CN107884465B - Online monitoring system and method for early warning of red tide - Google Patents
Online monitoring system and method for early warning of red tide Download PDFInfo
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Abstract
The invention discloses an online monitoring system and method for early warning of red tide, wherein the system comprises a sampling tube, a filter, a solution distribution system, a detection pool, a ferro-manganese detection electrode, an integrated circuit and a power supply; the solution distribution system comprises a six-position valve, a pure water bottle, a mercury plating liquid bottle, an iron standard liquid bottle, a manganese standard liquid bottle, a quantitative ring and an injection pump; a solution distribution system is constructed by using a syringe pump, a quantitative ring, a six-position valve and the like to reduce the dead volume of a pipeline, a ferro-manganese detection electrode consisting of a working electrode, a reference electrode and a counter electrode is used as a detection method by combining a differential pulse stripping voltammetry, and the ferro-manganese ion concentration value serving as a red tide induction factor in seawater is obtained by a standard addition method, so that the blind spot of the initial stage existing in the current red tide online monitoring is solved, and early warning information of red tide can be provided for a monitoring department.
Description
Technical Field
The invention relates to the technical field of ocean red tide early warning, in particular to a red tide early warning on-line monitoring system and method based on iron-manganese ion detection.
Background
Due to the rapid development of modern industry and agriculture and the continuous growth of population, industrial and agricultural wastewater and domestic sewage are discharged into the sea in large quantity, so that the sea water is eutrophicated, and the red tide is a worldwide public hazard. Red tide is an abnormal phenomenon of the marine ecosystem, and its growth and elimination can be roughly divided into four stages of initiation, development, maintenance and elimination. The sea area in the initial stage of red tide has a certain number of red tide organism species and has physical and chemical conditions suitable for the growth and reproduction of a certain red tide organism; a certain red tide organism in the sea area reaches a certain quantity in the development stage, and the external environments such as temperature, salinity, illumination, nutrition and the like reach the most suitable range for growth and proliferation of the red tide organism, namely the red tide organism can enter an exponential proliferation stage; the maintenance stage mainly depends on the physical stability of the water body and the rich degree of various nutrient salts, and the supplementing rate and supplementing quantity after the nutrient salts are consumed in a large amount; the death stage can be caused by factors such as physical stability loss of the water body, depleted nutrient salt consumption or weather and tide. The red tide extinction process is usually the most serious stage of harm to fishery, after a large number of red tide organisms die, dissolved oxygen in seawater can be excessively consumed in the decomposition process of the red tide organisms, so that an anoxic environment is caused, the normal ecological structure of the ocean is destroyed, the existence of the ocean organisms is threatened, a large number of death of fishes, shrimps and shellfish is caused, and finally huge economic loss is caused. Therefore, the monitoring of the ocean environment, especially the monitoring of the physical and chemical parameters of the seawater which influence the red tide in the initial stage, and the early warning of the red tide can be realized.
At present, methods adopted by an online monitoring system for red tide early warning mainly comprise a water color remote sensing method, an image analysis method, a total organic carbon method, an environmental parameter method and the like. (1) The water color remote sensing method utilizes satellite sensors to obtain data such as sea surface water-leaving radiance of visible light and infrared wave bands, extracts remote sensing reflectivity of each wave band from the data, calculates inherent optical characteristics of water body by utilizing a model, and communicatesExtracting red tide information and an occurrence range through inherent optical quantity; (2) The image analysis method utilizes an image acquisition system arranged on an unmanned fixed monitoring station or a navigation mark in a water area to shoot on site to obtain image information of algae in seawater, and the type, the quantity and the growth state of the algae in the photo are identified through image identification software and are compared with historical data in a database so as to achieve the aim of early warning red tide outbreak; (3) The total organic carbon method is to collect seawater surface water sample containing planktonic microorganism, acidify to form and remove CO of inorganic source 2 Then, the organic matters contained in the seawater are completely oxidized into CO with organic source 2 Converting the planktonic microorganism amount according to the total organic carbon content, and providing early warning for red tide according to the change trend; (4) The environmental parameter method utilizes seawater environmental parameters obtained by buoy online monitoring, such as chlorophyll, dissolved oxygen, pH value and the like as red tide discrimination factors, and carries out red tide short-term early warning according to the change trend. Wherein (1) belongs to a physical method, has wide sea area coverage, and is suitable for identifying the occurrence range in the red tide maintenance stage; (2) And (3) belongs to biological methods, and can monitor plankton content in seawater in the development and maintenance stages of red tide; (4) Belongs to a chemical method, and can carry out short-term early warning on red tide according to chemical parameter changes in seawater in the development stage of the red tide.
