CN114166747A - Discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution - Google Patents

Discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution Download PDF

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CN114166747A
CN114166747A CN202111462748.XA CN202111462748A CN114166747A CN 114166747 A CN114166747 A CN 114166747A CN 202111462748 A CN202111462748 A CN 202111462748A CN 114166747 A CN114166747 A CN 114166747A
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absorption spectrum
water
spectrum
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fluorescence
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CN114166747B (en
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侯迪波
尹航
薛方家
夏戚宇
马志强
喻洁
黄平捷
曹云琦
张光新
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Zhejiang University ZJU
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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
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • 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
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • 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
    • G01N2021/0106General arrangement of respective parts
    • G01N2021/0112Apparatus in one mechanical, optical or electronic block
    • 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
    • G01N2021/3129Determining multicomponents by multiwavelength light
    • 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
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N2021/6417Spectrofluorimetric devices
    • 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
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N2021/6417Spectrofluorimetric devices
    • G01N2021/6419Excitation at two or more wavelengths

Abstract

The invention discloses a discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution, which integrates a water path, a circuit and a light path, adopts a small spectrometer and a prism light splitting module, and has low cost and convenient carrying and maintenance; the discrete three-dimensional fluorescence spectrum and the absorption spectrum can be obtained simultaneously in one-time field detection, and the characteristic peak is enhanced by utilizing the correlation of the absorption spectrum and the fluorescence mechanism. After the set cyclic sampling, the uninterrupted in-situ continuous measurement can be realized, the obtained spectrum data covers the water quality abnormal information and the pollution type information at different time, and the data obtained by the device can be used for quickly judging whether the pollution is generated or not and the pollution type. Through the mode of limit cloud cooperation, can need not upload the bottom data that detect to the high in the clouds analysis, computational resource can be shared by a plurality of detection device, saves water quality analysis's network flow, has promoted processing speed and operating efficiency.

Description

Discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution
Technical Field
The invention belongs to the field of fluorescence/visible light absorption spectrum detection, and particularly relates to a discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution.
Background
The core content of water quality monitoring is to use an on-line or off-line technical means to monitor the water body condition for a long time, store related water quality historical data, analyze and research the change rule of water quality, provide corresponding scientific decision basis for related departments in coping with water quality emergency disasters, developing and utilizing water resources and the like. The data acquisition mode of water quality monitoring comprises an off-line means and an on-line means, wherein the data acquisition mode comprises an environment quality monitoring mode and a pollution source monitoring and monitoring mode, data factors are parameters related in GB5749-2006 sanitary standard for drinking water, CJ-T206-2005 urban water supply water quality standard and GB3838-2002 surface water environment quality standard, and the monitoring parameters actually improve the water quality monitoring level and the water quality.
However, the existing water quality monitoring system also has the following limitations:
1) the means for acquiring the water quality information mainly comprises a fixed automatic monitoring station and laboratory analysis, the detection period is long, the detection means is complex, only the overall indexes of the water quality macroscopical river channels can be controlled, and the monitoring on the dynamically changed water quality condition is insufficient.
2) The intelligent level is not high, heavy data monitoring and light data analysis are performed, most systems only perform quantitative detection on water quality parameters, alarm is performed according to standard exceeding, and relative change and hidden information in large data cannot be fully mined.
3) A few systems with a timely early warning function can only detect the abnormity, cannot identify and judge the abnormity, still need to take a water sample for laboratory analysis, and delay the opportunity of emergency accident treatment.
Therefore, in the face of severe situations and problems in the aspect of water environment treatment, research on a method suitable for intelligent anomaly detection and identification of a water body and improvement of emergency treatment capacity of sudden pollution are urgently needed, the problems of three-dimensional water quality monitoring and analysis, intelligent water quality analysis, intelligent cloud platform construction and the like are solved, and support of multiple layers is provided for water body treatment and maintenance work.
Disclosure of Invention
The invention aims to provide a discrete three-dimensional fluorescence/visible light absorption spectrum detection device for judging water quality pollution aiming at the defects of the prior art. The invention builds detection hardware of discrete three-dimensional fluorescence/visible light absorption spectrum, and realizes a water pollution discrimination method based on the hardware; the device of the invention has simple operation and convenient carrying, can continuously sample and detect, and can realize real-time on-site, continuous and rapid water pollution detection by matching with an algorithm.
