CN115839925B - Seawater nutrient salt online monitoring system and seawater nutrient salt detection method - Google Patents

Seawater nutrient salt online monitoring system and seawater nutrient salt detection method Download PDF

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CN115839925B
CN115839925B CN202310145101.7A CN202310145101A CN115839925B CN 115839925 B CN115839925 B CN 115839925B CN 202310145101 A CN202310145101 A CN 202310145101A CN 115839925 B CN115839925 B CN 115839925B
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detection
mixture
quantitative
detection reagent
seawater
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CN115839925A (en
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陈令新
付龙文
孙西艳
赵荣芳
夏春雷
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Yantai Institute of Coastal Zone Research of CAS
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Yantai Institute of Coastal Zone Research of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation

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Abstract

The invention discloses a seawater nutrient salt online monitoring system and a seawater nutrient salt detection method, wherein the monitoring system comprises a sealed cabin, a main control module, a detection module, a reagent accommodating device, a liquid inlet interface and an air interface; the detection modules comprise a first detection module for detecting nitrate and nitrite, a second detection module for detecting phosphate, a third detection module for detecting ammonium salt and a fourth detection module for detecting silicate which are arranged independently of each other; during detection, the first detection module, the second detection module, the third detection module and the fourth detection module work independently, different nutritive salts in seawater are detected respectively, and air clusters are introduced in detection to perform defoaming. The invention has high detection precision, small drift amount, stable and reliable operation, small detection reagent amount and small detection waste liquid amount, and can simultaneously or independently complete in-situ on-line analysis and monitoring of 5 nutrient salts of nitrate, nitrite, ammonia nitrogen, phosphate and silicate.

Description

Seawater nutrient salt online monitoring system and seawater nutrient salt detection method
Technical Field
The invention relates to the technical field of water quality monitoring, in particular to a seawater nutritive salt online monitoring system and a seawater nutritive salt detection method.
Background
The nutrient salt in the seawater mainly comprises inorganic nitrogen, active phosphate, active silicate and other components, and is a necessary nutrient element for the growth of marine phytoplankton. The different concentrations and compositions of the nutrient salt in the seawater not only can influence the primary productivity of the ocean, but also can regulate the community structure of phytoplankton, thereby influencing the structure of the ocean ecosystem. Therefore, monitoring the concentration distribution and change of nutrient salt in seawater has important scientific significance for evaluating the eutrophication of water body and knowing the geochemical circulation of nitrogen, phosphorus and silicon elements in the ocean and the key process of the ocean ecosystem.
At present, the analysis of nutritive salt in sea water mainly adopts a method of on-site sampling-laboratory measurement, and the method has the defects of poor instantaneity, easiness in pollution of a sample to be detected, waste of manpower and material resources and the like.
Some online seawater nutritive salt analyzers exist for measuring nutritive salt in seawater, but due to the limitation of the volume of the online seawater nutritive salt analyzers, the existing online seawater nutritive salt analyzers generally adopt a single module for sequential detection, the seawater to be detected flows in a plurality of detection modules, and the detection of the nutritive salt is carried out when the seawater to be detected flows to a specific detection module, the measurement error is generally about-20% - +45%, the measurement error is large, and the reagent consumption is large. Marine monitoring studies over the past decades have demonstrated that existing online seawater nutrient salt analyzers are unable to meet the increasingly urgent requirements for marine ecological environmental monitoring and protection.
Therefore, it is necessary to provide a new solution to the above-mentioned problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides the seawater nutrient salt online monitoring system which can improve the accuracy of online monitoring of the seawater nutrient salt, reduce the generation of waste liquid in the seawater nutrient salt detection process, reduce water pollution, and improve the accuracy, the reliability and the service life of the online monitoring system.
The technical scheme adopted by the invention is as follows.
An on-line monitoring system for seawater nutrient salts, comprising:
sealing the cabin;
the main control module is arranged in the sealed cabin;
the detection module is arranged in the sealed cabin and comprises a first detection module for detecting nitrate and nitrite, a second detection module for detecting phosphate, a third detection module for detecting ammonium salt and a fourth detection module for detecting silicate; the first detection module, the second detection module, the third detection module and the fourth detection module are mutually independent;
the reagent containing device is arranged outside the sealed cabin and is communicated with the detection module through a pipeline;
The liquid inlet is communicated with the detection module;
and the air interface is communicated with the detection module.
Preferably, the detection module comprises an injection device and a photoelectric detection device; the injection device includes a syringe pump and a multi-position valve, the syringe pump being in communication with the multi-position valve.
Preferably, the photodetection device comprises a flow cell, a light source and a receiver; the flow cell, light source and receiver are configured to detect an optical path and a reference optical path; the flow cell is in communication with the multi-position valve.
Preferably, the device further comprises a waste liquid storage device; the waste liquid storage device is communicated with the flow cell.
Preferably, the mobile terminal also comprises a handheld terminal; the handheld terminal is connected with the main control module in a wired communication or wireless communication mode.
Preferably, the device also comprises a navigation filtering device; the navigation filter device comprises a filter body with a filter cavity and an end cover; a filter element is arranged in the filter cavity; the end cover is fixed on the upper part of the filter body; the end cover is provided with a liquid inlet and a liquid outlet; the liquid outlet is connected with the filter element through a connecting pipe; the bottom of the filter body is provided with a slag discharging port communicated with the liquid inlet; the navigation filtering device is configured to enable seawater to be detected to enter the filtering cavity from the liquid inlet and be discharged from the slag discharging port in a non-detection state, and enable the seawater to be detected to be stored in the filtering cavity in a detection state.
The invention also provides a seawater nutrient salt detection method, which utilizes the seawater nutrient salt online monitoring system to detect the seawater nutrient salt, and comprises the following steps:
measuring absorbance values of deionized water and a standard solution respectively;
drawing a standard curve according to the deionized water, the concentration of the standard solution and the absorbance value of the deionized water and the absorbance value of the standard solution;
fully mixing a water sample with a detection reagent, and measuring the absorbance value of the mixture of the water sample and the detection reagent;
and (3) taking the absorbance value of the mixture of the water sample and the detection reagent into a standard curve and calculating to obtain the concentration parameter of the nutrient salt to be detected in the water sample.
Preferably, when detecting the absorbance values of the deionized water, the standard solution and the detection reagent, introducing air into the seawater nutrient salt on-line monitoring system for defoaming.
