CN111610161A - Circulation system, seawater nutrient salt in-situ measurement device and measurement method - Google Patents
Circulation system, seawater nutrient salt in-situ measurement device and measurement method Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 39
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- 235000015097 nutrients Nutrition 0.000 title claims abstract description 20
- 238000012625 in-situ measurement Methods 0.000 title claims abstract description 11
- 238000000691 measurement method Methods 0.000 title abstract description 8
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- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 35
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 35
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
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Abstract
The invention discloses a circulation system, a seawater nutrient salt in-situ measurement device and a measurement method. The circulation system comprises a filtering device, a sample cell, a sample feeding pump, a sample gate valve and a pure water storage device. By adopting a micro-flow total reflection sample pool as a sample detection pool, the optical path length can be effectively increased by changing the length of the total reflection sample pool; therefore, the method breaks through the defects of the conventional nitrate optical measurement method by means of the modes of a filtering device, a pure water storage device, a pure water bag/bottle water, a sample gate valve and the like, measures pure water once before nitrate measurement, is used as a substrate for calculating the absorbance of the nitrate on-site measurement, filters a water sample, can effectively influence the ultraviolet absorption light signals of the nitrate by turbidity, particles and the like, and improves the measurement precision.
Description
Technical Field
The invention relates to the technical field of seawater analysis, in particular to a circulation system, a seawater nutrient salt in-situ measurement device and a measurement method.
Background
The nitrate in seawater is one of the indexes necessary for marine investigation, and is the basis of marine food chain, and the research on the content or distribution characteristics of the nitrate in seawater is the basis of the research on the geochemical cycle process of marine organisms.
The nitrate nitrogen in seawater is generally determined by a cadmium column/zinc sheet reduction wet chemical spectrophotometry, the measurement result is relatively stable and reliable, but the operation is complex, the analysis time is long, the maintenance cost is high, and the chemical reaction can cause secondary environmental pollution.
In recent years, rapid nitrate measurement is carried out by adopting an ultraviolet absorption spectrometry, the basic principle is that an ultraviolet photometry is utilized to directly measure the absorption of an original water sample in an ultraviolet band (between 210nm and 240 nm), the concentration of nitrate is inverted according to absorbance, the method is high in measurement speed and easy to maintain, and is a preferred method for field in-situ/section measurement, but experimental results show that the measurement precision of the method is seriously influenced by water quality, particularly water turbidity and the like, the subsequent calibration difficulty is higher, the measurement precision is limited, the method is influenced by the effective optical path length (at present, the maximum can reach 1cm), the light attenuation is strong, and the detection sensitivity is low. The effective optical path length, water quality and the like are mainly determined by a seawater sample flow system, so the design quality of the seawater sample flow system is crucial to the measurement and detection sensitivity of seawater nitrate, and the defects (short optical path and no pretreatment) of a flow cell in the prior art cause low optical rapid measurement precision and sensitivity of nutritive salt and large calibration difficulty.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a micro-flow sample flowing system, a seawater nutrient salt in-situ measuring device and a measuring method.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect, an embodiment of the present invention provides a micro-flow sample circulation system, which is used in a seawater nutrient salt in-situ measurement device, and includes a filtering device, a sample cell, a sample pump, a sample gate valve, and a pure water storage; wherein,
the sample pool is a flow-through pool of a sample to be detected and comprises a flow-through pipe and light-liquid coupling joints with watertight function, wherein the light-liquid coupling joints are arranged at two ends of the flow-through pipe; the circulating tube is made of a total reflection material, the length and the aperture of the circulating tube are variable, and the optical path is adjustable; the optical-liquid coupling joint is made of corrosion-resistant materials, and the pressure resistance is not lower than 5 KPa;
the water outlet of the sample injection pump is communicated with the liquid path inlet of the optical-liquid coupling joint at one end of the sample cell, and the liquid path outlet of the optical-liquid coupling joint at the other end of the sample cell is arranged in a water environment;
the sample gate valve comprises a public water outlet channel and at least two sample selection channels, the water outlet of the public water outlet channel is communicated with the water inlet of the sample pump, at least one sample selection channel is communicated with the pure water storage device, and at least one sample selection channel is communicated with the water outlet of the filtering device;
the filtering device is used for filtering a water sample in situ.