The purpose of the invention is realized by the following technical scheme: a discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution comprises a spectrum acquisition module and an upper computer.
The spectrum acquisition module comprises a light source, a light splitting module, a spectrum detection module and a water pump.
The light splitting module comprises a prism, a diaphragm, a flow cell, a lens and a stepping motor. The triple prism is connected with a stepping motor.
The spectrum detection module comprises two spectrometers.
The water pump comprises an emptying pump, a flushing pump and a sample injection pump. The drainage pump is connected with air, the flushing pump is connected with pure water, and the sampling pump is connected with a sample. The circulation tank is provided with an upper port and a lower port, the lower end is connected with three water pumps at the same time, and the upper end is a water outlet.
The light source is collimated by the lens, then is split by the prism and the diaphragm in sequence, then the incident light obtained after being focused by the lens is vertically incident into the flow cell, the absorption spectrum is obtained in the light path transmission direction, and the fluorescence spectrum is obtained in the direction vertical to the light path transmission direction. Controlling the prism to move through a stepping motor so as to change the wavelength of incident light; different wavelengths of incident light correspond to different absorption and fluorescence spectra. The absorption spectrum of the sample is the average value of the absorption spectra corresponding to different incident light wavelengths; the fluorescence spectrum of the sample is a vector splicing matrix of fluorescence spectra corresponding to different incident light wavelengths.
The absorption spectrum and the fluorescence spectrum are respectively input into a spectrometer.
The upper computer is communicated with the spectrum acquisition module and comprises a step motor, a prism, a water pump and a spectrometer, wherein the step motor is controlled to change the position of the prism, the water pump is controlled to open and close the time sequence, and the spectrometer is controlled to open and close the sampling channel.
Further, the communication of host computer and step motor, water pump specifically is: the upper computer is used as a TCP client and sends an i-j-T instruction to realize corresponding control. The stepping motor and the water pump are used as TCP server ends and wait for instructions of an upper computer all the time. i represents a control object and comprises a stepping motor and a water pump; j represents the execution action of the current control object, the execution action of the stepping motor comprises positive rotation and negative rotation, and the execution action of the water pump comprises opening of an emptying pump, a flushing pump and a sampling pump; t represents the parameters of the execution action of the current control object, and for the stepping motor, T is the pulse number given to the stepping motor, and p is the pulse number corresponding to one turn, so that the number of turns of the stepping motor is T/p; for the water pump, T is the water pump running time.
Further, comprising:
(1) wavelength calibration: calibrating the corresponding relation between different positions of the triple prism and the wavelength of the incident light to obtain a relation table of the number of rotation turns of the stepping motor and the wavelength of the incident light.
(2) Dark background detection: opening a spectrometer connected with an absorption spectrum in an empty flow cell under a light source-free environment to obtain absorption spectrum dark environment data alphad
(3) Pure water spectrum detection: pure water detection sets wavelengths to k groups. The absorption spectrum data and fluorescence spectrum data of pure water corresponding to the ith wavelength are alphaw(i) And betaw(i) In that respect Turn on the light source, the edgePlacing the mirror at the position of initial emission wavelength, filling the flow cell with pure water, respectively opening the spectrometer detection channels corresponding to the absorption spectrum and the fluorescence spectrum, and measuring the absorption spectrum data alpha of the pure waterw(1) And fluorescence spectrum data betaw(1). Then, the detection is continued by changing the next wavelength. When all the k groups of wavelengths are measured, the flow cell is emptied and the prism is reset to the initial position.
(4) Sample spectrum detection: the wavelengths to be measured are also k groups and are the same as the set wavelengths for pure water detection. The absorption spectrum data and fluorescence spectrum data of pure water corresponding to the ith wavelength are alphas(i) And betas(i) In that respect Filling the flow cell with a sample water sample, respectively opening the spectrometer detection channels corresponding to the absorption spectrum and the fluorescence spectrum, and measuring absorption spectrum data alphas(1) And fluorescence spectrum data betas(1). Then, the detection is continued by changing the next wavelength. And when the k groups of wavelengths are measured, finishing the detection and emptying the flow cell.
