CN106932373B - Seawater total organic carbon optical in-situ sensor - Google Patents
Seawater total organic carbon optical in-situ sensor Download PDFInfo
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/49—Scattering, i.e. diffuse reflection within a body or fluid
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6495—Miscellaneous methods
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- G01N2201/066—Modifiable path; multiple paths in one sample
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Abstract
The invention relates to a seawater total organic carbon optical in-situ sensor, which comprises a light source module, a reference light detection module, a sample cell, a scattered light detection module, a reflected fluorescence detection module and a signal driving and processing module, wherein the light source module provides monochromatic ultraviolet light for TOC detection, the reference light detection module realizes detection of the reference light, the seawater scattered light and the reflected fluorescence, and the signal driving and processing module provides driving signals for the light source module and processes signals obtained by the detection module; the three-dimensional fluorescence spectrum of the seawater is obtained by the diffraction grating and the electron multiplication CCD, and the sensor is self-compensated through the background light information and the turbidity information, so that the accurate measurement of the TOC is completed. The invention does not need to add chemical reagent, is convenient for integration, and can realize high-precision in-situ detection of the TOC of the seawater.
Description
Technical Field
The invention relates to a detection device, in particular to a TOC concentration detection device.
Background
The total organic carbon (Total Organic Carbon, TOC) represents the total sum of organic substances contained in the water body and is an important index of the pollution degree of the water body by the organic substances. At present, TOC measurement is widely applied to aspects such as river, lake and ocean monitoring, and the TOC measurement has become a main detection means for controlling the quality of water bodies in the world. In the newly issued pollution discharge charge collection standard management method, the TOC is formally listed in the water pollutant pollution equivalent value table by the fourth ministry of China in 2003.
The current detection method of the seawater TOC mainly comprises the following two types: the first category is the laboratory classical detection method. The method mainly comprises high-temperature catalytic combustion oxidation-non-dispersive infrared detection (NDIR), wet oxidation (persulfate) -non-dispersive infrared detection and the like, the main problems of the methods are that the testing method is complex, secondary pollution is caused by using chemical reagents, the measuring time is long, the measuring speed is low and the like, and the methods can only be completed in a laboratory. The second type is a shore-based or shipborne online detection method, which mainly comprises a spectrum method, a resistance method, a conductivity method, an ozone oxidation method, an ultrasonic cavitation sonoluminescence method and the like, however, the shipborne online detection technology is limited by the number of times of sea emergence, and the shore-based online detection technology can only cope with the situation of seaside or sea entrance. These methods are difficult to meet the all-round, three-dimensional and uninterrupted monitoring needs of marine surveys.
Disclosure of Invention
The invention aims to provide the seawater total organic carbon optical in-situ sensor which can automatically measure and process data without adding chemical reagents, can realize online in-situ detection of TOC and has higher measurement precision.
The invention comprises a light source module, a reference light detection module, a sample cell, a scattered light detection module, a reflected fluorescence detection module and a signal driving and processing module. The light source module comprises an LED array and a linear adjustable filter array, wherein the LED array is a light-emitting device, the output end of the LED array is connected with the linear adjustable filter array, and the linear adjustable filter array filters light output by the LED array into adjustable monochromatic ultraviolet light;
the reference light detection module comprises a spectroscope and a first light detector, wherein the spectroscope is positioned on a light path from which the adjustable monochromatic light source exits, the mirror surface of the spectroscope forms a 45-degree angle with the light source exit direction, and the reflectivity is 10-30%; the spectroscope divides the adjustable monochromatic ultraviolet light into two beams of light which are mutually perpendicular, one beam is used as detection light, the other beam is used as reference light, the first optical detector is positioned on the optical path of the reference light and forms an angle of 90 degrees with the emergent direction of the light source, and the detection signal is used for background reference light compensation;
the sample cell and scattered light detection module comprises a binary transparent mirror, a first collimator, a sample cell, a second collimator and a second photodetector, wherein the binary transparent mirror is positioned behind the spectroscope, the mirror surface forms an angle of 45 degrees with the light irradiation direction, the first collimator and the sample cell are sequentially arranged on a reflected light path at one side of the binary transparent mirror, and the first collimator is positioned between the binary transparent mirror and the sample cell to ensure that adjustable monochromatic ultraviolet light is converged in the sample cell; the second collimator and the second optical detector are positioned at the side surface of the incident light path outside the sample cell, the second optical detector is aligned with the collimating light path of the second collimator, and the second optical detector detection signal is used for turbidity compensation;
the reflected fluorescence detection module comprises a third collimator, a diffraction grating and an electron multiplication CCD, wherein the third collimator and the diffraction grating are positioned on the other side of the binary transparent reflecting mirror and are used for collecting fluorescence reflected from the sample cell, the diffraction grating expands the reflected fluorescence passing through the third collimator into a spectrum arranged according to wavelengths, and the electron multiplication CCD is positioned at a spectrum position formed by the dispersion of the diffraction grating and converts an optical signal of the fluorescence spectrum into an electric signal;
the output electric signals of the reference light detection module, the sample cell, the scattered light detection module and the reflection fluorescence detection module are connected to the signal driving and processing module through signal wires, and the signal driving and processing module realizes the functions of light source driving, data processing of each detection module, signal compensation and the like by using an FPGA+DSP as a data processing core.