Further, the filtering device comprises an outer filtering net and an inner filtering core; the outer filter screen is made of a pressure-resistant and corrosion-resistant material, the inner filter core is made of a corrosion-resistant sintered filter rod, and the aperture of the outer filter screen is larger than that of the inner sintered rod; the outer filter screen directly contacts the seawater.
Further, the filtration pore size of the inner filtration filter element is not more than 0.49 um.
Further, the liquid path outlet is higher than the liquid path inlet.
Further, the pure water storage is in a pure water bag/bottle mode.
In a second aspect, an embodiment of the present invention provides an in-situ measurement apparatus for seawater nutrient salts, including a sample introduction and ultraviolet absorption measurement module, an auxiliary parameter measurement module, a sealed cabin, and a power supply module; wherein,
the sample feeding and ultraviolet absorption measuring module comprises the micro-flow sample flowing system, an ultraviolet light source and an ultraviolet visible fiber spectrometer; the ultraviolet light source is connected with the optical input end of the optical-liquid coupling joint of the micro-flow sample circulation system through an optical fiber; the ultraviolet visible fiber spectrometer is connected with the optical output end of the optical-liquid coupling joint of the micro-flow sample flowing system through an optical fiber, so as to measure the absorbance of the sample in the micro-flow sample flowing system;
the auxiliary parameter measuring module is integrated with a temperature probe, a salinity probe and a depth probe so as to synchronously monitor the water quality parameters of the water body to be measured;
the main control module comprises a sample injection control unit, a spectrum information acquisition unit, an auxiliary parameter acquisition unit and a communication unit; the sample injection control unit is used for controlling the work of the sample gate valve and the sample injection pump so as to control sample injection; the spectrum information acquisition unit is used for controlling the ultraviolet visible optical fiber spectrometer to measure the absorbance of the sample; the auxiliary parameter acquisition unit is used for controlling the auxiliary parameter measurement module to acquire corresponding temperature, salt and depth information according to needs so as to synchronously correct the absorbance measured by the ultraviolet visible fiber spectrometer; the communication unit is used for realizing information transmission and exchange between the device and the upper computer;
the power supply module is respectively and electrically connected with the main control module, the sample introduction and ultraviolet absorption measurement module and the auxiliary parameter measurement module, and the power supply module determines whether to supply power to the main control module, the sample introduction and ultraviolet absorption measurement module and the auxiliary parameter measurement module or not through the on-off of the power supply switch;
the ultraviolet light source, the ultraviolet visible optical fiber spectrometer, the power supply module and the power supply control switch in the main control module and the sample introduction and ultraviolet absorption measurement module are all sealed in the sealed cabin body; the micro-flow sample circulation systems are all arranged outside the sealed cabin and can be directly contacted with seawater to be detected; and the probe integrated by the auxiliary parameter measuring module is arranged on the sealed cabin body and is directly contacted with the seawater to be measured.
Further, the main control module further comprises an information storage unit for storing the information measured by the external visible fiber spectrometer and the information measured by the auxiliary parameter measuring module in a self-contained manner in real time.
Further, the power supply control switch is mechanically controlled by a non-contact switch key arranged on the sealed cabin body.
Further, the light source is an SMA905 optical fiber output type deuterium lamp light source.
In a third aspect, the embodiment of the invention provides an in-situ measurement method for seawater nutrient salts, which is performed by using the device and comprises the following steps;
pressing down a power supply switch to control the measurement device to be powered on, wherein the measurement device is in a work waiting state;
before the measuring device is started up to measure the nitrate each time, measuring pure water once as a substrate for calculating the field measurement absorbance of the nitrate;
the measuring device performs underwater full-automatic measurement, the measurement result is uploaded to an upper computer, the upper computer combines the measurement result with the pure water measurement result, the absorbance of the sample to be measured in the characteristic wave band is obtained through calculation, and the concentration of the solution to be measured is inverted by combining the Lamborber law.
The measurement process is judged and controlled by depth information obtained by the depth probe in the auxiliary parameter measurement module through real-time measurement so as to ensure that the instrument is carried out in a certain single way in the process of putting down or recovering;
and after the work is finished, the power supply switch is used for controlling the power-off of the measuring device.