None of the above techniques allow on-line monitoring of red tides at the initial stage. In the development, maintenance and extinction stage of red tide, the temperature, water color and other physical properties of the seawater in the red tide area and the pH value, dissolved oxygen, chlorophyll and other chemical properties of the seawater can change in series along with the rapid proliferation and death of red tide organisms; more prospective, the concentration of iron and manganese in the sea water will reach the maximum value in the initial stage of red tide, and the microelements iron and manganese are the induction factors for red tide formation and are the key for inducing red tide formation. There are studies showing that in seawater without iron and manganese elements, the density of red tide organism population is not increased even under the most suitable temperature, salinity, pH and basic nutrition conditions. Therefore, the invention is based on the seawater iron-manganese ion real-time online detection technology, and aims to develop an online monitoring system for early warning of red tides, break through blind points of monitoring and early warning in the early stage of red tides, and reduce economic losses of fishery and aquaculture industry as much as possible.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an on-line monitoring system and method for early warning of red tide.
The aim of the invention is realized by the following technical scheme: an on-line monitoring system for early warning of red tide comprises a sampling tube, a filter, a solution distribution system, a detection pool, a ferro-manganese detection electrode, an integrated circuit and a power supply;
the solution distribution system comprises a six-position valve, a pure water bottle, a mercury plating liquid bottle, an iron standard liquid bottle, a manganese standard liquid bottle, a quantitative ring and an injection pump;
the six-position valve is provided with 7 external interfaces and 1 central interface, the central interface is positioned at the central position of the valve, and the central interface can be gated in the valve body with any 6 external interfaces uniformly distributed at the edge of the valve at a time; the central interface is connected to one end of the quantitative ring, and the 6 external interfaces are respectively connected with the sampling tube, the pure water bottle, the mercury plating liquid bottle, the iron standard liquid bottle, the manganese standard liquid bottle and the detection tank through pipelines; a filter is arranged on the sampling tube;
the upper end of the injection pump is provided with 3 interfaces: the left interface, the upper interface and the right interface are internally provided with 1 solution cavity, the solution cavity can be gated with any one interface at the upper end at a time, the left interface is connected with the other end of the quantitative ring, the upper interface is connected to the detection tank through a pipeline, and the right interface is connected to the waste liquid pipe through a pipeline;
the ferro-manganese detection electrode comprises a reference electrode, a working electrode and a counter electrode; the three electrode tips are each connected to the integrated circuit by electrode leads.
Further, the sampling tube is a polyether-ether-ketone plastic tube with an inner diameter of 0.25mm.
Further, the filter membrane has a pore size of 100 μm.
Further, the quantitative ring is an annular plastic pipe made of polyether-ether-ketone with threaded fasteners at two ends, the internal capacity is 5mL, and when a seawater sample, pure water, mercury plating solution, iron standard solution and manganese standard solution are transferred to the detection tank, the solution is pumped into the quantitative ring through a six-position valve by using a syringe pump, and then the solution in the quantitative ring is pushed into the detection tank.
Further, the solution cavity inside the injection pump is 10mL.
Further, the reference electrode is a silver/silver chloride electrode formed by electroplating silver chloride on the surface of a silver wire electrode with the diameter of 500 mu m; the working electrode is a gold wire electrode with the diameter of 100 mu m; the counter electrode is a platinum wire electrode with the diameter of 500 mu m.
Further, the system also comprises a GPRS transmitter connected with the integrated circuit, and the detection data is transmitted to a server of the monitoring department in real time through the GPRS transmitter.
Further, the ferro-manganese detection electrode detects the seawater sample by using a differential pulse stripping voltammetry.