Further, the absorption spectrum a of the sample is solved by:
Figure BDA0003380097190000031
wherein the content of the first and second substances,
Figure BDA0003380097190000032
the sample three-dimensional fluorescence spectrum data F is solved by the following formula:
F=Bs-Bw
Bs=[βs(1),βs(2),…,βs(i)…,βs(k)]
Bw=[βw(1),βw(2),…,βw(i)…,βw(k)]
wherein, Bs、BwThe matrix is a vector splicing matrix of fluorescence spectra of the sample and pure water under each incident light wavelength i.
Further, the upper computer stores the spectral data collected by the spectrometer locally. The upper computer is accessed to the internet and realizes data acquisition, storage and algorithm issuing requests based on the edge computing interface. The upper computer sends the spectrometer data to the edge computing node, and the quantitative and qualitative algorithm for water pollution is tested and finished before measurement, and is packaged into a mirror image to be uploaded to the cloud node. After the cloud computing node receives the algorithm issuing request, the required algorithm is issued to the edge computing node through scheduling, and detection work is carried out depending on edge computing power. And the detection result is notified to the upper computer by the edge node.
Further, the light source is a halogen light source.
Further, the flow cell is connected with three water pumps through a four-way pipe.
Further, the wavelength of the incident light is selected from 400nm, 450nm, 475nm, 500nm, 525nm, 550nm, 575nm, 600nm, 650nm, and 700 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) spectral detection equipment generally needs manual sampling and manual sample changing, and different types of spectrograms can be obtained by operating on different equipment. The device integrates a water path, a circuit and a light path, adopts a small spectrometer and a prism light splitting module, and is low in cost and convenient to carry and maintain; the discrete three-dimensional fluorescence spectrum and the absorption spectrum can be obtained simultaneously in one-time field detection, and the characteristic peak is enhanced by utilizing the relevance of the absorption spectrum and the fluorescence mechanism;
(2) after the device sets cyclic sampling, uninterrupted in-situ continuous measurement can be realized, the obtained spectral data covers water quality abnormal information and pollution type information at different times, and the data obtained by the device can be used for quickly judging whether pollution exists or not and pollution type;
(3) by means of the edge cloud cooperation mode, detected bottom data do not need to be uploaded to a cloud end for analysis, computing resources can be shared by a plurality of detection devices, network flow of water quality analysis is saved, and processing speed and operation efficiency are improved;
(4) all components of the device are controlled by the communication between the user upper computer and the user lower computer, so that the operation is simple; the system is designed for batch deployment, a plurality of users can work simultaneously, the time-space associated data of the monitored object can be obtained, and the limitation that the single-site monitoring of the online spectrograph on the market is not intelligent at present is overcome.
Drawings
FIG. 1 is a schematic diagram of a discrete three-dimensional fluorescence/visible absorption spectrum detection device;
FIG. 2 is an absorption curve diagram of a VB2 pure water sample under the detection of a discrete three-dimensional fluorescence/visible light absorption spectrum detection device;
FIG. 3 is a three-dimensional fluorescence spectrum of a VB2 pure water sample under the detection of a discrete three-dimensional fluorescence/visible light absorption spectrum detection device;
FIG. 4 is a schematic diagram of an internal communication protocol instruction decision tree;
FIG. 5 is a flowchart of the procedure for discrete three-dimensional fluorescence/visible absorption spectrum detection;
fig. 6 is a schematic diagram of spectral edge cloud collaborative computing.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
As shown in figure 1, the discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution comprises a spectrum acquisition module and an upper computer.
The spectrum collection module comprises a light path part and a water path part. The light path part comprises a light source, a light splitting module and a spectrum detection module. The light source adopts a halogen light source. The light splitting module consists of a prism, a stepping motor (not shown), an optical plate, a diaphragm, a flow cell and a matched lens. The spectrum detection module consists of 2 spectrometers. The waterway part comprises 3 water pumps which are respectively an emptying pump, a flushing pump and a sample injection pump; the drainage pump is connected with air, the flushing pump is connected with pure water, and the sampling pump is connected with the coarsely filtered sample. The stepping motor is connected with the optical plate and controls the optical plate to move on the parallel plane where the split light beam is located, as shown by an arrow in fig. 1.
The flow-through cell lower extreme is the water sample entry, links to each other with 3 water pumps through the four-way pipe, and flow-through cell upper end coupling hose is as the end of arranging in line, and the drain pump inserts the air and can makes the water sample discharge from the end of arranging in line. Because other chemical operations are not needed in the detection process, the spectral detection does not influence environmental samples, and the washing is also carried out by pure water, so the on-site direct discharge can be realized.
