CN110132922A - A kind of rapid on-line detecting method of chlorophyll concentration - Google Patents
A kind of rapid on-line detecting method of chlorophyll concentration Download PDFInfo
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- CN110132922A CN110132922A CN201910449171.5A CN201910449171A CN110132922A CN 110132922 A CN110132922 A CN 110132922A CN 201910449171 A CN201910449171 A CN 201910449171A CN 110132922 A CN110132922 A CN 110132922A
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- G—PHYSICS
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- 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
- G01N21/62—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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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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
- G01N21/65—Raman scattering
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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
- G01N21/62—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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- G01N2021/6417—Spectrofluorimetric devices
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Abstract
The present invention proposes that a kind of rapid on-line detecting method of chlorophyll concentration, laser emit laser, be incident in water sample to be measured；Acquire the Raman signal and laser induced fluorescence signal of water sample to be measured；Signal collected is subjected to optical filtering processing by optical filter, light-splitting processing is carried out later, the signal after light splitting is focused to the surface of photodetector by optical lens, electric signal is converted to by photodetector；Above electrical signal is acquired by data collecting card, and transmits it to and carries out data processing in processor, and show the curve of spectrum；In the processor, according to formulaCalculate the concentration C of chlorophylla, R1Indicate raman scattering intensity of the water sample to be measured at Raman wavelength；R2Indicate the fluorescence intensity of water sample Determination of Chlorophyll to be measured；R3Indicate fluorescence background of the water sample to be measured at Raman wavelength；R0Indicate background noise；K is related coefficient constant.The above method has the advantages that detection speed is fast, real-time is good, consumption any reagent is not required to, without complicated operating procedure.
Description
Technical field
The present invention relates to water quality inspection technique field more particularly to a kind of rapid on-line detecting methods of chlorophyll concentration.
Background technique
Chlorophyll is most important pigment in green plants photosynthesis, is present in algae, phytoplankton in a variety of manners
And in other water plants, it is reflection phytoplankton or even the horizontal most effective index of primary productivity, is water eutrophication
Important parameter.When there is eutrophication in water body, due to phytoplankton bloom, cause water body generate blue, it is red,
The wawter blooms phenomenon such as brown can cause to seriously endanger to water quality, constitute to human health, livestock, wild animals and plants and aquatic environment
Significant damage.Therefore quickly the chlorophyll content in detection water can early warning water nutrition degree and water pollution situation in time,
It is a big event of water quality detection.
In recent years, with ocean, water body in lake pollution is increasingly serious, realizes that the real-time detection of chlorophyll has been compeled in eyebrow
The measurement method of eyelash, current existing water body chlorophyll mainly has high performance liquid chromatography (HPLC), spectrophotometer method, remote sensing
Method and fluorescence method, their advantage and disadvantage are as follows:
The advantage and disadvantage table of comparisons of the measurement method of various water body chlorophylls in the prior art of table 1
First two method belongs to laboratory method, does not have real-time, chlorophyll can be by portion during transportation for water sample
Divide microorganism decomposition, influences the accuracy of data, and liquid chromatography operation is extremely complex, need testing staff that there is profession
Relevant knowledge；And spectrophotometer method sensitivity is poor, there are other pigment interference measurements.Remote sensing method is a kind of online
Measurement method, but it is only applicable to the waters of large area, and very high to job requirement of taking photo by plane, it is not easy to real-time quick detection.
Fluorescence method is easy to operate, sample be not required to make any processing can real-time monitoring substance at the scene concentration, and have high sensitivity,
The advantages that selectivity is good, detection limit is low, distinctive is good, various countries are never interrupted the research of fluorescence spectrometry chlorophyll in recent years
It crosses, 2010, chlorophyll fluorescence spectrometer, Emperor Yao's bases in 2012 and horse has been made according to blue light activated fluorescence spectrum in Wang Gang etc.