A method for carrying out online monitoring and red tide early warning on iron and manganese ions in seawater according to the system comprises the following steps:
(1) Electrode pretreatment: extracting the mercury plating solution into a detection pool, immersing a ferro-manganese detection electrode, depositing a mercury film on the surface of a working electrode to form a gold/mercury electrode, and then discharging the mercury plating solution; extracting pure water to clean the detection pool for more than three times, and removing residual mercury plating solution;
(2) Detecting a seawater sample: filtering impurities in the seawater through a filter, and extracting a seawater sample to a detection pool; the ferro-manganese detection electrode detects a seawater sample by using a differential pulse stripping voltammetry, and records a stripping voltammetry curve;
(3) And (3) adding standard solution for detection: extracting a proper amount of iron and manganese standard liquid from an iron standard liquid bottle and a manganese standard liquid bottle, adding the iron and manganese standard liquid into a seawater sample, detecting again by using a differential pulse stripping voltammetry under the same parameter condition, and recording a stripping voltammetry curve; discharging the seawater sample from the detection tank, extracting pure water to clean the detection tank for more than three times, and waiting for the next detection of the seawater sample;
(4) And (3) data processing and sending: according to the values of the dissolution peak currents respectively corresponding to the iron ions and the manganese ions in the two groups of dissolution volts An Quxian, concentration values of the iron ions and the manganese ions in the sea water sample are converted, detection data are sent to a monitoring department in real time, the detection data are compared with historical data of the iron ions and the manganese ions in normal sea water, and early warning of red tide is sent when the concentration values show rising trend and exceed a threshold value.
Further, the ferro-manganese detection electrode detects a seawater sample by using a differential pulse stripping voltammetry, and specifically comprises the following steps: firstly, applying constant potential on a working electrode, and reducing ferro-manganese ions into atomic states to be enriched on the surface of the working electrode; and then, the ferro-manganese atoms are electrolyzed and dissolved, namely, on the basis of applying a linear-change direct-current scanning voltage on a working electrode, a rectangular pulse potential with small amplitude is superposed, and the difference value of current at a certain time before pulse superposition and a certain time before pulse termination is recorded, so that a dissolution volt-ampere curve is obtained.
The invention has the technical advantages that:
1. the quantitative ring is used as a temporary storage container for transferring seawater samples, pure water, mercury plating solution, iron standard solution and manganese standard solution in the solution distribution system, and the dead volume in a pipeline is effectively reduced and the accuracy of the quantitative volume of the solution is improved through the process of leading the solution into and out of the quantitative ring.
2. Through the optimal design of the pipeline structure of the solution distribution system, the power of all solution circulation comes from a single injection pump, so that the uniformity of a solution transfer mode is ensured, the complexity of the whole system structure is reduced, and the reliability of the system is improved.
3. The concentration of iron and manganese ions in the seawater sample is calculated by using a standard addition method according to two groups of stripping voltammetry curves detected before and after the standard solution of iron and manganese is added.
The invention has the beneficial effects that a solution distribution system is constructed by adopting a syringe pump, a quantitative ring, a six-position valve and the like, a ferro-manganese detection electrode consisting of a working electrode, a reference electrode and a counter electrode is combined with a differential pulse stripping voltammetry to be used as a detection method, and the ferro-manganese ion concentration value which is used as a red tide induction factor in seawater is obtained by a standard adding method, so that the blind spot of the initial stage existing in the current red tide on-line monitoring is solved, and early warning information of the red tide can be provided for a monitoring department.
Drawings
FIG. 1 is a schematic diagram of an embodiment of an on-line monitoring system for early warning of red tides;
in the figure, 1-sampling tube, 2-filter, 3-pure water bottle, 4-mercury plating liquid bottle, 5-iron standard liquid bottle, 6-manganese standard liquid bottle, 7-quantitative ring, 8-six-position valve, 9-center interface, 10-first external interface, 11-second external interface, 12-third external interface, 13-fourth external interface, 14-fifth external interface, 15-sixth external interface, 16-syringe pump, 17-left interface, 18-upper interface, 19-right interface, 20-solution cavity, 21-detection cell, 22-reference electrode, 23-working electrode, 24-counter electrode, 25-electrode wire, 26-GPRS emitter, 27-integrated circuit, 28-power supply, 29-waste liquid tube.
Detailed Description
The technical scheme of the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments, but the scope of protection is not limited thereto.
Examples
The on-line monitoring system for early warning of red tide provided in this embodiment, as shown in fig. 1, mainly includes a sampling tube 1, a filter 2, a solution distribution system, a detection cell 21, a ferro-manganese detection electrode, an integrated circuit 27 and a power supply 28, wherein the solution distribution system includes a six-position valve 8, a pure water bottle 3, a mercury plating solution bottle 4, a ferro-standard solution bottle 5, a manganese standard solution bottle 6, a quantitative ring 7 and a syringe pump 16, and the ferro-manganese detection electrode includes a reference electrode 22, a working electrode 23 and a counter electrode 24.