The working process of the invention comprises the following steps: the light emitted by the LED array outputs adjustable monochromatic ultraviolet light through the linear adjustable filter array, and then the detection light and the reference light are obtained through the spectroscope; the reference light is used for eliminating background light interference, and the detection light is diverted into the sample cell after passing through the binary transparent reflector and irradiates on the sea water to be detected, so as to generate transmission light, reflection fluorescence and scattering light; the reflected fluorescence is changed into an electric signal from an electron multiplication CCD (charge coupled device) through a diffraction grating to form a spectrum arranged according to the wavelength, fluorescence generated by different excitation wavelengths is collected to form a three-dimensional fluorescence spectrum, and the spectrum, reference background light information and light turbidity information are used for realizing internal self-compensation of the TOC sensor through a signal driving and processing system to finish TOC measurement.
Compared with the prior art, the invention has the following advantages:
1. detection is carried out based on a spectrum method without adding chemical reagents;
2. the equipment is small and exquisite, the integration level is high, and the in-situ online measurement can be realized;
3. the three-dimensional fluorescence spectrum information is combined with reference background light and turbidity information, so that the detection precision is effectively improved.
Drawings
Fig. 1 is a schematic diagram of the structure of the present invention.
In the figure: 1-LED array, 2-linear adjustable filter array, 3-spectroscope, 4-binary transparent mirror, 5-collimator I, 6-sample cell, 7-collimator II, 8-collimator III, 9-diffraction grating, 10-electron multiplication CCD, 11-photodetector I, 12-photodetector II, 13-signal drive and process module, 14-probe light, 15-reference light.
Detailed Description
In the schematic diagram of the seawater total organic carbon optical in-situ sensor shown in fig. 1, an LED array 1 in a light source module is a light-emitting device, the output end of the LED array is connected with a linear adjustable filter array 2, and the linear adjustable filter array filters light output by the LED array into adjustable monochromatic ultraviolet light; the spectroscope 3 in the reference light detection module is positioned on the light path of the adjustable monochromatic ultraviolet light source, the mirror surface of the spectroscope forms an angle of 45 degrees with the light source emitting direction, the reflectivity is 10-30%, the spectroscope divides the adjustable monochromatic ultraviolet light into two beams of light which are mutually perpendicular, one beam is used as detection 14, the other beam is used as reference light 15, the first optical detector 12 is positioned on the light path of the reference light and forms an angle of 90 degrees with the light source emitting direction, and the detection signal is used for background reference light compensation; a binary transparent mirror 4 in the sample cell and the scattered light detection module is positioned behind the spectroscope, the mirror surface and the light irradiation direction form a 45-degree angle, a collimator I5 and a sample cell 6 are sequentially arranged on a reflected light path at one side of the binary transparent mirror, and the collimator I is positioned between the binary transparent mirror and the sample cell so as to ensure that adjustable monochromatic ultraviolet light is converged in the sample cell; the second collimator 7 and the second optical detector 12 are positioned at the side surface of an incident light path outside the sample cell, the second optical detector is aligned with a collimation light path of the second collimator, and a detection signal of the second optical detector is used for turbidity compensation; the third collimator 8 and the diffraction grating 9 in the reflection fluorescence detection module are positioned on the other side of the binary transparent reflector and are used for collecting fluorescence reflected from the sample cell, the diffraction grating expands the reflection fluorescence passing through the third collimator into a spectrum arranged according to wavelengths, and the electron multiplication CCD10 is positioned at a spectrum position formed by the dispersion of the diffraction grating and converts an optical signal of the fluorescence spectrum into an electric signal; the output electric signals of the reference light detection module, the sample cell, the scattered light detection module and the reflection fluorescence detection module are connected to the signal driving and processing module 13 through signal wires, and the signal driving and processing module realizes the functions of light source driving, data processing of each detection module, signal compensation and the like by using an FPGA+DSP as a data processing core.