Compared with the prior art, the invention has the beneficial effects that:
1. the micro-flow total reflection sample pool is adopted as the sample detection pool, the optical path length can be effectively increased by changing the length of the total reflection sample pool, meanwhile, the closed detection pool structure can effectively avoid the influence of stray light such as background light and the like on the absorbed optical signals, the defects of the prior art can be effectively overcome by the two innovative combined designs, the rapid detection sensitivity of nitrate/nitrite is improved, and the micro-flow total reflection sample pool is very suitable for in-situ monitoring and early warning of underwater long-time sequences.
2. The method breaks through the defects of the conventional nitrate optical measurement method, filters the water sample, can effectively influence the ultraviolet absorption light signals of the nitrate by turbidity, particles and the like, and improves the measurement precision
3. The temperature and salt depth probe is innovatively integrated, the water quality parameters of the water body to be detected can be synchronously monitored and used for synchronously correcting the absorbance of the nitrate, the detection accuracy of the nitrate is improved, and meanwhile, the correction efficiency is greatly improved.
4. The instrument works fully automatically underwater, the working process is automatically controlled, and the effectiveness of data acquisition can be ensured.
5. The seawater nutrient salt in-situ measuring device provided by the invention has the advantages that the optical, electrical and mechanical circuit systems are clearly divided, the optical, electrical and mechanical rotating parts are completely and hermetically assembled, and the liquid circuit part is completely and externally arranged in a water environment, so that the safety of field use of the instrument is improved.
Drawings
FIG. 1 is a schematic structural diagram of an in-situ seawater nitrate analysis apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a seawater nitrate ultraviolet spectrophotometric measuring method;
FIG. 3 is a schematic diagram of the structure of a micro-flow sample flow system;
FIG. 4 is a schematic diagram of a main control module;
in the figure: 1. a sample introduction and ultraviolet absorption measurement module; 2. a main control module; 3. an auxiliary parameter measurement module; 4. a power supply module; 5. a power supply control switch; 6. sealing the cabin body; 11. an ultraviolet light source; 12. a micro-flow sample flow-through system; 13. an ultraviolet visible fiber optic spectrometer; 14. an ultraviolet silica optical fiber; 21. a sample introduction control unit; 22. a spectral information acquisition unit; 23. an auxiliary parameter acquisition unit; 24. a communication unit; 25. an information storage module; 41. a power supply/charging plug; 51. a non-contact switch; 121. a filtration device; 122. a sample cell; 123. a sample injection pump; 124. a sample gate valve; 125. a pure water reservoir; 241. a communication connector; 1211. an outer filter screen; 1212. an inner filter element; 1221. a flow-through tube; 1222. light-liquid coupling joint.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and detailed description.
Example (b):
referring to fig. 1, a schematic structural diagram of the in-situ measurement device for seawater nutrient salts provided in this embodiment mainly includes a sample introduction and ultraviolet absorption measurement module 1 for sample introduction and nitrate absorbance measurement, a main control module 2 for controlling measurement and self-contained storage control in a device working process (in-situ sample introduction, spectrum information acquisition, self-contained storage, information interaction with an upper computer, and the like), an auxiliary parameter measurement module 3 for temperature and salt depth measurement, a power supply module 4, a power supply control switch 5, and a sealed cabin 6. In the present embodiment, the power supply module 4 is a power supply battery, and the power supply/charging plug 41 is connected to the power supply battery, and the power supply/charging plug 41 is mounted on the sealed cabin 6.
As shown in fig. 2, the sample injection and ultraviolet absorption measurement module 1 is used for in-situ automatic selection, filtration, sample injection and nitrate absorbance measurement, and specifically includes an ultraviolet light source 11, a micro-flow sample flow system 12, a micro ultraviolet visible fiber spectrometer 13, and an ultraviolet quartz fiber 14.