The sampling tube 1 is a plastic tube made of polyether-ether-ketone with the inner diameter of 0.25mm. The pore size of the filter 2 is 100 μm. The quantitative ring 7 is an annular plastic tube made of polyether-ether-ketone material with threaded fasteners at two ends, and the internal volume is 5mL. The reference electrode 22 is a silver/silver chloride electrode formed by electroplating silver chloride on the surface, the working electrode 23 is a gold wire electrode with a diameter of 100 μm, the counter electrode 24 is a platinum wire electrode with a diameter of 500 μm, and the three electrode terminals are all connected to the integrated circuit 26 through the electrode wire 25.
As shown in fig. 1, the six-position valve 8 has 7 ports, the center port 9 is located at the center of the valve, and can be connected with any one of 6 external ports uniformly distributed on the edge of the valve at a time: the first external interface 10, the second external interface 11, the third external interface 12, the fourth external interface 13, the fifth external interface 14 and the sixth external interface 15 are gated inside the valve body, and each interface is connected with a polyether-ether-ketone plastic pipe through a threaded fastener. The central interface 9 is connected to one end of the dosing ring 7, and the other 6 external interfaces are respectively connected to the sampling tube 1, the pure water bottle 3, the mercury plating liquid bottle 4, the iron standard liquid bottle 5, the manganese standard liquid bottle 6 and the detection tank 21 through pipelines. The upper end of the injection pump 16 is provided with 3 interfaces, 1 solution cavity 20 with the volume of 10mL is contained in the injection pump, the injection pump can be gated with any one interface at the upper end at a time, the left interface 17 is connected to the other end of the quantitative ring 7, the upper interface 18 is connected to the detection tank 21 through a pipeline, and the right interface 19 is connected to the waste liquid port 20 through a pipeline.
The working process comprises four steps of electrode pretreatment, seawater sample detection, standard liquid addition detection and data processing and sending.
The working process of the electrode pretreatment is as follows: the internal passage of the six-position valve 8 is regulated, the central interface 9 is gated with the second external interface 11, the injection pump 16 gates the upper left interface 17, 0.1mol/L of mercury nitrate solution of 0.05mol/L nitric acid substrate in the mercury plating solution bottle 4 is pumped by the injection pump 16 and temporarily stored in the quantitative ring 7, then the central interface 9 and the fifth external interface 14 are gated, the mercury plating solution in the quantitative ring 7 is injected into the detection tank 21 by the injection pump 16, and the surface of the ferromanganese detection electrode is ensured to be immersed by the mercury plating solution. By control of the integrated circuit 27, an enrichment voltage of 0.1V lower than the fixed potential of the reference electrode 22 was applied to the working electrode 23 for 4 minutes, the working electrode 23 and the counter electrode 24 formed a polarized loop to transport electrons, and the surface of the working electrode 23 was subjected to the following chemical reaction:
Hg 2+ +2e - ->Hg (1)
thereby depositing a mercury film on the surface of the working electrode 23 to form a gold/mercury electrode for standby. The injection pump 16 gates the upper port 18 on the upper end, pumps the mercury plating solution in the detection tank 21 into the solution cavity 20, gates the right port 19, and discharges the mercury plating solution from the waste liquid pipe 29. After the mercury plating solution is discharged, the ultra-pure water is used for cleaning the detection pool 21 for more than three times, the internal passage of the six-position valve 8 is regulated during cleaning, the central interface 9 is gated with the sixth external interface 15, the injection pump 16 gates the upper left interface 17, the ultra-pure water with the resistivity larger than 18MΩ & cm in the pure water bottle 3 is pumped by the injection pump 16 and temporarily stored in the quantitative ring 7, then the central interface 9 and the fifth external interface 14 are gated, the ultra-pure water in the quantitative ring 7 is injected into the detection pool 21 for cleaning by the injection pump 16, and the seawater sample can be detected after the cleaning solution is discharged.