Preferably, the detection method of nitrite comprises the following steps:
respectively extracting a quantitative water sample, a quantitative detection reagent A and quantitative air, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture A; the volume ratio of the water sample to the detection reagent A to the air is 0.3:0.1:0.1;
pushing the mixture A into a photoelectric detection device to detect the absorbance value of the mixture A;
Carrying the absorbance value of the mixture A into a nitrite detection standard curve for operation to obtain the concentration parameter of nitrite in the water sample;
the quantitative detection reagent A comprises the following raw materials in proportion: 5.0 g of sulfanilamide, 0.25 g of NEDD (N- (1-naphthyl) -ethylenediamine dihydrochloride, 50 ml of 37% concentrated hydrochloric acid, 450 ml of deionized water.
Preferably, the method for detecting nitrate comprises the following steps:
pushing the quantitative water sample into a first detection module for reduction to obtain a mixture B;
taking the mixture B and the quantitative detection reagent A, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture C; the volume ratio of the water sample to the detection reagent A to the air is 0.3:0.1:0.1;
pushing the mixture C into a photoelectric detection device to detect the absorbance value of the mixture C;
carrying the absorbance value of the mixture C into a nitrate detection standard curve for operation to obtain a concentration parameter of nitrate in the water sample;
the quantitative detection reagent A comprises the following raw materials in proportion: 5.0 g of sulfanilamide, 0.25 g of NEDD (N- (1-naphthyl) -ethylenediamine dihydrochloride, 50 ml of 37% concentrated hydrochloric acid, 450 ml of deionized water.
Preferably, the method for detecting phosphate comprises the following steps:
respectively extracting a quantitative water sample, a quantitative detection reagent B, a quantitative detection reagent C and quantitative air, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture D; the volume ratio of the water sample to the detection reagent B to the detection reagent C to the air is 0.2:0.1:0.1:0.1;
Pushing the mixture D into a photoelectric detection device to detect the absorbance value of the mixture D;
carrying the absorbance value of the mixture D into a phosphate detection standard curve for operation to obtain the concentration parameter of phosphate in the water sample;
the quantitative detection reagent B comprises the following raw materials in proportion: 1.2 g ammonium molybdate tetrahydrate, 4.4 ml of potassium antimony tartrate solution and 10.4 ml of concentrated sulfuric acid;
the quantitative detection reagent C comprises the following raw materials in proportion: 1.6 g ascorbic acid, 200 ml deionized water.
Preferably, the method for detecting ammonium salt comprises the following steps:
heating the third detection module to a preset temperature;
extracting a quantitative water sample, a quantitative detection reagent D and quantitative air, and fully mixing in a circulating pushing-out and sucking mode to obtain a mixture E;
extracting a quantitative detection reagent E and fully mixing the mixture E in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture F;
extracting a quantitative detection reagent F and fully mixing the reagent F with the mixture F in a circulating pushing-out and sucking-in mode to obtain a mixture G;
pushing the mixture G into a photoelectric detection device to detect the absorbance value of the mixture G;
carrying the absorbance value of the mixture G into an ammonium salt detection standard curve for operation to obtain the concentration parameter of ammonium salt in the water sample;
The volume ratio of the water sample to the detection reagent D to the detection reagent E to the detection reagent F to the air is 0.3:0.05:0.05:0.05:0.05;
the quantitative detection reagent D comprises the following raw materials in proportion: 120 g sodium citrate, 250 mL water, 10 mL NaOH solution;
the quantitative detection reagent E comprises the following raw materials in proportion: 120 Sodium salicylate, 0.2g sodium nitroprusside, 500 mL water;
the quantitative detection reagent F comprises the following raw materials in proportion: 2.7 The mLNaClO was sized to 200 mL.
Preferably, the silicate detection method comprises the following steps:
respectively extracting a quantitative water sample, a detection reagent G and air, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture H;
taking a certain amount of detection reagent H and the mixture H, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture I;
taking a certain amount of detection reagent I and the mixture I, and fully mixing in a mode of circularly pushing out and sucking the mixture I into a flow cell to obtain a mixture J;
pushing the mixture J into a photoelectric detection device to detect the absorbance value of the mixture J;
carrying the absorbance value of the mixture J into a silicate detection standard curve for operation to obtain concentration parameters of silicate in the water sample;
the volume ratio of the water sample to the detection reagent G to the detection reagent H to the detection reagent I to the air is 0.3:0.05:0.05:0.05:0.05;
The quantitative detection reagent G comprises the following raw materials in proportion: 2.4 g ammonium molybdate, 3.375, mL concentrated sulfuric acid, 246, mL deionized water;
the quantitative detection reagent H comprises the following raw materials in proportion: 10 g oxalic acid, 200 mL deionized water;
the quantitative detection reagent I comprises the following raw materials in proportion: 4.0g ascorbic acid, 200 mL deionized water.
Preferably, the quantitative detection reagent A comprises the following raw materials in proportion: 5.0 g of sulfanilamide, 0.25 g of NEDD (N- (1-naphthyl) -ethylenediamine dihydrochloride, 50 ml of 37% concentrated hydrochloric acid, 450 ml of deionized water.
Preferably, the quantitative detection reagent B comprises the following raw materials in proportion: 1.2 g of ammonium molybdate tetrahydrate, 4.4 ml of potassium antimonate solution and 10.4 ml of concentrated sulfuric acid.
The quantitative detection reagent C comprises the following raw materials in proportion: 1.6 g ascorbic acid, 200 ml deionized water.
Preferably, the quantitative detection reagent D comprises the following raw materials in proportion: 120 g sodium citrate, 250 mL water, 10 mL NaOH solution;
the quantitative detection reagent E comprises the following raw materials in proportion: 120 Sodium salicylate, 0.2g sodium nitroprusside, 500 mL water;
the quantitative detection reagent F comprises the following raw materials in proportion: 2.7 The mLNaClO was sized to 200 mL.
Preferably, the quantitative detection reagent G comprises the following raw materials in proportion: 2.4 g ammonium molybdate, 3.375, mL concentrated sulfuric acid, 246, mL deionized water;
The quantitative detection reagent H comprises the following raw materials in proportion: 10 g oxalic acid, 200 mL deionized water;
the quantitative detection reagent I comprises the following raw materials in proportion: 4.0g ascorbic acid, 200 mL deionized water.
Preferably, the introducing air into the seawater nutrient salt on-line monitoring system for defoaming specifically comprises:
after the injection pump sucks the liquid to be detected, the multi-position valve is controlled by the main control module, so that the injection pump is connected with the air interface through a pipeline, and a certain amount of air is introduced into the front end of the solution to be detected, so that an air column is formed in the pipeline;
the multi-position valve is controlled by the main control module, the passage of the injection pump and the air interface is closed, the injection pump is used for pushing the air column and the liquid to be detected to flow along the pipeline, the liquid to be detected is pushed into the flow cell, and the air column is pushed out of the flow cell.