Mountain has detected the content of chlorophyll a with synchronous fluorescence detection method respectively forever.But their fluorescence detector is all than heavier, volume
Also bigger, it is not readily portable, and be not the detection of real-time online, with advances in technology, need to realize to chlorophyll concentration
Quick online detection.
Summary of the invention
In order to solve the problems in the existing technology, the invention proposes a kind of quick online detections of chlorophyll concentration
Method has the advantages that detection speed is fast, real-time is good, can be widely used for reservoir, the water bodys richness such as lake, river, ocean battalion
The on-site test of feedingization.
To achieve the goals above, the invention proposes a kind of rapid on-line detecting method of chlorophyll concentration, the sides
Method the following steps are included:
Laser in step 1, laser fluorescence spectrum instrument emits laser, is incident in water sample to be measured；
Step 2, the Raman signal that water sample to be measured is acquired by the laser fluorescence spectrum instrument and 670nm~690nm
Laser induced fluorescence signal；
Step 3, by the laser induced fluorescence signal of the Raman signal of water sample to be measured collected and 670nm~690nm
Optical filtering processing is carried out by optical filter, light-splitting processing is carried out by grating splitting system later, the signal after light splitting is passed through into light
Lens focus is learned to the surface of photodetector, optical signal is converted to by electric signal by the photodetector；
Step 4 acquires above electrical signal by the data collecting card in laser fluorescence spectrum instrument, and extremely by electric signal transmission
Data processing is carried out in processor, and shows the curve of spectrum；
Step 5, in the processor, Raman of the water sample to be measured at Raman wavelength obtained in the curve of spectrum is strong
Degree, the fluorescence background and background noise of the fluorescence intensity of water sample Determination of Chlorophyll to be measured, water sample to be measured at Raman wavelength, according to
The calculation formula of chlorophyll concentration calculates the concentration C of the water sample Determination of Chlorophyll to be measureda, the calculation formula of the chlorophyll concentration
ForWherein, R1Indicate raman scattering intensity of the water sample to be measured at Raman wavelength；R2Indicate that the water sample middle period to be measured is green
The fluorescence intensity of element；R3Indicate fluorescence background of the water sample to be measured at Raman wavelength；R0Indicate background noise；K is that related coefficient is normal
Amount.
Preferably, using the laser fluorescence spectrum instrument based on y-type optical fiber, based on y-type optical fiber laser fluorescence spectrum instrument
The rapid on-line detecting method of chlorophyll concentration the following steps are included:
Step 1, the survey that the sound end insertion of the y-type optical fiber in y-type optical fiber laser fluorescence spectrum instrument is filled to water sample to be measured
In trial jar, and the sound end of y-type optical fiber will be inserted under the water surface of water sample to be measured；
Laser in step 2, y-type optical fiber laser fluorescence spectrum instrument emits laser, and the laser is input to y-type optical fiber
Transmitting terminal, by the sound end of y-type optical fiber by laser light incident into water sample to be measured；
The induced with laser of step 3, the Raman signal that water sample to be measured is acquired by reception optical fiber and 670nm~690nm is glimmering
Optical signal is transmitted to the receiving end of y-type optical fiber；
Step 4, by the laser induced fluorescence signal of the Raman signal of water sample to be measured collected and 670nm~690nm
Optical filtering processing is carried out by optical filter, light-splitting processing is carried out by grating splitting system later, the signal after light splitting is passed through into light
Lens focus is learned to the surface of photodetector, optical signal is converted to by electric signal by the photodetector；
Step 5 acquires above electrical signal by data collecting card in y-type optical fiber laser fluorescence spectrum instrument, and by telecommunications
It number is transmitted in processor and to carry out data processing, and show the curve of spectrum；
Step 6, in the processor, Raman of the water sample to be measured at Raman wavelength obtained in the curve of spectrum is strong
Degree, the fluorescence background and background noise of the fluorescence intensity of water sample Determination of Chlorophyll to be measured, water sample to be measured at Raman wavelength, according to
The calculation formula of chlorophyll concentration calculates the concentration C of the water sample Determination of Chlorophyll to be measureda, the calculation formula of the chlorophyll concentration
ForWherein, R1Indicate raman scattering intensity of the water sample to be measured at Raman wavelength；R2Indicate that the water sample middle period to be measured is green
The fluorescence intensity of element；R3Indicate fluorescence background of the water sample to be measured at Raman wavelength；R0Indicate background noise；K is that related coefficient is normal
Amount.