The seawater sample detection working process comprises the following steps: the internal passage of the six-position valve 8 is regulated, the central interface 9 is gated with the first external interface 10, the injection pump 16 is gated with the upper left interface 17, the injection pump 16 is used for extracting a seawater sample from the sampling tube 1, impurities are removed through the filter 2 with the filter membrane aperture of 100 mu m and temporarily stored in the quantitative ring 7, then the central interface 9 and the fifth external interface 14 are gated, the seawater sample in the quantitative ring 7 is injected into the detection tank 21 by the injection pump 16, and the seawater sample is ensured to be immersed on the surface of the ferro-manganese detection electrode. Under the control of the integrated circuit 27, an enrichment voltage 1.8V lower than the fixed potential of the reference electrode 22 is first applied to the working electrode 23 for 3 minutes, the working electrode 23 and the counter electrode 24 form a polarized loop to transmit electrons, and the following chemical reaction occurs on the surface of the working electrode 23:
Fe 2+ +Hg+2e - ->Fe(Hg) (2)
Mn 2+ +Hg+2e - ->Mn(Hg) (3)
the ferro-manganese ions are reduced to atomic state and enriched on the surface of the working electrode 23, and then the ferro-manganese atoms are electrolyzed and dissolved by using a differential pulse dissolution voltammetry, namely, on the basis of applying a linear-change direct-current scanning voltage on the working electrode, a small-amplitude rectangular pulse potential is superposed, a scanning initial potential of-1.8V, a scanning end potential of-0.05V, a scanning speed of 10mV/s, a pulse period of 0.2s, a pulse amplitude of 0.05V and a pulse width of 0.05s are set, and the surface of the working electrode 23 is subjected to the following chemical reaction:
Fe(Hg)->Fe 2+ +Hg+2e - (4)
Mn(Hg)->Mn 2+ +Hg+2e - (5)
recording the difference value of the current at a certain time before each pulse superposition and a certain time before the pulse termination, and obtaining the stripping voltammetry curve of the seawater sample detection.
The working process of adding standard liquid is as follows: firstly, adding a certain amount of iron and manganese standard liquid into a seawater sample, regulating the internal passage of a six-position valve 8, gating a central interface 9 with a third external interface 12, gating an upper left interface 17 by a syringe pump 16, temporarily storing the iron standard liquid into a quantitative ring 7 by the syringe pump 16 after the iron standard liquid is extracted from an iron standard liquid bottle 5, then gating the central interface 9 with a fifth external interface 14, and injecting the iron standard liquid in the quantitative ring 7 into a detection tank 21 by the syringe pump 16; the internal passage of the six-position valve 8 is regulated, the central interface 9 is gated with the fourth external interface 13, the injection pump 16 is gated with the upper left interface 17, the injection pump 16 extracts the manganese standard solution from the manganese standard solution bottle 6 to be temporarily stored in the quantitative ring 7, then the central interface 9 and the fifth external interface 14 are gated, and the injection pump 16 injects the manganese standard solution in the quantitative ring 7 into the detection tank 21. Under the control of an integrated circuit 27, an enrichment voltage which is 1.8V lower than the fixed potential of a reference electrode 22 is applied to a seawater sample added with the iron and manganese standard solution on a working electrode 23 for 3 minutes, the working electrode 23 and a counter electrode 24 form a polarized loop to transmit electrons, chemical reactions (2) and (3) are carried out on the surface of the working electrode 23, iron and manganese ions are reduced to atomic states and enriched on the surface of the working electrode 23, then the iron and manganese atoms are electrolyzed and dissolved by using a differential pulse stripping voltammetry under the same parameter conditions as those of the seawater sample detection, chemical reactions (4) and (5) are carried out on the surface of the working electrode 23, and the difference value between a certain time before each pulse superposition and a certain time before the pulse termination is recorded, thus obtaining a stripping voltammetry curve of the seawater sample detection after the iron and manganese standard solution is added. Finally, ultrapure water is extracted to wash the detection tank 21 for 3 times, and the next seawater sample detection is waited.
The data processing and transmitting working process comprises the following steps: according to the values of the corresponding dissolution peak currents of the iron ions and the manganese ions in the two groups of dissolution volts An Quxian, concentration values of the iron ions and the manganese ions in the sea water sample are converted, detection data are sent to a server of a monitoring department in real time through a GPRS transmitter 26, the detection data are compared with historical data of the iron ions and the manganese ions in normal sea water, and early warning of red tide is sent when the concentration values show rising trend and exceed a threshold value.
Claims (10)
1. An on-line monitoring system for early warning of red tide is characterized by comprising a sampling tube, a filter, a solution distribution system, a detection pool, a ferro-manganese detection electrode, an integrated circuit and a power supply;
the solution distribution system comprises a six-position valve, a pure water bottle, a mercury plating liquid bottle, an iron standard liquid bottle, a manganese standard liquid bottle, a quantitative ring and an injection pump;
the six-position valve is provided with 6 external interfaces and 1 central interface, the central interface is positioned at the central position of the valve, and the central interface can be gated in the valve body with any 6 external interfaces uniformly distributed at the edge of the valve at a time; the central interface is connected to one end of the quantitative ring, and the 6 external interfaces are respectively connected with the sampling tube, the pure water bottle, the mercury plating liquid bottle, the iron standard liquid bottle, the manganese standard liquid bottle and the detection tank through pipelines; a filter is arranged on the sampling tube;
the upper end of the injection pump is provided with 3 interfaces: the left interface, the upper interface and the right interface are internally provided with 1 solution cavity, the solution cavity can be gated with any one interface at the upper end at a time, the left interface is connected with the other end of the quantitative ring, the upper interface is connected to the detection tank through a pipeline, and the right interface is connected to the waste liquid pipe through a pipeline;
the ferro-manganese detection electrode comprises a reference electrode, a working electrode and a counter electrode; the three electrode tips are each connected to the integrated circuit by electrode leads.