Compared with the prior art, the invention has at least the following beneficial effects:
1. the seawater nutrient salt online monitoring system adopts mutually independent detection modules to detect seawater nutrient salt, has high detection precision, small drift amount, stable and reliable operation, small detection reagent amount and small detection waste liquid amount, can simultaneously or independently realize in-situ and navigation online analysis and monitoring of 5 nutrient salts of nitrate, nitrite, ammonium salt, phosphate and silicate, and improves the seawater nutrient salt real-time online monitoring capability of marine ecological environment;
2. The seawater nutrient salt on-line monitoring system comprises a navigation filtering device, wherein the surface seawater can be stored in a filtering cavity or can flow according to a detection state or a non-detection state, and the fixed-point rapid detection of the seawater nutrient salt under the navigation state is realized.
3. When the seawater nutrient salt is detected, the influence of the water color per se on the detection is subtracted by adopting an actual water sample, so that the interference of environmental factors is avoided; the reference light path in the detection module controls the brightness of the LED, so that detection inconsistency caused by LED attenuation is reduced, and the detection precision is improved; an air group is introduced to perform defoaming, so that the influence of small bubbles in a detection flow path on a detection result is effectively avoided, meanwhile, the air group can also seal a detection tank, other liquid is prevented from entering the detection tank, the detection tank is not polluted, and the detection precision is further improved; the instrument reagent is in direct contact with the environmental water body, so that the influence of the environmental temperature on detection is reduced, and meanwhile, the reagent is prevented from losing efficacy in a high-temperature environment by utilizing the water body temperature.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an on-line monitoring system for seawater nutrient salts according to the present invention;
FIG. 2 is a schematic diagram of a seawater nutrient salt on-line monitoring system with a hidden protective cover;
FIG. 3 is a schematic diagram of the internal structure of an on-line monitoring system for seawater nutrient salts according to the present invention;
FIG. 4 is a schematic structural view of a photoelectric detection device of an on-line monitoring system for seawater nutrient salt;
FIG. 5 is a schematic diagram of the liquid inlet of the photoelectric detection device of the seawater nutrient salt on-line monitoring system;
FIG. 6 is a schematic diagram of a navigation filter device of the seawater nutrient salt on-line monitoring system of the invention;
FIG. 7 is a state diagram of the use of the navigation filter of the seawater nutrient salt on-line monitoring system of the invention;
FIG. 8 is a schematic diagram of the overall flow of a method for detecting seawater nutrient salts according to the present invention;
FIG. 9 is a plot of 200 samples measured by the pilot in an embodiment of the invention;
FIG. 10 is a diagram showing the spatial and temporal distribution of nitrite in the sea area of yellow river;
FIG. 11 is a diagram showing the spatial and temporal distribution of nitrate in the sea area of yellow river;
FIG. 12 is a diagram showing the spatial and temporal distribution of ammonium salt in the sea area of yellow river;
FIG. 13 is a diagram showing the spatial and temporal distribution of phosphate in the sea area of yellow river;
FIG. 14 is a graph showing the spatiotemporal distribution of the sub-silicate in the sea area of yellow river.
Wherein the above figures include the following reference numerals:
1. a protective cover 2, a sealed cabin 3, a handle 4, a waterproof joint 5, a liquid inlet interface 6, an air interface 7, a reagent holding device fixing piece 8, a supporting rod 9 and a supporting plate, 10, a main control module, 11, a power supply module, 12, a communication module, 13, a first detection module, 14, a second detection module, 15, a third detection module, 16 and a fourth detection module; 17. reagent accommodating device 18, photoelectric detection device 19 and navigation filtering device;
201. A hatch cover, 202, a hatch body;
501. an internal thread cavity 502, an external thread part 503, a limiting part 504, a throat part 505 and a vertebral canal part;
1801. a flow cell 1802, a detection light source 1803, a reference light source 1804, a detection fixing seat 1805, a reference light path receiver 1806 and a detection light path receiver;
1901. end cover 1902, filter body 1903, slag discharging hopper, 1904, exhaust valve, 1905, liquid outlet, 1906, liquid inlet, 1907, connecting pipe, 1908, filter element, 1909, slag discharging port, 1910, liquid supply pipe, 1911, slag discharging pipe, 1912 and liquid supply valve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, an on-line monitoring system for seawater nutrient salts, comprising: a protective cover 1, a sealed cabin 2 and a handle 3. The protection cover 1 covers the outside of the sealed cabin 2 and is used for protecting the sealed cabin 2. The lifting handle 3 is fixed on the top of the sealed cabin 2 and is used for fixing the seawater nutrient salt on-line monitoring system with an external buoy or a ship body and the like for monitoring.
As shown in fig. 2 and referring to fig. 3, the sealed cabin 2 includes a cabin cover 201 and a cabin body 202. The waterproof connector 4, the liquid inlet connector 5 and the air connector 6 are all arranged on the upper portion of the cabin cover 201, and the liquid inlet connector 5 is communicated with an external detection water sample pipe or a detection reagent pipe and used for correspondingly detecting water samples or detection reagents entering the cabin body 202. The waterproof joint 4 is used for electrically connecting the components inside the sealed cabin 2 with the external components. The air interface 6 is used for introducing external air into the sealed cabin 2 for introducing air in seawater nutrient salt detection. The reagent holding apparatus fixing member 7 is provided on the outer wall of the nacelle 202 for fixing the reagent holding apparatus 17.
As shown in fig. 3, the sealed cabin 2 has a cavity therein, and the support plate 9 has a plurality of layers provided in the sealed cabin 2 to divide the cavity into a plurality of independent spaces. The backup pad 9 relies on bracing piece 8 to carry out fixed stay, improves the stability of backup pad 9. The main control module 10, the power supply module 11, the communication module 12 and the detection module are all fixed in the sealed cabin 2. The detection modules comprise a first detection module 13 for detecting nitrate or nitrite, a second detection module 14 for detecting phosphate, a third detection module 15 for detecting ammonium salts and a fourth detection module 16 for detecting silicate. The first detection module 13, the second detection module 14, the third detection module 15 and the fourth detection module 16 are mutually independent, and can respectively and independently detect nitrate or nitrite, phosphate, ammonium salt and silicate, so that the detection modules are not polluted, and the structure can shorten a circulating pipeline, can detect the corresponding nutrient salt content under the condition of a small amount of water sample, reduce the use of detection reagents, improve the detection precision and reduce the generation of detection waste liquid. The first detection module 13 has a cadmium ring therein for reducing nitrate. The detection module includes an injection device (not shown) including an injection pump in communication with the multi-position valve and a multi-position valve, and a photo detection device 18. The injection pump and the multi-position valve are both of the conventional type sold in the market.