Preferably, the sound end of the y-type optical fiber uses " N+1 " structure, and wherein N is positive integer, and the value of N is in 1≤N
≤ 10, i.e. center is launching fiber, and N root receiving fiber is distributed adjacent to or around launching fiber.
It is dense that the beneficial effect of the program of the present invention is that the rapid on-line detecting method of above-mentioned chlorophyll concentration is suitable for
The detection in the chlorophyll of 0~3.6mg/l is spent, has the advantages that detection speed is fast, real-time is good, the method is not required to consumption and appoints
What reagent, without complicated operating procedure, the detection for water quality industry chlorophyll provides easy advantageous approach, can use extensively
In reservoir, the on-site test of the water eutrophications such as lake, river, ocean.
Detailed description of the invention
Fig. 1 shows the structure of device based on the rapid on-line detecting method of chlorophyll concentration according to the present invention
Schematic diagram.
Fig. 2 shows testing principles based on the rapid on-line detecting method of chlorophyll concentration according to the present invention
Figure.
Appended drawing reference: 1- test bottle, 2- water sample to be measured, 3-Y type optical fiber, 4- laser, 5- laser controlling power supply, 6- processing
Device, 7- optical filter, 8- grating splitting system, 9- optical lens, 10- photodetector, 11- data collecting card.
Specific embodiment
A specific embodiment of the invention is further described with reference to the accompanying drawing.
As shown in Figs. 1-2, chlorophyll concentration according to the present invention rapid on-line detecting method the following steps are included:
Laser 4 in step 1, laser fluorescence spectrum instrument emits laser, is incident in water sample 2 to be measured.Can specifically it lead to
It crosses the control laser controlling power supply 5 of processor 6 to power for laser 4, the touching of the laser 4 in Lai Shixian laser fluorescence spectrum instrument
Hair.
Step 2, the Raman signal that water sample 2 to be measured is acquired by the laser fluorescence spectrum instrument and 670nm~690nm
Laser induced fluorescence signal.In the present embodiment, the laser 4 is then swashed by described using the semiconductor laser of 405nm
The laser induced fluorescence signal of photoluminescence spectrum instrument acquisition 685nm.
Step 3, by the laser induced fluorescence signal of the Raman signal of water sample 2 to be measured collected and 670nm~690nm
Optical filtering processing is carried out by optical filter 7, light-splitting processing is carried out by grating splitting system 8 later, the signal after light splitting is passed through
Optical lens 9 focuses to the surface of photodetector 10, and optical signal is converted to electric signal by the photodetector 10.
Step 4 acquires above electrical signal by data collecting card 11 in laser fluorescence spectrum instrument, and by electric signal transmission
Data processing is carried out into processor 6, and shows the curve of spectrum.
Step 5, in the processor 6, obtain Raman of the water sample to be measured 2 at Raman wavelength in the curve of spectrum
The fluorescence background and background noise of intensity, the fluorescence intensity of 2 Determination of Chlorophyll of water sample to be measured, water sample to be measured 2 at Raman wavelength,
The concentration C of 2 Determination of Chlorophyll of water sample to be measured is calculated according to the calculation formula of chlorophyll concentrationa, the meter of the chlorophyll concentration
Calculating formula isWherein, R1Indicate raman scattering intensity of the water sample 2 to be measured at Raman wavelength；R2Indicate water to be measured
The fluorescence intensity of 2 Determination of Chlorophyll of sample；R3Indicate fluorescence background of the water sample 2 to be measured at Raman wavelength；R0Indicate background noise；K is
Related coefficient constant.