The light source is collimated by the matched lens, then is subjected to slit light splitting by the triple prism and the diaphragm in sequence, then is focused by the matched lens (not shown in the figure) to obtain incident light with good monochromaticity, and the incident light is vertically irradiated into the incident surface of the flow cell. The prism is fixed to a stepping motor and can be changed in position by the stepping motor to change the wavelength of incident light. After the incident light vertically irradiates a water sample in the flow cell, an absorption spectrum can be obtained in the light path transmission direction, and a fluorescence spectrum can be obtained in the direction perpendicular to the light path transmission direction. The wavelength of the incident light is continuously changed, so that the absorption spectrum of different incident lights and the fluorescence spectrum of different incident lights can be obtained. In this embodiment, the wavelengths are selected from 400nm, 450nm, 475nm, 500nm, 525nm, 550nm, 575nm, 600nm, 650nm, and 700 nm. The absorption spectrum of the sample is the average value of the absorption spectrum set of the incident light with different wavelengths, and the discrete three-dimensional fluorescence spectrum of the sample is a vector splicing matrix of the fluorescence spectra of the incident light with different wavelengths. And the absorption spectrum and the fluorescence spectrum are respectively input into an absorption spectrum detection channel spectrometer and a fluorescence spectrum detection channel spectrometer for water quality monitoring. In the embodiment of the invention, 5mg/L VB2 sample solution is used, and three-dimensional fluorescence (figure 2) and visible light absorption spectrum (figure 3) are respectively obtained by a 2-small spectrometer.
The invention adopts an external upper computer to set the position of the optical plate and the timing sequence of the water pump, thereby controlling the wavelength of incident light, controlling spectrum collection and the timing sequence of the inlet and the outlet of a sample. The upper computer adopts a Huashundantian selection notebook computer in the embodiment of the invention, is configured as R7-4800H/16G/512G, and can also use any miniaturized equipment which is provided with a Windows, MacOS or Linux operating system and can run a spectrometer to secondarily develop the SDK.
The upper computer is in internal communication with the spectrum acquisition module and comprises an optical plate position of the program control light splitting module, a water pump time sequence of the program control water path part and a spectrum sampling module of the program control spectrum detection module.
In the embodiment of the invention, the upper computer controls the output wavelength of the light source and the internal communication of the water pump, self-develops protocol organization data based on a TCP/IP (transmission control protocol/Internet protocol) and a Socket interface, and can also realize the remote communication between the client user interface of the upper computer and the lower computer based on other protocols, such as field bus, serial port communication and other protocols capable of transmitting field data.
The protocol is described in detail in fig. 4, where the i parameter represents a control object, the j parameter represents a specific serial number of the current control object, and the T parameter represents a specific action of the control object with a specific serial number. The lower computer is used as a TCP server side, waits for a specific numerical value of the client instruction i-j-T constantly, and controls the operation of a water pump or a stepping motor; the upper computer is used as a TCP client and sends corresponding instructions according to detection requirements to realize equipment control. Specifically, i is 0, and T is the water pump operation time. The upper computer controls the opening and closing time sequence of the water pump through a program, and can automatically complete the operations of water inlet cleaning, sample introduction and emptying in cooperation with a spectrum detection link. j is 0, the water inlet pump operates for T seconds, and the water inlet operation instruction is 0-0-T; j is 1, the evacuation pump runs for T seconds, and evacuation is 0-1-T; j is 3, the sample injection pump runs for T seconds, and the sample injection is 0-2-T. For example, the water flush 30s command is 0-0-30. i is 1, the number of turns of the stepping motor is T/p, T is the number of pulses given to the stepping motor, and p is the number of pulses corresponding to one turn; and p is determined by the stepping angle of the stepping motor and the fine division number of a driver of the stepping motor, and appropriate parameters can be selected according to the precision required by actual measurement. The upper computer controls the stepping motor to change the position of the optical plate through a program, so that the wavelength of incident light of the flow cell is changed. The forward rotation instruction is 1-0-T, the reverse rotation instruction is 1-1-T, wherein T/p is the number of turns of the stepping motor; in this embodiment, if p is 4800, the command for 2 forward rotations of the stepping motor is 1-0-9600.