Specifically, as shown in fig. 3, the micro flow sample circulation system 12 includes a filter 121, a sample cell 122, a sample pump 123, a sample selector valve 124, and a pure water reservoir 125; the sample cell 122 is a flow cell for a sample to be measured, and is composed of a liquid sample flow tube 1221 with a certain length and an optical-hydraulic coupling joint 1222 which is installed at two ends of the flow tube and has a watertight function, and the optical-hydraulic coupling joint 1222 is made of a corrosion-resistant material and has a pressure resistance of not less than 5 KPa; preferably, in order to improve the detection sensitivity, the flow tube 1221 is made of a total reflection material, and has a variable length and aperture and an adjustable optical path. A water outlet of the sample pump 123 is communicated with a liquid path inlet of the optical liquid coupling joint 1222 at one end of the sample cell 122, a liquid path outlet of the optical liquid coupling joint 1222 at the other end of the sample cell 122 is placed in a water environment through a hose, and preferably, the liquid path outlet is higher than the liquid path inlet to ensure the accuracy of measurement; the sample gate valve 124 comprises a common water outlet channel and at least two sample selecting channels, the common water outlet channel is communicated with the water inlet of the sample pump 123, at least one sample selecting channel is communicated with the pure water storage 125, and at least one sample selecting channel is communicated with the water outlet of the filter 121; and the filtering device 121 is used for in-situ filtering of the water sample. In the present embodiment, the pure water storage 125 is provided in the form of a pure water bag/bottle. That is, the sample gate valve 124 may select pure water or a seawater sample to enter the flow pipe 1221 for measurement.
Therefore, by adopting the micro-flow total reflection sample cell as the sample detection cell, the optical path length can be effectively increased by changing the length of the total reflection sample cell; therefore, the method breaks through the defects of the conventional nitrate optical measurement method by means of the modes of a filtering device, a pure water storage device, a pure water bag/bottle water, a sample gate valve and the like, measures pure water once before nitrate measurement, is used as a substrate for calculating the absorbance of the nitrate on-site measurement, filters a water sample, can effectively influence the ultraviolet absorption light signals of the nitrate by turbidity, particles and the like, and improves the measurement precision.
The auxiliary parameter measuring module 3 is integrated with temperature, salinity and depth probes to synchronously monitor the water quality parameters of the water body to be measured. Therefore, the temperature and salt depth probe is innovatively integrated, the water quality parameters of the water body to be detected can be synchronously monitored and used for synchronously correcting the absorbance of the nitrate, and the correction efficiency is greatly improved while the detection accuracy of the nitrate is improved.
As shown in fig. 4, the main control module 2 includes a sample injection control unit 21, a spectrum information collecting unit 22, an auxiliary parameter collecting unit 23, and a communication unit 24; wherein, the sample injection control unit 21 is used for controlling the work of the sample gate valve 124 and the sample injection pump 123 to control the sample injection; the spectrum information acquisition unit 22 is used for controlling the ultraviolet visible fiber spectrometer 13 to measure the absorbance of the sample; the auxiliary parameter acquisition unit 23 is used for controlling the auxiliary parameter measurement module 3 to acquire corresponding temperature, salt and depth information as required so as to synchronously correct the absorbance measured by the ultraviolet-visible fiber spectrometer 13; the communication unit 24 is used for realizing information transmission and exchange between the device and an upper computer, so that the device can be controlled and analyzed to obtain results, the device can work fully automatically underwater, the working process is automatically controlled, and the effectiveness of data acquisition can be ensured. Preferably, the main control module 2 further includes an information storage module 25, which is mainly used for storing the acquired spectrum information and the auxiliary parameter information in a real-time self-contained manner.
The power supply module 4 is respectively electrically connected with the main control module 2, the sample introduction and ultraviolet absorption measuring module 1 and the auxiliary parameter measuring module 3, and the power supply module 4 determines whether to perform the main control module 2, the sample introduction and ultraviolet absorption measuring module 1 and the auxiliary parameter measuring module 3 through the on-off of the power supply switch 5. That is, the power supply module 4 supplies power to the entire apparatus under the control of the power supply process control switch 5.
The main control module 2, the ultraviolet light source 11, the ultraviolet visible optical fiber spectrometer 13, the power supply module 4 and the power supply control switch 5 in the sample introduction and ultraviolet absorption measurement module 1 are all sealed in the sealed cabin 6; the micro-flow sample circulation system 12 is arranged outside the sealed cabin 6 and can be directly contacted with seawater to be detected, so that a user can conveniently replace the sample pool 122, the filter device 121, the sample pump 123, the sample selective valve 124 and the like; the probe sensor integrated by the auxiliary parameter measuring module 3 is arranged on the sealed cabin body in a watertight manner and is directly contacted with the seawater to be measured. That is to say, the seawater nutrient salt in-situ measuring device clearly divides an optical-mechanical-electrical and liquid path system, the optical, electrical and mechanical rotating parts are completely sealed and assembled, and the liquid path part is completely externally arranged in a water environment, so that the safety of field use of the instrument is improved.