In order to improve detection accuracy, the laser fluorescence spectrum instrument based on y-type optical fiber can be used, such spectrometer is because using
Optical signal transmission fiber can be avoided light and be interfered in communication process, establish base for the Stability and veracity of instrument
Plinth, such spectrometer have micromation, and integrated advantage realizes the portability of detecting instrument, with waterproof, anti-corruption
Many advantages, such as erosion, electromagnetism interference, high temperature resistant.
The rapid on-line detecting method of chlorophyll concentration based on y-type optical fiber laser fluorescence spectrum instrument the following steps are included:
The sound end insertion of y-type optical fiber 3 in y-type optical fiber laser fluorescence spectrum instrument is filled water sample 2 to be measured by step 1
In test bottle 1, and the sound end of y-type optical fiber 3 will be inserted under the water surface of water sample 2 to be measured.
Laser 4 in step 2, y-type optical fiber laser fluorescence spectrum instrument emits laser, and the laser is input to y-type optical fiber 3
Transmitting terminal, by the sound end of y-type optical fiber 3 by laser light incident into water sample 2 to be measured.It can specifically be controlled and be swashed by processor 6
Photocontrol power supply 5 is the power supply of laser 4, the triggering of the laser 4 in Lai Shixian laser fluorescence spectrum instrument.
The induced with laser of step 3, the Raman signal that water sample 2 to be measured is acquired by reception optical fiber and 670nm~690nm is glimmering
Optical signal is transmitted to the receiving end of y-type optical fiber 3.
Step 4, by the laser induced fluorescence signal of the Raman signal of water sample 2 to be measured collected and 670nm~690nm
Optical filtering processing is carried out by optical filter 7, light-splitting processing is carried out by grating splitting system 8 later, the signal after light splitting is passed through
Optical lens 9 focuses to the surface of photodetector 10, and optical signal is converted to electric signal by the photodetector 10.
Step 5 acquires above electrical signal by the data collecting card 11 in y-type optical fiber laser fluorescence spectrum instrument, and will be electric
Signal, which is transmitted in processor 6, carries out data processing, and shows the curve of spectrum.
Step 6, in the processor 6, obtain Raman of the water sample to be measured 2 at Raman wavelength in the curve of spectrum
The fluorescence background and background noise of intensity, the fluorescence intensity of 2 Determination of Chlorophyll of water sample to be measured, water sample to be measured 2 at Raman wavelength,
The concentration C of 2 Determination of Chlorophyll of water sample to be measured is calculated according to the calculation formula of chlorophyll concentrationa, the meter of the chlorophyll concentration
Calculating formula isWherein, R1Indicate raman scattering intensity of the water sample 2 to be measured at Raman wavelength；R2Indicate water to be measured
The fluorescence intensity of 2 Determination of Chlorophyll of sample；R3Indicate fluorescence background of the water sample 2 to be measured at Raman wavelength；R0Indicate background noise；K is
Related coefficient constant.
In the present embodiment, the y-type optical fiber 3 sound end use " 8+1 " structure, i.e., center be launching fiber, eight
Reception optical fiber is circumferentially uniformly distributed around launching fiber, and center launching fiber is single silica fibre of diameter 400um, receives light
Fibre is the silica fibre of eight diameter 200um.
The rapid on-line detecting method of chlorophyll concentration according to the present invention is suitable for concentration in the leaf of 0~3.6mg/l
The detection of green element has the advantages that detection speed is fast, real-time is good, and the method is not required to consumption any reagent, without complexity
Operating procedure, the detection for water quality industry chlorophyll provide easy advantageous approach, can be widely used for reservoir, lake, river,
The on-site test of the water eutrophications such as ocean.