The internal communication between the upper computer and the spectrometer adopts a secondary development SDK communication protocol built in the spectrometer. The upper computer respectively controls the opening and closing of the spectrometer detection channels corresponding to the absorption spectrum and the fluorescence spectrum through a program; and the data collected by the spectrometer is stored locally.
As shown in fig. 5, the control sequence flow of the spectrum detection module can be divided into wavelength calibration, dark background detection, pure water fluorescence data detection and sample fluorescence data detection. The wavelength calibration is completed in a factory preparation stage, and other steps are completed in field detection, and the method specifically comprises the following steps:
(1) wavelength calibration: before the device is used, a relation table of the number of turns of the stepping motor and the emission wavelength of the light source needs to be calibrated. When in use, the rotation number of turns of the stepping motor corresponding to the required wavelength is obtained by looking up the table according to the relation table, so as to realize the switching of different emission wavelengths. The calibration method comprises the following steps: and starting the absorption detection channel in a lamp-on environment, operating the stepping motor to rotate for different turns, so as to place the prism at different positions, and recording corresponding emission wavelengths of the lamp spectrum center lines at different positions, so as to obtain a relation table of the turns and the wavelengths.
(2) Dark background detection: during dark background detection, an absorption spectrum detection channel (spectrometer) is opened to an empty cuvette (flow cell) in a light-off environment, and absorption spectrum dark environment data alpha is measuredd
(3) Pure water spectrum detection: and after the detection of the dark background is finished, performing pure water spectral detection. The set wavelengths for pure water detection are set to k groups. Let the absorption spectrum data and fluorescence spectrum data of pure water corresponding to the ith wavelength be alphaw(i) And betaw(i) In that respect After the light source is turned on and the glass is preheated for 1-2 minutes, the prism is placed at the position of the initial emission wavelength, the pump time sequence is controlled through the water inlet operation instruction of 0-0-T, and the flow cell is filled with pure water. Then fixing the incident wavelength, respectively opening an absorption spectrum detection channel and a fluorescence spectrum detection channel (spectrometer) to obtain the absorption spectrum data alpha of the pure waterw(1) And fluorescence spectrum data betaw(1). After the data of the group of wavelengths are measured, the next wavelength is changed to continue the detection. And when all the wavelengths are measured, the detection is finished, an emptying pump is started to empty the flow cell, and the prism is reset to the initial position.
(4) Sample spectrum detection: and setting the wavelength to be detected as k groups, wherein the k groups are consistent with the set wavelength for pure water detection. Let the absorption spectrum data and fluorescence spectrum data of pure water corresponding to the ith wavelength be alphas(i) And betas(i) In that respect And controlling the pump time sequence to fill the flow cell with the sample water through a sample introduction instruction of 0-2-T. Then fixing the incident wavelength, respectively opening an absorption spectrum detection channel and a fluorescence spectrum detection channel (spectrometer) to obtain absorption spectrum data alphas(1) And fluorescence spectrum data betas(1). MeasuringAfter the data of the group of wavelengths is completed, the next wavelength is changed to continue the detection. And when all the wavelengths are measured, the detection is finished, and the emptying pump is started to empty the flow cell.
The absorption spectrum a of the current sample can be solved by:
Figure BDA0003380097190000061
wherein the content of the first and second substances,
Figure BDA0003380097190000062
the current sample three-dimensional fluorescence spectrum data F can be solved by the following formula:
F=Bs-Bw
Bs=[βs(1),βs(2),…,βs(i)…,βs(k)]
Bw=[βw(1),βw(2),…,βw(i)…,βw(k)]
wherein, Bs、BwThe matrix is a vector splicing matrix of fluorescence spectra of the sample and pure water under each incident light wavelength i.
(5) And after the current sample is detected, injecting pure water to clean the flow cell, and preparing for detecting the next sample.
At the same time, a plurality of user operation systems can be respectively communicated with the server, so that the multi-user operation and control of the water body detection site are facilitated. The external communication mode of the upper computer and the edge cloud equipment is as follows:
the invention adopts an edge calculation mode to improve the data processing flow. Cloud computing is centralized and is far away from terminal equipment (such as a sensor device and the like), and the problems of long network delay, network congestion, reduced service quality and the like can be caused when computing is placed on the cloud. And the terminal equipment usually has insufficient computing power and cannot be compared with the cloud. In this case, the edge calculation is compliant, and the cloud computing capability is extended to the edge node near the terminal device by establishing the edge node near the terminal device, thereby solving the above problem. The cloud algorithm is issued to the edge computing nodes through the edge computing nodes to run, the capability of extending cloud applications to the edges is provided, the data of the edges and the cloud are linked, and the requirements of a user on remote control, data processing, analysis and decision and intellectualization of edge computing resources can be met.