Specifically, the ultraviolet light source 11 is an SMA905 optical fiber output type deuterium lamp light source, an optical-liquid coupling joint optical input end of the total reflection sample cell is communicated with the light source through an SMA905 watertight joint and an ultraviolet quartz optical fiber 14, and an optical output end of the total reflection sample cell is communicated with the ultraviolet visible micro optical fiber spectrometer through an SMA905 watertight joint and an ultraviolet quartz optical fiber 14.
Specifically, the filter device 121 is composed of an outer filter screen 1211 and an inner filter core 1212. Preferably, the outer filter screen 1211 is made of a pressure-resistant and corrosion-resistant material, the inner filter core is made of 1212 corrosion-resistant sintered filter rods, and the aperture of the outer filter screen 1211 is larger than that of the inner sintered rods; interior filter core 1212 filter pore size is not more than 0.49um, outer filter screen direct contact sea water former state. Through so design filter equipment, can filter the water sample normal position effectively to the accuracy of further assurance test.
Preferably, the communication unit 24 includes a long-range wireless communication unit, a short-range wireless/wired communication unit, and is mounted on the sealed enclosure by means of a communication joint 241. And the power supply control switch 5 is mechanically controlled by a non-contact switch 51 mounted on the sealed housing 6.
Correspondingly, the embodiment also provides an in-situ measurement method for the seawater nutrient salt, which is carried out by adopting the in-situ measurement device for the seawater nutrient salt and comprises the following steps;
s1, pressing a non-contact control switch to control the device to be powered on, and enabling the device to work in a waiting state.
And S2, measuring pure water once before the device is started to measure the nitrate every time, wherein the pure water is used as a substrate and is used for calculating the field measurement absorbance of the nitrate.
And S3, performing underwater full-automatic measurement by using the instrument, combining the measurement result with the pure water measurement result, calculating the absorbance of the sample to be measured in the characteristic wave band according to the formula (1), and performing inversion on the concentration of the solution to be measured by combining the Lambor law (A is Kbc, wherein A is the absorbance, and c is the concentration of the sample to be measured).
A＝lg(I0/It) (1)
Wherein, I0Is the intensity of incident light, ItIs the intensity of transmitted light
S4, the depth information obtained by the depth probe in the auxiliary parameter sensor through real-time measurement is judged and controlled in the measuring process, so that the instrument is ensured to be carried out in a single pass in the releasing or recovering process, and the repeated storage of data information is avoided;
and S4, after the work is finished, controlling the instrument to be powered off through the non-contact switch, and if the instrument is not used for a long time, cleaning the liquid core sample pool and then ventilating and storing the liquid core sample pool.
In summary, compared with the prior art, the invention has the following outstanding advantages:
1. the micro-flow total reflection sample pool is used as a sample detection pool, the optical path length can be effectively increased by changing the length of the total reflection sample pool, meanwhile, the micro-flow total reflection sample pool can effectively avoid the influence of stray light such as background light and the like on the absorbed optical signals, the defects of the prior art can be effectively overcome by the two innovative combined designs, the rapid detection sensitivity of the nitrate is improved, and the micro-flow total reflection sample pool is very suitable for in-situ monitoring and early warning of underwater long-time sequences.
2. The method breaks through the defects of the conventional nitrate optical measurement method, filters the water sample, can effectively influence the ultraviolet absorption light signals of the nitrate by turbidity, particles and the like, and improves the measurement precision
3. The temperature and salt depth probe is innovatively integrated, the water quality parameters of the water body to be detected can be synchronously monitored and used for synchronously correcting the absorbance of the nitrate, the detection accuracy of the nitrate is improved, and meanwhile, the correction efficiency is greatly improved.
4. The instrument works fully automatically underwater, the working process is automatically controlled, and the effectiveness of data acquisition can be ensured.