The reagent container 17 is provided outside the capsule 2 by a reagent container holder 7, and is used for accommodating a reagent, preferably a reagent container bag made of a flexible material. The reagent holding device 17 communicates with the detection module via a conduit and a liquid inlet port 5. The detection reagent is fast in deterioration and even fails after the temperature exceeds 30 ℃, so that the detection precision is affected, and the temperature of the existing in-situ nutrient salt analyzer cabin is over 40 ℃ or higher due to heat release caused by the operation of a plurality of components, so that the detection reagent has great influence on monitoring of the seawater nutrient salt. The reagent holding device 17 is arranged outside the sealed cabin 2 and is in contact with the external seawater, and the temperature of the seawater is not more than 30 ℃, so that the seawater is used for preservation, the detection reagent can be effectively prevented from going bad, meanwhile, the temperature of the detection reagent is equal to the temperature of the seawater, the detection precision is improved, and meanwhile, the volume of the sealed cabin 2 can be saved. In addition, an air interface 6 is communicated with the detection module and is used for introducing air in the detection of the seawater nutrient salt.
As shown in fig. 4, the photodetection device 18 includes a flow cell 1801, a detection light source 1802, a reference light source 1803, a detection holder 1804, a reference light path receiver 1805, and a detection light path receiver 1806. The flow cell 1801 communicates with the multi-position valve such that liquid and gas in the multi-position valve can be pumped into the flow cell 1801 by the syringe pump.
The detection light source 1802 is fixed on the detection fixing seat 1804, and a light beam emitted by the detection light source 1802 passes through the flow cell 1801 and is received by the detection light path receiver 1806, so as to form a detection light path. The reference light source 1803 is fixed on the detection fixing seat 1804, and a light beam emitted by the reference light source 1803 passes through the flow cell 1801 and is received by the reference light path receiver 1805, so as to form a reference light path.
The detection light source 1802 and the reference light source 1803 use LED light sources that are powered by the same circuit and are of the same specification and model. Meanwhile, the power supply circuits of the detection light source 1802 and the reference light source 1803 are electrically connected with the main control module 10, and the current of the power supply circuits is controlled by the main control module 10.
The reference light path can detect the light intensity of the reference light source 1803 when the device is started each time, and feed back to the main control module 10 to be compared with the light intensity when the standard solution is detected, so as to determine whether the light intensities of the detection light source 1802 and the reference light source 1803 are the same as the light intensity when the standard solution is detected. When the light intensities of the detection light source 1802 and the reference light source 1803 are different from those of the standard solution during detection, the main control module 10 sends out a control signal to adjust the light intensities of the reference light source 1803 and the detection light source 1802 in a mode of adjusting the current of a power supply circuit of the detection light source 1802 and the reference light source 1803, so that the light intensities of the detection light source 1802 and the reference light source 1803 are completely the same as those of the standard solution during detection during each start-up detection, and the accuracy of each detection is improved.
The detection light source 1802 and the reference light source 1803 both adopt single-wavelength LED light sources, and the wavelength selection of the LED light sources for different nutrient salts is different, specifically: the photo detection device 18 in the first detection module 13 for detecting nitrate or nitrite is selected as a 550nm LED light source; the photo-detection means 18 in the second detection module 14 for detecting phosphate is selected as an LED light source of 880 nm; the photodetection device 18 in the third detection module 15 for detecting ammonium salt is selected as an LED light source of 660 nm; the fourth detection module 16 for silicate detection selects an LED light source of 820 nm. In consideration of the complex mechanism in seawater, a part of light absorption substances and turbidity of the water body can be generated, so that the method directly deducts the absorbance value of the body water, and the influence of the water color on detection is deducted by adopting an actual water sample before each detection, thereby avoiding the interference of environmental factors.
As an embodiment of the present invention, as shown in fig. 5 and referring to fig. 2, the liquid inlet 5 includes an external threaded portion 502, a limiting portion 503, a throat portion 504, and a cone portion 505, which are integrally formed and sequentially connected. The externally threaded portion 502 includes an internally threaded cavity 501. The liquid inlet 5 is connected with the hatch 201 through threads on the outer wall of the external thread part 502, so that the liquid inlet 5 is fixed on the hatch 201. Meanwhile, the liquid inlet port 5 is positioned by the action of the limiting portion 503. In addition, an annular groove for placing a sealing ring is further arranged between the limiting part 503 and the external thread part 502, and is used for sealing the contact position of the limiting part 503 and the hatch cover 201, and placing external seawater into the hatch body 202. The internal thread cavity 501 can be in threaded connection with the internal pipeline through a threaded connection mode, so that the detachable fixed connection between the internal pipeline and the liquid inlet port 5 is realized. The cone portion 505 has a conical structure with a communication cavity inside, and can be inserted into an external hose, so that connection is facilitated. The outer diameter of the throat portion 504 is smaller than the diameter of the tail end of the cone portion 505, so that the external pipeline connected with the cone portion 505 can be effectively prevented from falling out.
As an embodiment of the present invention, the on-line monitoring system for seawater nutrient salts further comprises a waste liquid storage device (not shown in the figure), which is in communication with the flow cell 1801, and is capable of storing the post-detection reagent and water sample mixture, and preventing seawater pollution caused by direct discharge.
As an embodiment of the present invention, the seawater nutrient salt online monitoring system further comprises a hand-held terminal (not shown in the figure). The handheld terminal can be electrically connected with the power supply module 11 through a line, and is powered on site by means of the power supply module 11. The hand-held terminal is connected with the main control module 10 through the communication module 12 in a wired communication or wireless communication mode. The wired communication is preferably R485 communication. The wireless communication is preferably any one of bluetooth communication, infrared communication or zigbee communication. The handheld terminal adopts IP65 waterproof grade, has good waterproof nature. Because the existing in-situ nutritive salt analyzer mainly relies on a communication part and a notebook computer to carry out equipment debugging, data transmission and on-site calibration in a wired connection mode, the notebook computer is easy to wet in the marine seawater environment and has no 220V power supply, in addition, the notebook computer needs two hands to operate, the convenience is extremely poor, and the handheld terminal can improve the on-site debugging and calibration convenience of the seawater nutritive salt on-line monitoring system equipment.