Claims (3)
1. a kind of rapid on-line detecting method of chlorophyll concentration, it is characterised in that: the described method comprises the following steps:
Laser in step 1, laser fluorescence spectrum instrument emits laser, is incident in water sample to be measured；
Step 2 acquires the Raman signal of water sample to be measured and the laser of 670nm~690nm by the laser fluorescence spectrum instrument
Induced fluorescence signal；
Step 3 passes through the laser induced fluorescence signal of the Raman signal of water sample to be measured collected and 670nm~690nm
Optical filter carries out optical filtering processing, carries out light-splitting processing by grating splitting system later, the signal after light splitting is passed through optical frames
Head focuses to the surface of photodetector, and optical signal is converted to electric signal by the photodetector；
Step 4 is acquired above electrical signal by the data collecting card in laser fluorescence spectrum instrument, and electric signal transmission is extremely handled
Data processing is carried out in device, and shows the curve of spectrum；
Step 5, in the processor, obtain raman scattering intensity of the water sample to be measured in the curve of spectrum at Raman wavelength,
Fluorescence background and background noise of the fluorescence intensity, water sample to be measured of water sample Determination of Chlorophyll to be measured at Raman wavelength, according to leaf
The calculation formula of green element concentration calculates the concentration C of the water sample Determination of Chlorophyll to be measureda, the calculation formula of the chlorophyll concentration isWherein, R1Indicate raman scattering intensity of the water sample to be measured at Raman wavelength；R2Indicate water sample Determination of Chlorophyll to be measured
Fluorescence intensity；R3Indicate fluorescence background of the water sample to be measured at Raman wavelength；R0Indicate background noise；K is that related coefficient is normal
Amount.
2. the rapid on-line detecting method of chlorophyll concentration according to claim 1, it is characterised in that: using based on Y type
The laser fluorescence spectrum instrument of optical fiber, the rapid on-line detecting method of the chlorophyll concentration based on y-type optical fiber laser fluorescence spectrum instrument
The following steps are included:
Step 1, the test bottle that the sound end insertion of the y-type optical fiber in y-type optical fiber laser fluorescence spectrum instrument is filled to water sample to be measured
In, and the sound end of y-type optical fiber will be inserted under the water surface of water sample to be measured；
Laser in step 2, y-type optical fiber laser fluorescence spectrum instrument emits laser, and the laser is input to the transmitting of y-type optical fiber
End, by the sound end of y-type optical fiber by laser light incident into water sample to be measured；
The laser induced fluorescence of step 3, the Raman signal that water sample to be measured is acquired by reception optical fiber and 670nm~690nm is believed
Number, it is transmitted to the receiving end of y-type optical fiber；
Step 4 passes through the laser induced fluorescence signal of the Raman signal of water sample to be measured collected and 670nm~690nm
Optical filter carries out optical filtering processing, carries out light-splitting processing by grating splitting system later, the signal after light splitting is passed through optical frames
Head focuses to the surface of photodetector, and optical signal is converted to electric signal by the photodetector；
Step 5 acquires above electrical signal by the data collecting card in y-type optical fiber laser fluorescence spectrum instrument, and electric signal is passed
It transports to and carries out data processing in processor, and show the curve of spectrum；
Step 6, in the processor, obtain raman scattering intensity of the water sample to be measured in the curve of spectrum at Raman wavelength,
Fluorescence background and background noise of the fluorescence intensity, water sample to be measured of water sample Determination of Chlorophyll to be measured at Raman wavelength, according to leaf
The calculation formula of green element concentration calculates the concentration C of the water sample Determination of Chlorophyll to be measureda, the calculation formula of the chlorophyll concentration isWherein, R1Indicate raman scattering intensity of the water sample to be measured at Raman wavelength；R2Indicate water sample Determination of Chlorophyll to be measured
Fluorescence intensity；R3Indicate fluorescence background of the water sample to be measured at Raman wavelength；R0Indicate background noise；K is that related coefficient is normal
Amount.
3. the rapid on-line detecting method of chlorophyll concentration according to claim 2, it is characterised in that: the y-type optical fiber
Sound end use " N+1 " structure, wherein N is positive integer, and the value of N is launching fiber, N piece-root grafting in 1≤N≤10, i.e. center
Optical fiber is received to be distributed adjacent to or around launching fiber.
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