As shown in fig. 6, the device of the present invention uses a 4G network module to access the internet through an internal upper computer device, and realizes data acquisition, data transmission and algorithm issuing requests based on an edge computing interface. The deep learning algorithm should be debugged before measurement and packaged into a mirror image to be uploaded to the cloud end node. After receiving an algorithm issuing request of the upper computer, the cloud computing node issues a required algorithm to a computing node appointed by the upper computer or an edge computing node with minimum network congestion from the upper computer through scheduling, and the upper computer sends spectrometer data to the edge computing node to carry out detection work depending on edge computing power. The detection result is notified to the upper computer device of the apparatus by the edge node. The cloud service adopts a cloud server and provides database service by adopting a mysql5.6 local deployment mode. The Java-based Web application software container Tomcat is utilized to realize the support of Servlet and JavaServer Page (JSP) according to the technical specification provided by Sun Microsystems, and provides some special functions as a Web server.
The operation of the device of the invention comprises the following general steps:
(1) in the field detection, a water path must be installed first. The sample inlet pipeline of the water pump needs to be communicated with the water body to be detected, and the sample outlet pipeline needs to be suspended and cannot be inserted into any liquid to prevent reverse pumping.
(2) And (3) turning on a power supply, connecting the local upper computer, entering a graphical interface or inputting a starting instruction, continuously sampling to obtain three-dimensional fluorescence and visible light absorption spectrums arranged according to a time sequence, and locally storing the data.
(3) The local upper computer sends a request to the cloud end, applies an algorithm and sends the algorithm to the edge computing nodes, and the edge computing resources are used for storing and analyzing the acquired data.
(4) And obtaining a conclusion whether the water body is polluted or not through an algorithm, and simultaneously assisting with material category information.
The device is packaged into a hand push box type, and is provided with a power supply which uses an energy storage lithium battery and can be converted into 220v alternating current commercial power through an inverter. The power module can be charged through mains supply, and can be charged at any time, and after charging, the power supply of all elements in the box can be realized.
The present invention is not limited to the above-mentioned embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any inventive work are within the scope of the present invention, in the same or similar way as the above-mentioned embodiments of the present invention.

Claims (8)

1. A discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution is characterized by comprising a spectrum acquisition module and an upper computer.
The spectrum acquisition module comprises a light source, a light splitting module, a spectrum detection module and a water pump.
The light splitting module comprises a prism, a diaphragm, a flow cell, a lens and a stepping motor. The triple prism is connected with a stepping motor.
The spectrum detection module comprises two spectrometers.
The water pump comprises an emptying pump, a flushing pump and a sample injection pump. The drainage pump is connected with air, the flushing pump is connected with pure water, and the sampling pump is connected with a sample. The circulation tank is provided with an upper port and a lower port, the lower end is connected with three water pumps at the same time, and the upper end is a water outlet.
The light source is collimated by the lens, then is split by the prism and the diaphragm in sequence, then the incident light obtained after being focused by the lens is vertically incident into the flow cell, the absorption spectrum is obtained in the light path transmission direction, and the fluorescence spectrum is obtained in the direction vertical to the light path transmission direction. Controlling the prism to move through a stepping motor so as to change the wavelength of incident light; different wavelengths of incident light correspond to different absorption and fluorescence spectra. The absorption spectrum of the sample is the average value of the absorption spectra corresponding to different incident light wavelengths; the fluorescence spectrum of the sample is a vector splicing matrix of fluorescence spectra corresponding to different incident light wavelengths.
The absorption spectrum and the fluorescence spectrum are respectively input into a spectrometer.
The upper computer is communicated with the spectrum acquisition module and comprises a step motor, a prism, a water pump and a spectrometer, wherein the step motor is controlled to change the position of the prism, the water pump is controlled to open and close the time sequence, and the spectrometer is controlled to open and close the sampling channel.