As an embodiment of the present invention, as shown in fig. 6 and referring to fig. 2, an on-line monitoring system for seawater nutrient salts further comprises a navigation filter device 19 for filtering seawater to be detected entering the interior of the system. The navigation filter device 19 includes a filter body 1902 and an end cap 1901. The filter 1902 has a filter chamber (not shown) therein. An end cap 1901 is secured to an upper portion of filter body 1902. The end cap 1901 is provided with a liquid inlet 1906 and an exhaust valve 1904 which are communicated with the interior of the filter cavity. The intake 1906 is used to pump external seawater through a pipe into the filter cavity inside the filter body 1902. The vent valve 1904 is capable of venting gas from the filter cavity within the filter body 1902 in an open state. In addition, the end cover 1901 is further provided with liquid outlets 1905, the number of which is the same as that of the liquid inlet ports 5. The filter chambers inside the filter body 1902 are provided with filter cores 1908 the same in number as the liquid outlets 1905. The filter element 1908 is communicated with the liquid outlet 1905 through a connecting pipe 1907, so that seawater to be detected filtered by the filter element 1908 can enter the liquid outlet 1905. In addition, a slag discharge hopper 1903 is provided at the bottom of the filter chamber inside the filter body 1902. The slag discharging hopper 1903 is funnel-shaped, and a slag discharging opening 1909 is arranged at the bottom of the slag discharging hopper.
As shown in fig. 7 and referring to fig. 6 and 3, in a use state, the liquid inlet 1906 of the navigation filter device 19 is connected with a surface water inlet pump of the monitoring ship through a liquid supply pipe 1910, and a liquid supply valve 1912 is arranged on the liquid supply pipe 1910. The slag discharge port 1909 is connected with a waste liquid well of the monitoring ship through a slag discharge pipe 1911. The liquid outlets 1905 are respectively connected with the corresponding liquid inlet interfaces 5 through pipelines, so that the seawater to be detected discharged by each liquid outlet 1905 can enter the seawater nutrient salt on-line monitoring system through the liquid inlet interfaces 5 for detection. Before use, the vent valve 1904 is opened and the air in the filter cavity inside the filter 1902 is closed after being exhausted. In the sailing state, the exhaust valve 1904 is normally closed, and the liquid supply valve 1912 is normally open. At this time, the surface seawater pumped by the surface water intake pump of the monitoring ship enters the filter cavity inside the filter 1902 through the liquid supply pipe 1910, and is discharged into the waste liquid well of the monitoring ship through the slag discharge port 1909 and the slag discharge pipe 1911. When it is desired to determine the sea nutrient at a certain coordinate point, the fluid supply valve 1912 is closed. At this time, seawater in the filter chamber inside the filter body 1902 remains therein due to the presence of atmospheric pressure. The syringe pumps in the first detection module 13, the second detection module 14, the third detection module 15 and the fourth detection module 16 can pump seawater to be detected filtered by the filter element 1908 for detection. After the test is completed, the feed valve 1912 is opened and the seawater in the filter cavity inside the filter body 1902 is again allowed to flow.
The navigation filter device 19 can seal the seawater to be detected in the filter cavity inside the filter body 1902 by means of the sealing effect of the end cover 1901, the filter body 1902, the exhaust valve 1904 and the liquid supply valve 1912 in the closed state, so that fixed-point water taking in the navigation process of the ship is realized, and the condition of inaccurate detection points caused by navigation of the ship is avoided. Meanwhile, after the liquid supply valve 1912 is opened, impurities and wastes in the filter cavity inside the filter body 1902 can be washed away by means of the flow of seawater, so that self-cleaning is realized. In addition, the funnel-shaped slag discharge opening 1909 can increase the local flow rate, further improving the discharge effect of impurities and waste in the filter cavity inside the filter body 1902.
The parameter comparison of the seawater nutrient salt online monitoring system and the WIZ in-situ nutrient salt analyzer of Systea company in Italy is shown in the following table:
Figure SMS_1
the components of the seawater nutrient salt online monitoring system are closely connected to form a complete whole, so that the online monitoring function of the seawater nutrient salt can be realized, the detection precision of the nutrient salt in the seawater is improved, compared with the existing equipment, the online monitoring system has a good monitoring effect, the components cannot be independently split, and the corresponding technical problems of the invention cannot be solved by the superposition of similar functional independent components.
As shown in fig. 8, the invention further provides a method for detecting seawater nutritive salt, which uses the seawater nutritive salt on-line monitoring system to detect seawater nutritive salt, and comprises the following steps:
s1, respectively measuring absorbance values of deionized water and a standard solution;
s2, drawing a standard curve according to the deionized water, the concentration of the standard solution and the absorbance value of the deionized water and the absorbance value of the standard solution;
s3, fully mixing the water sample with the detection reagent, and measuring the absorbance value of the mixture of the water sample and the detection reagent;
s4, carrying the absorbance value of the mixture of the water sample and the detection reagent into a standard curve, and calculating to obtain the concentration parameter of the nutrient salt to be detected in the water sample.
Wherein, the absorbance calculation formula is as follows:
Figure SMS_2
wherein A is absorbance value, I 0 Is the photovoltage value of deionized water, standard solution or water sample, I 1 The photovoltage value of deionized water, standard solution or mixture of water sample and detection reagent;
the calculation formula of the sample concentration is as follows:
Figure SMS_3
wherein C is Sample of For the concentration value of the sample, A Sample of Is the absorbance value of a water sample, A Blank space Absorbance value of deionized water, A Standard sample Absorbance value of standard solution, C Standard sample Is the concentration value of the standard solution.
In addition, when the absorbance values of deionized water, standard solution and detection reagent are detected, air is introduced into the seawater nutrient salt on-line monitoring system, so that small bubbles in the seawater nutrient salt on-line monitoring system pipeline can be broken after contacting the introduced air and are fused with the introduced air, and defoaming is realized.
The method comprises the following steps: after the liquid to be detected is sucked into the injection pump, the main control module 10 controls the multi-position valve, so that the injection pump is connected with the air interface 6 through a pipeline, and a certain amount of air is introduced into the front end of the liquid to be detected, so that an air column is formed in the pipeline. The multi-position valve is controlled by the main control module 10, the passage between the injection pump and the air interface 6 is closed, the injection pump is used for pushing the air column and the liquid to be detected to flow along the pipeline, the liquid to be detected is pushed into the flow cell 1801, and the air column is pushed out of the flow cell 1801. In the process that the air column moves along the pipeline along with the liquid to be detected, small bubbles hanging on the pipeline can be fused, defoaming of the small bubbles is achieved, and the small bubbles in the pipeline are prevented from entering the flow cell 1801 to affect absorbance detection. Preferably, the amount of air introduced during defoaming is 0.2ML.