5. The seawater nutrient salt in-situ measuring device provided by the invention has the advantages that the optical, electrical and mechanical circuit systems are clearly divided, the optical, electrical and mechanical rotating parts are completely and hermetically assembled, and the liquid circuit part is completely and externally arranged in a water environment, so that the safety of field use of the instrument is improved.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (10)
1. A micro-flow sample circulation system is used in a seawater nutrient salt in-situ measuring device and is characterized by comprising a filtering device, a sample pool, a sample feeding pump, a sample selective valve and a pure water memory; wherein,
the sample cell is a flow cell of a sample to be detected and comprises a flow tube and light-liquid coupling joints with watertight functions, wherein the light-liquid coupling joints are arranged at two ends of the flow tube; the circulating tube is made of a total reflection material, the length and the aperture of the circulating tube are variable, and the optical path is adjustable; the optical-liquid coupling joint is made of corrosion-resistant materials, and the pressure resistance is not lower than 5 KPa;
the water outlet of the sample injection pump is communicated with the liquid path inlet of the optical-liquid coupling joint at one end of the sample cell, and the liquid path outlet of the optical-liquid coupling joint at the other end of the sample cell is arranged in a water environment;
the sample gate valve comprises a public water outlet channel and at least two sample selection channels, the water outlet of the public water outlet channel is communicated with the water inlet of the sample pump, at least one sample selection channel is communicated with the pure water storage device, and at least one sample selection channel is communicated with the water outlet of the filtering device;
the filtering device is used for filtering a water sample in situ.
2. The micro-fluidic sample flow-through system of claim 1, wherein the filtering device comprises an outer filter mesh and an inner filter cartridge; the outer filter screen is made of a pressure-resistant and corrosion-resistant material, the inner filter core is made of a corrosion-resistant sintered filter rod, and the aperture of the outer filter screen is larger than that of the inner sintered rod; the outer filter screen directly contacts the seawater.
3. The micro-fluidic sample flow-through system of claim 1 wherein the inner filter cartridge filter pore size is no greater than 0.49 um.
4. The micro-fluidic sample flow-through system of claim 1, wherein the fluid path outlet is higher than the fluid path inlet.
5. The micro-fluidic sample flow-through system of claim 1, wherein the pure water reservoir is in the form of a pure water bag/bottle.
6. An in-situ measuring device for seawater nutrient salt is characterized by comprising a sample introduction and ultraviolet absorption measuring module, an auxiliary parameter measuring module, a sealed cabin and a power supply module; wherein,
the sample introduction and ultraviolet absorption measurement module comprises the micro-flow sample circulation system, an ultraviolet light source and an ultraviolet-visible fiber spectrometer of any one of claims 1 to 5; the ultraviolet light source is connected with the optical input end of the optical-liquid coupling joint of the micro-flow sample circulation system through an optical fiber; the ultraviolet visible fiber spectrometer is connected with the optical output end of the optical-liquid coupling joint of the micro-flow sample flowing system through an optical fiber, so as to measure the absorbance of the sample in the micro-flow sample flowing system;
the auxiliary parameter measuring module is integrated with a temperature probe, a salinity probe and a depth probe so as to synchronously monitor the water quality parameters of the water body to be measured;
the main control module comprises a sample injection control unit, a spectrum information acquisition unit, an auxiliary parameter acquisition unit and a communication unit; the sample injection control unit is used for controlling the work of the sample gate valve and the sample injection pump so as to control sample injection; the spectrum information acquisition unit is used for controlling the ultraviolet visible optical fiber spectrometer to measure the absorbance of the sample; the auxiliary parameter acquisition unit is used for controlling the auxiliary parameter measurement module to acquire corresponding temperature, salt and depth information according to needs so as to synchronously correct the absorbance measured by the ultraviolet visible fiber spectrometer; the communication unit is used for realizing information transmission and exchange between the device and the upper computer;
the power supply module is respectively and electrically connected with the main control module, the sample introduction and ultraviolet absorption measurement module and the auxiliary parameter measurement module, and the power supply module determines whether to supply power to the main control module, the sample introduction and ultraviolet absorption measurement module and the auxiliary parameter measurement module or not through the on-off of the power supply switch;
the ultraviolet light source, the ultraviolet visible optical fiber spectrometer, the power supply module and the power supply control switch in the main control module and the sample introduction and ultraviolet absorption measurement module are all sealed in the sealed cabin body; the micro-flow sample circulation systems are all arranged outside the sealed cabin and can be directly contacted with seawater to be detected; and the probe integrated by the auxiliary parameter measuring module is arranged on the sealed cabin body and is directly contacted with the seawater to be measured.
