (algae density 3.5×10⁻⁶) after biological treatment. 5 Algae (e.g., algae per mL) and organic matter must be treated before being discharged into the landscape lake. The algae removal rate must be ≥90%, while reducing the organic matter content of the effluent.

[0166] System design: It adopts a shore-based fixed and multi-unit combination mode, integrating three-level units of preprocessing, main processing and deep processing to form a complete processing link.

[0167] Pretreatment unit: mechanical filtration (0.5mm pore size) + coagulation sedimentation tank, to remove suspended particles and some colloidal organic matter in the effluent, reducing the load on subsequent treatment; Main processing unit: 3 sets of shore-based electrolytic treatment units (total processing capacity 10,000 m³) 3 / d), employing the activity threshold regulation strategy of this invention, precisely induces programmed cell death in algae; Advanced treatment unit: biological filter (filled with modified activated carbon packing) plus ultraviolet disinfection unit, to further remove small molecule organic matter generated by electrolytic oxidation and kill residual algae cells and bacteria; Control unit: Full-process online monitoring (algae density, COD, pH, dissolved oxygen), realizing the linkage and control of parameters of each unit to ensure stable effluent water quality.

[0168] Processing parameters: The current density of the main electrolysis processing unit is set to 2.2 mA / cm². 2 Treatment time: 1.2 hours; hydraulic retention time in biological filter: 0.8 hours; UV disinfection dose: 30 mJ / cm³ 2 .

[0169] Operating data: The system processes an average of 10,000 MB per day. 3 The effluent had an average algae removal rate of 92.3% and an algae density of <10. 5 COD removal rate 45%, effluent COD ≤ 30 mg / L; total energy consumption 0.45 kWh / m³ 3 Operating cost: 0.23 yuan / m 3 The quality of the effluent meets the requirements for replenishing the landscape lake.

Claims

1. A method for electrolytic algae removal based on a programmed cell death induction threshold, characterized in that, Includes the following steps: S1. Real-time detection of algal pollution indicators and Caspase enzyme activity values ​​in the water to be treated; S2. Based on the data detected in step S1, and according to the preset programmed cell death induction threshold and process parameter optimization model, dynamically calculate the optimal electrolysis treatment time and optimal current density; the induction threshold is when the Caspase activity value reaches 150% of its baseline value; S3. Control the electrolytic algae removal device to operate according to the optimal parameters calculated in step S2, and continuously monitor the Caspase activity value; S4. Once the Caspase activity value reaches the induction threshold and stabilizes, the electrolysis process is stopped.

2. The electrolytic algae removal method based on the programmed cell death induction threshold according to claim 1, characterized in that, Processing time calculation formula: ， Formula for calculating current density: ， in: t represents the processing time, and k is a process coefficient, with a value ranging from 0.

5. 2.0; C represents the real-time algal cell density or phycocyanin content, and C0 is its baseline value. E represents the real-time Caspase activity value, and E0 is its baseline value; n is a correction factor, with a value ranging from 0.

8. 1.5; J represents the current density, and α is the current density coefficient, with a value ranging from 1.

0. 5.0; T, DO, and pH represent real-time water temperature, dissolved oxygen, and pH value, respectively. T0, DO0, and pH0 are the corresponding baseline values.

3. The electrolytic algae removal method based on the programmed cell death induction threshold according to claim 2, characterized in that, The process coefficient k is taken as 1.5 in open water with high flow. 2.0, and 0.5 in enclosed waters with low flow. 1.0; The correction factor n is set to 1.3 for cyanobacteria with dense cell membrane structures. 1.5, for cyanobacteria with thinner cell membranes, use 0.

8. 1.0; The current density coefficient α is used when the algal concentration is higher than 10. 7 When the concentration is 3.0 mg / mL, take 3.0 mg / mL. 5.0, below 10 6 When the concentration is 1.0 μg / mL, take 1.0 μg / mL. 2.

0.

4. The electrolytic algae removal method based on the programmed cell death induction threshold according to claim 2, characterized in that, The Caspase activity baseline value E0 was determined by experimentally measuring the initial activity of the dominant cyanobacteria species in the target water body. The induction threshold is 150% of E0. When the activity value reaches this threshold, the algal cells undergo programmed cell death, and the intracellular algal toxin release is less than 1 μg / L.

5. The electrolytic algae removal method based on the programmed cell death induction threshold according to claim 1, characterized in that, Real-time monitoring of the content of reactive oxygen quenching substances in water bodies; When the content of the active oxygen quenching substance is detected to exceed the set threshold, the current density is dynamically adjusted or the treatment time is extended to ensure that the preset Caspase activity induction effect is achieved.

6. The electrolytic algae removal method based on the programmed cell death induction threshold according to any one of claims 1-5, characterized in that, The method is applicable to large bodies of water, including lakes, reservoirs, and rivers, and is suitable for water temperatures of 5°C. 65℃, pH 6.0 11. Algae concentration 10 4 10 10 Water quality range per mL; The method adapts to different types of algae, including cyanobacteria, diatoms, green algae, and dinoflagellates, by adjusting process parameters.

7. An electrolytic algae-eliminating system based on a programmed cell death induction threshold, characterized in that, include: An electrolytic processing unit includes an anode, a cathode, and a modular reactor. The anode includes any one of a ruthenium-iridium-titanium coated electrode, an iridium-tantalum-titanium coated electrode, a platinum-titanium coated electrode, a lead dioxide-titanium coated electrode, a tin-antimony-titanium coated electrode, and a sub-titanium oxide coated electrode. The cathode includes any one of a stainless steel electrode, a titanium electrode, an iron electrode, a nickel electrode, an aluminum electrode, and a copper electrode. The real-time monitoring unit includes sensors for detecting algal contamination indicators, a Caspase activity detection device, and sensors for water temperature, pH, and dissolved oxygen. The intelligent control unit, which is communicatively connected to the electrolysis processing unit and the real-time monitoring unit, is configured to execute claim 1.

6. The steps of any one of the methods described.

8. The electrolytic algae-eliminating system based on programmed cell death induction threshold according to claim 7, characterized in that, The distance between the anode and cathode in the electrolysis unit is 1. 100mm adjustable; The real-time monitoring unit is distributed and covers different areas of the large water surface, with a data acquisition frequency of no less than once every 5 minutes. The intelligent control unit includes a data processing module, a parameter calculation module, and an execution control module, with a response delay of ≤1 minute.

9. The electrolytic algae-eliminating system based on programmed cell death induction threshold according to claim 7, characterized in that, The system also includes: The wireless communication unit adopts 5G or LoRa communication protocols to realize remote monitoring and data transmission; The power supply unit, including a solar power module, an energy storage battery pack, and / or a diesel generator, supports off-grid operation of the system.

10. The electrolytic algae-eliminating system based on programmed cell death induction threshold according to claim 7, characterized in that, The system can be deployed in any of the following forms: shore-based fixed type, shipborne mobile type, floating platform fixed type, or combination type. The combined system includes a pretreatment unit, an electrolysis main treatment unit, and a deep treatment unit, and is suitable for algae removal from wastewater treatment plant effluent or pretreatment of industrial production water.

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