As one embodiment of the invention, the mixture of the water sample and the detection reagent can be collected for a plurality of times to detect the photovoltage value I during the detection process 1 The method can effectively remove the influence of photovoltage values caused by different factors such as chromaticity, turbidity or pH in the water sample, repeatedly extract and push out the water sample for 3-5 times, and can achieve the effects of moistening water sample tubes, injectors, detectors, isolating waste liquid from suck-back pollution and the like.
The seawater nutrient salt detection method comprises a nitrite detection method, a nitrate detection method, a phosphate detection method, an ammonium salt detection method and a silicate detection method.
The nitrite detection adopts a naphthalene ethylenediamine colorimetric method, and specifically, the nitrite detection method comprises the following steps:
step Sa1, extracting 0.3ml of water sample;
step Sa2, extracting 0.1ml of quantitative detection reagent A;
step Sa3, extracting 0.1ml of air;
step Sa4, pushing out 0.5ml of a mixture A consisting of a water sample, a quantitative detection reagent A and air, sucking 0.5ml, and fully mixing according to 0.5ml in a circulating pushing-out and sucking mode;
step Sa5, pushing all the fully mixed mixture A into the photoelectric detection device 18, and turning on a light source;
step Sa6, reading the absorbance value of the mixture A, and turning off the light source;
step Sa7, the absorbance value of the mixture A is brought into a standard curve A and calculated, and the concentration parameter of nitrite in the water sample is obtained.
The nitrate detection adopts a cadmium ring reduction-naphthalene ethylenediamine colorimetric method, and specifically, the detection method of the nitrate comprises the following steps:
step Sb1, extracting 0.65ml of water sample;
step Sb2, pushing a water sample into a cadmium ring of the first detection module 13 for reduction, and respectively pushing out and sucking 0.2ml to obtain a mixture B;
step Sb3, taking 0.3ml of the mixture B;
step Sb4, taking 0.1ml of quantitative detection reagent A;
step Sb5, taking 0.1ml of air;
step Sb6, pushing out 0.5ml of a mixture C consisting of the mixture B, the detection reagent A and air, sucking 0.5ml, and fully mixing in a mode of circularly pushing out and sucking 0.5 ml;
step Sb7, pushing all the fully mixed mixture C into the photodetection device 18, and turning on the light source;
step Sb8, reading the absorbance value of the mixture C, and turning off the light source;
step Sb9, bringing the absorbance value of the mixture C into a standard curve B and calculating to obtain the concentration parameter of nitrate in the water sample;
the detection of phosphate adopts a phosphomolybdenum blue colorimetric method, and specifically, the detection method of phosphate comprises the following steps:
step Sc1, extracting 0.2ml of water sample;
step Sc2, extracting 0.1ml of quantitative detection reagent B;
sc3, extracting 0.1ml of quantitative detection reagent C;
Sc4, extracting 0.1ml of air;
pushing out 0.5ml of a mixture D consisting of a water sample, a quantitative detection reagent B, a quantitative detection reagent C and air, sucking 0.5ml, and fully mixing in a mode of cyclic pushing out and sucking 0.5 ml;
step Sc6, pushing all the fully mixed mixture D into the photoelectric detection device 18, and turning on a light source;
step Sc7, reading the absorbance value of the mixture D, and turning off the light source;
and step Sc8, carrying the absorbance value of the mixture D into a standard curve C, and calculating to obtain the concentration parameter of the phosphate in the water sample.
The detection of the ammonium salt adopts a salicylic acid colorimetric method, and specifically, the detection method of the ammonium salt comprises the following steps:
step Sd1, heating the third detection module 15 to a preset temperature of 45 degrees;
sd2, extracting 0.3ml of water sample;
sd3, extracting 0.05ml of quantitative detection reagent D;
sd4, extracting 0.05ml of air;
step Sd5, pushing out 0.5ml of a mixture E consisting of a water sample, a quantitative detection reagent D and air, sucking 0.5ml, and fully mixing in a mode of circularly pushing out and sucking 0.5 ml;
step Sd6, extracting 0.05ml of quantitative detection reagent E;
step Sd7, sucking the mixture E back to the injection pump;
step Sd8, fully mixing the mixture F consisting of the mixture E and the quantitative detection reagent E in a mode of circularly pushing out and sucking in 0.5 ml;
Step Sd9, extracting 0.05ml of quantitative detection reagent F;
step Sd10, fully mixing a mixture G consisting of the mixture F and the quantitative detection reagent F in a mode of pushing out and sucking in 0.5ml of the mixture in a circulating way;
sd11, pushing the fully mixed mixture G into the photoelectric detection device 18 completely, and turning on a light source;
step Sd12, reading the absorbance value of the mixture G, and turning off the light source;
step Sd13, stopping heating the third detection module 15;
and step Sd14, carrying the absorbance value of the mixture G into a standard curve D and calculating to obtain the concentration parameter of the ammonium salt in the water sample.
The detection of silicate adopts a silicomolybdenum blue colorimetric method, and specifically, the detection method of silicate comprises the following steps:
se1, extracting 0.3ml of water sample;
se2, extracting 0.05ml of quantitative detection reagent G;
se3, extracting 0.05ml of air;
step Se4, pushing out 0.5ml of a mixture H consisting of a water sample, a quantitative detection reagent G and air, sucking 0.5ml, and then fully mixing in a mode of circularly pushing out and sucking 0.5 ml;
se5, extracting 0.05ml of quantitative detection reagent H;
step Se6, fully mixing the mixture I consisting of the mixture H and the quantitative detection reagent H in a way of pushing out and sucking in 0.5ml circularly;
Se7, extracting 0.05ml of quantitative detection reagent I;
step Se8, mixing the mixture I with the quantitative detection reagent I to obtain a mixture J, and fully mixing the mixture J in a mode of circularly pushing out and sucking in 0.5 ml;
step Se9, pushing the fully mixed mixture J into the photoelectric detection device 18 completely, and turning on a light source;
step Se10, reading absorbance value of the mixture J;
and step Se11, carrying the absorbance value of the mixture J into a standard curve E and calculating to obtain the concentration parameter of silicate in the water sample.