Claims (6)
1. An optical in-situ sensor for seawater total organic carbon, comprising:
the light source module is used for emitting monochromatic ultraviolet light;
the reference light detection module comprises a spectroscope, wherein the spectroscope is positioned on a light path from which the monochromatic ultraviolet light exits and is used for dividing the monochromatic ultraviolet light into detection light and reference light, and the detection light and the reference light are mutually perpendicular;
the sample cell and scattered light detection module comprises a binary transparent reflector, a collimator I, a collimator II, a sample cell and a light detector II, wherein the binary transparent reflector reflects the detection light to the collimator I, the collimator I is used for converging the detection light in the sample cell, the detection light reaches the light detector II after passing through the sample cell and the collimator II, and a signal generated by the light detector II is used for turbidity compensation;
the reflected fluorescence detection module is connected with the sample cell and the scattered light detection module and is used for collecting fluorescence reflected from the sample cell and converting optical signals of the spectrum of the fluorescence into electric signals;
the signal driving and processing module is connected with the light source module, the reference light detection module, the sample cell, the scattered light detection module and the reflected fluorescence detection module, and is used for driving the light source module, the reference light detection module, the sample cell, the scattered light detection module and the reflected fluorescence detection module, and performing data processing and signal compensation.
2. The seawater total organic carbon optical in-situ sensor of claim 1, wherein the light source module comprises an LED array and a linear tunable filter array, the LED array is a light emitting device, the output end of the LED array is connected with the linear tunable filter array, and the linear tunable filter array filters light output by the LED array into tunable monochromatic ultraviolet light.
3. The seawater total organic carbon optical in-situ sensor according to claim 2, wherein the reference light detection module further comprises a first photodetector, the beam splitter is positioned on an optical path of the light emitted by the LED array, a mirror surface of the beam splitter forms a 45 ° angle with an emitting direction of the light passing through the linear adjustable filter array, and a specular reflectivity of the beam splitter is 10-30%; the first light detector is positioned on the light path of the reference light and forms an angle of 90 degrees with the emergent direction of the light emitted by the light source module, and is used for detecting signals and compensating background reference light.
4. The seawater total organic carbon optical in-situ sensor according to claim 3, wherein the binary transparent mirror is positioned behind the spectroscope, the mirror surface of the binary transparent mirror forms an angle of 45 degrees with the light transmission direction, the collimator I and the sample cell are sequentially arranged on the reflected light path at one side of the binary transparent mirror, and the collimator I is positioned between the binary transparent mirror and the sample cell so as to ensure that the adjustable monochromatic ultraviolet light is converged in the sample cell; the second collimator and the second photodetector are positioned at the side surface of the incident light path outside the sample cell, and the second photodetector is aligned with the collimating light path of the second collimator.
5. The seawater total organic carbon optical in-situ sensor of claim 4, wherein the reflected fluorescence detection module comprises a third collimator, a diffraction grating and an electron multiplying CCD, wherein the third collimator and the diffraction grating are positioned on the other side of the binary transflector for collecting fluorescence reflected back from the sample cell, the diffraction grating expands the reflected fluorescence passing through the third collimator into a spectrum arranged by wavelength, and the electron multiplying CCD is positioned at a spectral position formed by dispersion of the diffraction grating, and converts an optical signal of the fluorescence spectrum into an electrical signal.
6. The seawater total organic carbon optical in-situ sensor of claim 1, wherein the output electrical signals of the reference light detection module, the sample cell and scattered light detection module, and the reflected fluorescence detection module are connected to the signal driving and processing module through signal lines.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108279225A (en) * | 2018-02-09 | 2018-07-13 | 秦皇岛红燕光电科技有限公司 | Phytoplankton ＆ Suspension red tide and its toxicity detection optics home position sensing |
| CN109655110A (en) * | 2019-01-02 | 2019-04-19 | 南京大学 | Composite package LED light source and water monitoring device based on the light source |
| CN111175260B (en) * | 2020-01-07 | 2022-05-10 | 燕山大学 | Ocean TOC sensor based on ultraviolet three-dimensional fluorescence and using method |
| CN113933242B (en) * | 2021-09-16 | 2022-08-16 | 燕山大学 | Multi-source spectrum total organic carbon in-situ sensor optical path structure and application method thereof |
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