2. The on-line monitoring system for early warning of red tide according to claim 1, wherein the sampling tube is a polyether-ether-ketone plastic tube with an inner diameter of 0.25mm.
3. The on-line monitoring system for early warning of red tide according to claim 1, wherein the pore size of the filter membrane is 100 μm.
4. The on-line monitoring system for early warning of red tide according to claim 1, wherein the quantitative ring is an annular plastic pipe made of polyether-ether-ketone material with threaded fasteners at two ends, the internal capacity is 5mL, and when transferring a seawater sample, pure water, mercury plating solution, iron standard solution and manganese standard solution to a detection tank, the solution is pumped into the quantitative ring through a six-position valve by using a syringe pump, and then the solution in the quantitative ring is pushed into the detection tank.
5. The on-line monitoring system for early warning of red tide according to claim 1, wherein the solution cavity inside the injection pump is 10mL.
6. The on-line monitoring system for early warning of red tide according to claim 1, wherein the reference electrode is a silver/silver chloride electrode formed by electroplating silver chloride on the surface of a silver wire electrode with a diameter of 500 μm; the working electrode is a gold wire electrode with the diameter of 100 mu m; the counter electrode is a platinum wire electrode with the diameter of 500 mu m.
7. The on-line monitoring system for early warning of red tide according to claim 1, further comprising a GPRS transmitter connected to the integrated circuit, through which the detection data is transmitted in real time to a server of the monitoring department.
8. The on-line monitoring system for early warning of red tides according to claim 1, wherein the ferro-manganese detection electrode detects the seawater sample by using a differential pulse stripping voltammetry.
9. A method for online monitoring of iron and manganese ions in seawater and early warning of red tide by using the system of any one of claims 1-8, comprising the steps of:
(1) Electrode pretreatment: extracting the mercury plating solution into a detection pool, immersing a ferro-manganese detection electrode, depositing a mercury film on the surface of a working electrode to form a gold/mercury electrode, and then discharging the mercury plating solution; extracting pure water to clean the detection pool for more than three times, and removing residual mercury plating solution;
(2) Detecting a seawater sample: filtering impurities in the seawater through a filter, and extracting a seawater sample to a detection pool; the ferro-manganese detection electrode detects a seawater sample by using a differential pulse stripping voltammetry, and records a stripping voltammetry curve;
(3) And (3) adding standard solution for detection: extracting a proper amount of iron and manganese standard liquid from an iron standard liquid bottle and a manganese standard liquid bottle, adding the iron and manganese standard liquid into a seawater sample, detecting again by using a differential pulse stripping voltammetry under the same parameter condition, and recording a stripping voltammetry curve; discharging the seawater sample from the detection tank, extracting pure water to clean the detection tank for more than three times, and waiting for the next detection of the seawater sample;
(4) And (3) data processing and sending: according to the values of the dissolution peak currents respectively corresponding to the iron ions and the manganese ions in the two groups of dissolution volts An Quxian, concentration values of the iron ions and the manganese ions in the sea water sample are converted, detection data are sent to a monitoring department in real time, the detection data are compared with historical data of the iron ions and the manganese ions in normal sea water, and early warning of red tide is sent when the concentration values show rising trend and exceed a threshold value.
10. The method according to claim 9, wherein the ferro-manganese detection electrode uses differential pulse stripping voltammetry to detect seawater samples, in particular: firstly, applying constant potential on a working electrode, and reducing ferro-manganese ions into atomic states to be enriched on the surface of the working electrode; and then, the ferro-manganese atoms are electrolyzed and dissolved, namely, on the basis of applying a linear-change direct-current scanning voltage on a working electrode, a rectangular pulse potential with small amplitude is superposed, and the difference value of current at a certain time before pulse superposition and a certain time before pulse termination is recorded, so that a dissolution volt-ampere curve is obtained.
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