As an embodiment of the invention, the raw materials and the proportion of the quantitative detection reagent are important, and the highest color development intensity of the detection module, namely the highest absorbance, can be realized. Specific:
the quantitative detection reagent A comprises the following raw materials in proportion: 5.0 g of sulfanilamide, 0.25 g of NEDD (N- (1-naphthyl) -ethylenediamine dihydrochloride, 50 ml of 37% concentrated hydrochloric acid, 450 ml of deionized water;
the quantitative detection reagent B comprises the following raw materials in proportion: 1.2 g ammonium molybdate tetrahydrate, 4.4 ml of potassium antimony tartrate solution and 10.4 ml of concentrated sulfuric acid;
the quantitative detection reagent C comprises the following raw materials in proportion: 1.6 g ascorbic acid, 200 ml deionized water;
the quantitative detection reagent D comprises the following raw materials in proportion: 120 g sodium citrate, 250 mL water, 10 mL NaOH solution;
The quantitative detection reagent E comprises the following raw materials in proportion: 120 Sodium salicylate, 0.2g sodium nitroprusside, 500 mL water;
the quantitative detection reagent F comprises the following raw materials in proportion: 2.7 mLNaClO is fixed to a volume of 200 mL;
the quantitative detection reagent G comprises the following raw materials in proportion: 2.4 g ammonium molybdate, 3.375, mL concentrated sulfuric acid, 246, mL deionized water;
the quantitative detection reagent H comprises the following raw materials in proportion: 10 g oxalic acid, 200 mL deionized water;
the quantitative detection reagent I comprises the following raw materials in proportion: 4.0g ascorbic acid, 200 mL deionized water.
The detection limit of the seawater nutrient salt on-line monitoring system can be realized as follows:
nitrite 0.2 mug/L, nitrate 0.3 mug/L, ammonium salt 2.8 mug/L, phosphate 1.2 mug/L, silicate 2.8 mug/L.
Table 1 detection limit comparison table
Figure SMS_4
The seawater nutrient salt online monitoring system can be used for in-situ online monitoring and sailing online monitoring, and is applied to the following fields.
Application example:
navigation type seawater nutrient salt on-line monitoring system
The seawater nutrient salt online monitoring system can realize five-parameter parallel monitoring, and can complete detection of 5 parameters in 20 minutes, as shown in fig. 9, 200 sampling points are actually measured in the yellow river mouth navigation, and the nutrient salt distribution conditions of the yellow river mouth sea areas of 2022, 5, 7, 11 months and 2023 months are obtained.
FIG. 10 is a diagram showing the spatial and temporal distribution of nitrite in the sea area of yellow river; FIG. 11 is a diagram showing the spatial and temporal distribution of nitrate in the sea area of yellow river; FIG. 12 is a diagram showing the spatial and temporal distribution of ammonium salt in the sea area of yellow river; FIG. 13 is a diagram showing the spatial and temporal distribution of phosphate in the sea area of yellow river; FIG. 14 is a graph showing the spatiotemporal distribution of the sub-silicate in the sea area of yellow river.
Table 2 is a table of nitrite different time detection conditions in the yellow river estuary; table 3 is a table of nitrate detection conditions in the yellow river estuary sea area; table 4 is a table of different time detection conditions of ammonium salts in the yellow river estuary; table 5 is a yellow river estuary sea area phosphate different time detection case table; table 6 shows the silicate detection conditions at different times in the sea area of yellow river.
TABLE 2 yellow river estuary nitrite different time detection Condition Meter
Figure SMS_5
TABLE 3 yellow river estuary sea area nitrate different time detection condition table
Figure SMS_6
TABLE 4 yellow river estuary sea area ammonium salt different time detection situation table
Figure SMS_7
TABLE 5 yellow river estuary phosphate different time detection case table
Figure SMS_8
TABLE 6 yellow river mouth sea area silicate different time detection condition table
Figure SMS_9
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As shown in fig. 10-14, and tables 2-6, the main source yellow river runoff; in the dry period, the nutrient salts input by the small river are highlighted. The ecological water supplementing period in spring is found, and the high-concentration nutrient salt mainly comprises N, P. 5 months, ecological moisturizing in spring: the runoff fresh water expands north from the gate to the sea and is conveyed south along the coastline to enter the Laizhou bay; 7 months, water-rich period: clearly, the estuary jet morphology, the plume spread mainly north-east and south to the entire Laozhou bay; 11 months, dry period: the Laizhou bay has a dilute water input and fresh water is transported from the west to the east of the Laizhou bay.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. An on-line monitoring system for seawater nutrient salts, comprising:
sealing the cabin;
the main control module is arranged in the sealed cabin;
the detection module is arranged in the sealed cabin and comprises a first detection module for detecting nitrate and nitrite, a second detection module for detecting phosphate, a third detection module for detecting ammonium salt and a fourth detection module for detecting silicate; the first detection module, the second detection module, the third detection module and the fourth detection module are mutually independent;
the reagent containing device is arranged outside the sealed cabin and is communicated with the detection module through a pipeline;
the liquid inlet is communicated with the detection module;
The air interface is communicated with the detection module;
the navigation filter device comprises a filter body with a filter cavity and an end cover; a filter element is arranged in the filter cavity; the end cover is fixed on the upper part of the filter body; the end cover is provided with a liquid inlet and a liquid outlet; the liquid outlet is connected with the filter element through a connecting pipe; the bottom of the filter body is provided with a slag discharging port communicated with the liquid inlet; the navigation filtering device is configured to enable seawater to be detected to enter the filtering cavity from the liquid inlet and be discharged from the slag discharging port in a non-detection state, and enable the seawater to be detected to be stored in the filtering cavity in a detection state;
the bottom of the filter cavity is also provided with a slag discharge hopper; the slag discharge hopper is funnel-shaped; the bottom of the slag discharging hopper is provided with the slag discharging port;
the number of the liquid outlets is the same as that of the liquid inlet ports; the liquid outlets are respectively connected with the corresponding liquid inlets through pipelines;
the liquid inlet is connected with a surface layer water inlet pump of the monitoring ship through a liquid supply pipe, and a liquid supply valve is arranged on a liquid supply pipe line;
and the end cover is also provided with an exhaust valve communicated with the inside of the filter cavity.
2. The seawater nutrient on-line monitoring system of claim 1, wherein the detection module comprises an injection device and a photoelectric detection device; the injection device includes a syringe pump and a multi-position valve, the syringe pump being in communication with the multi-position valve.
3. The seawater nutrient on-line monitoring system of claim 2, wherein the photo detection device comprises a flow cell, a light source, and a receiver; the flow cell, the light source and the receiver are configured to detect a light path and a reference light path; the flow cell is in communication with the multi-position valve.
4. A seawater nutrient on-line monitoring system as claimed in claim 3, further comprising a waste liquid storage device; the waste liquid storage device is communicated with the flow cell.
5. The seawater nutrient on-line monitoring system of claim 1, further comprising a hand-held terminal; the handheld terminal is connected with the main control module in a wired communication or wireless communication mode.