7. The in-situ measuring apparatus for seawater nutrient salt as claimed in claim 6, wherein the main control module further comprises an information storage unit for storing the information measured by the visible fiber spectrometer and the information measured by the auxiliary parameter measuring module in a self-contained manner in real time.
8. The in-situ seawater nutrient salt measurement device as claimed in claim 6, wherein the power supply control switch is mechanically controlled by a non-contact switch button installed on the sealed cabin.
9. The in-situ seawater nutrient salt measurement device as claimed in claim 6, wherein the light source is an SMA905 optical fiber output type deuterium lamp light source.
10. An in-situ measurement method for seawater nutrient salt, which is carried out by the device of claim 6, and is characterized by comprising the following steps;
pressing down a power supply switch to control the measurement device to be powered on, wherein the measurement device is in a work waiting state;
before the measuring device is started up to measure the nitrate each time, measuring pure water once as a substrate for calculating the field measurement absorbance of the nitrate;
the measuring device performs underwater full-automatic measurement, the measurement result is uploaded to an upper computer, the upper computer combines the measurement result with the pure water measurement result, the absorbance of the sample to be measured in the characteristic wave band is obtained through calculation, and the concentration of the solution to be measured is inverted by combining the Lamborber law.
The measurement process is judged and controlled by depth information obtained by the depth probe in the auxiliary parameter measurement module through real-time measurement so as to ensure that the instrument is carried out in a certain single way in the process of putting down or recovering;
and after the work is finished, the power supply switch is used for controlling the power-off of the measuring device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114235730A (en) * | 2022-02-21 | 2022-03-25 | 中国科学院烟台海岸带研究所 | Seawater nutrient salt online monitoring system and seawater nutrient salt detection method |
| CN115406835A (en) * | 2022-09-20 | 2022-11-29 | 山东大学 | Nitrate measuring method and system based on wavelength-tunable ultraviolet narrow-band light source |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101477034A (en) * | 2009-01-13 | 2009-07-08 | 中国科学院南海海洋研究所 | On-line high-spectrum monitoring instrument for water trace element |
| CN105403524A (en) * | 2015-11-06 | 2016-03-16 | 上海海秦环保科技有限公司 | Online low-energy consumption field in-situ nutritive salt detecting instrument and detecting method |
| CN108254367A (en) * | 2017-12-21 | 2018-07-06 | 国家海洋局第二海洋研究所 | Boat-carrying or bank base water nutrition detect and prior-warning device and its method automatically |
| CN208091910U (en) * | 2018-03-26 | 2018-11-13 | 山东省科学院海洋仪器仪表研究所 | A kind of device for analyzing on-line checking Nitrate In Sea Water content based on optofluidic |
| CN109030842B (en) * | 2018-08-09 | 2019-10-08 | 中国科学院南海海洋研究所 | A kind of nutrients in sea water in-situ study device |
-
2020
- 2020-04-29 CN CN202010355537.5A patent/CN111610161B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101477034A (en) * | 2009-01-13 | 2009-07-08 | 中国科学院南海海洋研究所 | On-line high-spectrum monitoring instrument for water trace element |
| CN105403524A (en) * | 2015-11-06 | 2016-03-16 | 上海海秦环保科技有限公司 | Online low-energy consumption field in-situ nutritive salt detecting instrument and detecting method |
| CN108254367A (en) * | 2017-12-21 | 2018-07-06 | 国家海洋局第二海洋研究所 | Boat-carrying or bank base water nutrition detect and prior-warning device and its method automatically |
| CN208091910U (en) * | 2018-03-26 | 2018-11-13 | 山东省科学院海洋仪器仪表研究所 | A kind of device for analyzing on-line checking Nitrate In Sea Water content based on optofluidic |
| CN109030842B (en) * | 2018-08-09 | 2019-10-08 | 中国科学院南海海洋研究所 | A kind of nutrients in sea water in-situ study device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114235730A (en) * | 2022-02-21 | 2022-03-25 | 中国科学院烟台海岸带研究所 | Seawater nutrient salt online monitoring system and seawater nutrient salt detection method |
| CN115406835A (en) * | 2022-09-20 | 2022-11-29 | 山东大学 | Nitrate measuring method and system based on wavelength-tunable ultraviolet narrow-band light source |
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