2. The discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water pollution according to claim 1, wherein the communication between the upper computer and the stepping motor and the water pump is specifically as follows: the upper computer is used as a TCP client and sends an i-j-T instruction to realize corresponding control. The stepping motor and the water pump are used as TCP server ends and wait for instructions of an upper computer all the time. i represents a control object and comprises a stepping motor and a water pump; j represents the execution action of the current control object, the execution action of the stepping motor comprises positive rotation and negative rotation, and the execution action of the water pump comprises opening of an emptying pump, a flushing pump and a sampling pump; t represents the parameters of the execution action of the current control object, and for the stepping motor, T is the pulse number given to the stepping motor, and p is the pulse number corresponding to one turn, so that the number of turns of the stepping motor is T/p; for the water pump, T is the water pump running time.
3. The apparatus for detecting a discrete three-dimensional fluorescence/visible light absorption spectrum for discriminating water pollution according to claim 1, comprising:
(1) wavelength calibration: calibrating the corresponding relation between different positions of the triple prism and the wavelength of the incident light to obtain a relation table of the number of rotation turns of the stepping motor and the wavelength of the incident light.
(2) Dark background detection: opening a spectrometer connected with an absorption spectrum in an empty flow cell under a light source-free environment to obtain absorption spectrum dark environment data alphad
(3) Pure water spectrum detection: pure water detection sets wavelengths to k groups. The absorption spectrum data and fluorescence spectrum data of pure water corresponding to the ith wavelength are alphaw(i) And betaw(i) In that respect Turning on a light source, arranging a prism at the position of initial emission wavelength, filling the flow cell with pure water, respectively turning on the detection channels of the spectrometer with absorption spectrum corresponding to the fluorescence spectrum, and measuring the absorption spectrum of the pure waterData aw(1) And fluorescence spectrum data betaw(1). Then, the detection is continued by changing the next wavelength. When all the k groups of wavelengths are measured, the flow cell is emptied and the prism is reset to the initial position.
(4) Sample spectrum detection: the wavelengths to be measured are also k groups and are the same as the set wavelengths for pure water detection. The absorption spectrum data and fluorescence spectrum data of pure water corresponding to the ith wavelength are alphas(i) And betas(i) In that respect Filling the flow cell with a sample water sample, respectively opening the spectrometer detection channels corresponding to the absorption spectrum and the fluorescence spectrum, and measuring absorption spectrum data alphas(1) And fluorescence spectrum data betas(1). Then, the detection is continued by changing the next wavelength. And when the k groups of wavelengths are measured, finishing the detection and emptying the flow cell.
4. The discrete three-dimensional fluorescence/visible light absorption spectrum detection device for discriminating water quality pollution according to claim 3, wherein:
the absorption spectrum a of the sample is solved by:
Figure FDA0003380097180000021
wherein the content of the first and second substances,
Figure FDA0003380097180000022
the sample three-dimensional fluorescence spectrum data F is solved by the following formula:
F=Bs-Bw
Bs=[βs(1),βs(2),…,βs(i)…,βs(k)]
Bw=[βw(1),βw(2),…,βw(i)…,βw(k)]
wherein, Bs、BwThe matrix is a vector splicing matrix of fluorescence spectra of the sample and pure water under each incident light wavelength i.
5. The discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water quality pollution according to claim 1, wherein the upper computer locally stores the spectral data acquired by the spectrometer. The upper computer is accessed to the internet and realizes data acquisition, storage and algorithm issuing requests based on the edge computing interface. The upper computer sends the spectrometer data to the edge computing node, and the quantitative and qualitative algorithm for water pollution is tested and finished before measurement, and is packaged into a mirror image to be uploaded to the cloud node. After the cloud computing node receives the algorithm issuing request, the required algorithm is issued to the edge computing node through scheduling, and detection work is carried out depending on edge computing power. And the detection result is notified to the upper computer by the edge node.
6. The apparatus for detecting a discrete three-dimensional fluorescence/visible light absorption spectrum for determining water quality pollution according to claim 1, wherein the light source is a halogen light source.
7. The discrete three-dimensional fluorescence/visible light absorption spectrum detection device for distinguishing water quality pollution according to claim 1, wherein the flow cell is connected with three water pumps through a four-way pipe.
8. The apparatus for detecting a discrete three-dimensional fluorescence/visible light absorption spectrum for discriminating water quality contamination according to claim 1, wherein the wavelength of the incident light is selected from 400nm, 450nm, 475nm, 500nm, 525nm, 550nm, 575nm, 600nm, 650nm, and 700 nm.
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