6. A method for detecting seawater nutrient salt, which is characterized by comprising a nitrite detection method, a nitrate detection method, a phosphate detection method, an ammonium salt detection method and a silicate detection method, wherein the seawater nutrient salt is detected by the seawater nutrient salt on-line monitoring system as claimed in claims 1-5, and the method comprises the following steps:
Measuring absorbance values of deionized water and a standard solution respectively;
drawing a standard curve according to the deionized water, the concentration of the standard solution and the absorbance value of the deionized water and the absorbance value of the standard solution;
fully mixing a water sample with a detection reagent, and measuring the absorbance value of the mixture of the water sample and the detection reagent;
carrying out standard curve and operation on the absorbance value of the mixture of the water sample and the detection reagent to obtain the concentration parameter of the nutrient salt to be detected in the water sample;
when detecting absorbance values of the deionized water, the standard solution and the detection reagent, introducing air into the seawater nutrient salt on-line monitoring system for defoaming, specifically:
after the injection pump sucks the liquid to be detected, the multi-position valve is controlled by the main control module, so that the injection pump is connected with the air interface through a pipeline, and a certain amount of air is introduced into the front end of the solution to be detected, so that an air column is formed in the pipeline;
the multi-position valve is controlled by the main control module, the passage between the injection pump and the air interface is closed, the injection pump is used for pushing the air column and the liquid to be detected to flow along the pipeline, the liquid to be detected is pushed into the flow cell, and the air column is pushed out of the flow cell;
the detection method of nitrite and nitrate comprises the following steps: the volume ratio of the water sample to the quantitative detection reagent A to the air is 0.3:0.1:0.1;
The phosphate detection method comprises the following steps: the volume ratio of the water sample to the quantitative detection reagent B to the quantitative detection reagent C to the air is 0.2:0.1:0.1:0.1;
the method for detecting the ammonium salt comprises the following steps: the volume ratio of the water sample to the quantitative detection reagent D to the quantitative detection reagent E to the quantitative detection reagent F to the air is 0.3:0.05:0.05:0.05:0.05;
the silicate detection method comprises the following steps: the volume ratio of the water sample to the quantitative detection reagent G to the quantitative detection reagent H to the quantitative detection reagent I to the air is 0.3:0.05:0.05:0.05:0.05;
the quantitative detection reagent A comprises the following raw materials in proportion: 5.0 g of sulfanilamide, 0.25 g of NEDD (N- (1-naphthyl) -ethylenediamine dihydrochloride, 50 ml of 37% concentrated hydrochloric acid, 450 ml of deionized water;
the quantitative detection reagent B comprises the following raw materials in proportion: 1.2 g ammonium molybdate tetrahydrate, 4.4 ml of potassium antimony tartrate solution and 10.4 ml of concentrated sulfuric acid;
the quantitative detection reagent C comprises the following raw materials in proportion: 1.6 g ascorbic acid, 200 ml deionized water;
the quantitative detection reagent D comprises the following raw materials in proportion: 120 g sodium citrate, 250 mL water, 10 mL NaOH solution;
the quantitative detection reagent E comprises the following raw materials in proportion: 120 g sodium salicylate, 0.2. 0.2 g sodium nitroprusside, 500 mL water;
The quantitative detection reagent F comprises the following raw materials in proportion: 2.7mLNaClO to 200mL;
the quantitative detection reagent G comprises the following raw materials in proportion: 2.4 g ammonium molybdate, 3.375, mL concentrated sulfuric acid, 246, mL deionized water;
the quantitative detection reagent H comprises the following raw materials in proportion: 10 g oxalic acid, 200mL deionized water;
the quantitative detection reagent I comprises the following raw materials in proportion: 4.0 g ascorbic acid, 200mL deionized water.
7. The method for detecting seawater nutrient salts as recited in claim 6, wherein the method for detecting nitrite comprises:
respectively extracting a quantitative water sample, a quantitative detection reagent A and quantitative air, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture A;
pushing the mixture A into a photoelectric detection device to detect the absorbance value of the mixture A;
and carrying the absorbance value of the mixture A into a nitrite detection standard curve for operation, and obtaining the concentration parameter of the nitrite in the water sample.
8. The method for detecting seawater nutrient salts as recited in claim 6, wherein the method for detecting nitrate comprises:
pushing the quantitative water sample into a first detection module for reduction to obtain a mixture B;
taking the mixture B and the quantitative detection reagent A, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture C;
Pushing the mixture C into a photoelectric detection device to detect the absorbance value of the mixture C;
and carrying the absorbance value of the mixture C into a nitrate detection standard curve for operation, and obtaining the concentration parameter of the nitrate in the water sample.
9. The method for detecting seawater nutrient salts as recited in claim 6, wherein the method for detecting phosphate comprises:
respectively extracting a quantitative water sample, a quantitative detection reagent B, a quantitative detection reagent C and quantitative air, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture D;
pushing the mixture D into a photoelectric detection device to detect the absorbance value of the mixture D;
and carrying the absorbance value of the mixture D into a phosphate detection standard curve for operation, and obtaining the concentration parameter of the phosphate in the water sample.
10. The method for detecting seawater nutrient salt according to claim 6, wherein,
the method for detecting the ammonium salt comprises the following steps:
heating the third detection module to a preset temperature;
extracting a quantitative water sample, a quantitative detection reagent D and quantitative air, and fully mixing in a circulating pushing-out and sucking mode to obtain a mixture E;
extracting a quantitative detection reagent E and fully mixing the mixture E in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture F;
Extracting a quantitative detection reagent F and fully mixing the reagent F with the mixture F in a circulating pushing-out and sucking-in mode to obtain a mixture G;
pushing the mixture G into a photoelectric detection device to detect the absorbance value of the mixture G;
and carrying the absorbance value of the mixture G into an ammonium salt detection standard curve for operation, and obtaining the concentration parameter of the ammonium salt in the water sample.
11. The method for detecting seawater nutrient salts as recited in claim 6, wherein the method for detecting silicate comprises:
respectively extracting a quantitative water sample, a detection reagent G and air, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture H;
taking a certain amount of detection reagent H and the mixture H, and fully mixing in a circulating pushing-out and sucking-in flow cell mode to obtain a mixture I;
taking a certain amount of detection reagent I and the mixture I, and fully mixing in a mode of circularly pushing out and sucking the mixture I into a flow cell to obtain a mixture J;
pushing the mixture J into a photoelectric detection device to detect the absorbance value of the mixture J;
and carrying the absorbance value of the mixture J into a silicate detection standard curve for operation, and obtaining the concentration parameter of silicate in the water sample.
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