CN109211803A - A kind of device that micro- plastics are quickly identified based on micro- multispectral technology - Google Patents
A kind of device that micro- plastics are quickly identified based on micro- multispectral technology Download PDFInfo
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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
- G01N21/17—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
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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
- G01N21/17—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
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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
- G01N21/17—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
- G01N21/17—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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
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- 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
- G01N21/17—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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
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Abstract
The present invention relates to a kind of device quickly identified based on micro- multispectral technology to micro- plastics, which includes multispectral light source, optical alignment system, microcobjective, motorized subject table, beam splitting system, ccd image acquisition device, data processing equipment and computer；The wide wavelength light source that multispectral light source issues is collimated into directional light by the first optical alignment system；Microcobjective is focused for focusing the micro- plastic sample placed on directional light to motorized subject table；Second optical alignment system to through the irreflexive multispectral signal of micro- plastic sample for collimating；Beam splitting system is used to the multispectral signal after the second optical alignment system collimation being divided into ultraviolet spectra, visible spectrum and infrared light；Ccd image acquisition device is for acquiring three kinds of spectral signals and being sent to data processing equipment；Data processing equipment is used to amplify the signal of acquisition and is sent to computer after AD conversion and analyses and compares.
Description
Technical field
The present invention relates to a kind of devices quickly identified based on micro- multispectral technology to micro- plastics, are related to environment
The detection technique field of micro- plastics in monitoring and surrounding medium.
Background technique
The extensive use of plastic products has brought great convenience.But discarded plastic product president when
Between accumulate in the environment, small plastic flakes are broken by physics, chemical action, and be able to carry out remote migration, one
Point plastic refuse wind-force, precipitation, the river-flow the effects of under enter marine environment, through solar irradiation, bioerosion, tide
Smaller fragment is broken into under the physical actions such as alluvion.The prior art by these sizes 1nm to 5mm plastics
Material fibers, particle and fragment are defined as micro- plastics.Micro- plastics are widely distributed in marine environment, due to its biggish specific surface
Product is easier to absorption organic pollutant and heavy metal.Meanwhile micro- plastics are easy to be absorbed by marine organisms, cause damages.Micro- plastics are just
Being increasingly becoming the novel environmental contaminants of one kind causes people widely to pay close attention to.
The pollution situation research for carrying out micro- plastics, needs the presence to plastics micro- in surrounding medium to detect, subsequent
Research needs to carry out qualitative analysis to micro- plastics, to obtain the specifying information of micro- plastic pollution.At present both at home and abroad with regard to plastics kind
Sentencing method for distinguishing mainly has Traditional materialized method and novel lossless detection method, Traditional materialized method according to appearance, density, burning and
Dissolubility property differentiates plastics kind, commonly used approach have appearance diagnostic method, density diagnostic method, solubility method,
Pyrolysismethod, burning differentiate, dual thermal analysis system, and the above method haves the shortcomings that different, causes to be difficult to largely to carry out.Micro- plastics
Novel qualitative analysis usually using scanning electron microscope, electron microscope scanning, infrared spectroscopy, Raman spectrum, pyrolysis inspiratory phase color
Spectrum-mass spectrum etc., these equipment are suitable for lab analysis, and generally existing analysis cost is higher, and analysis environmental condition is more demanding
Problem, it is difficult to the quick detection for sampling location.
Plastics compositing monomer type, processing technology and additive component and content are different, and performance characteristic has more bright
Aobvious difference.Spectral analysis technique is the feature for having absorption, transmitting and scattering spectrum pedigree according to substance, to measure its property
A kind of analytical technology of matter, structure or content has many advantages, such as sensitive, quick, accurate, easy.The prior art lacks a kind of high
Micro- plastics that effect is simple, accuracy rate is high, at low cost are separated, are purified, quantitative approach, become micro- plastics environment distribution and toxicology phase
Close the bottleneck of research.Therefore, it only first develops novel micro- plastics to isolate and purify and quantitative analysis method, can understand micro-
Plastics in the environment with biology it is intracorporal exist, migration and conversion process.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of high sensitivity, simple and easy, strong antijamming capability and inspection
Survey the high-efficient device quickly identified based on micro- multispectral technology to micro- plastics.
To achieve the above object, the present invention takes following technical scheme: one kind is based on micro- multispectral technology to micro- plastics
The device quickly identified, which is characterized in that the device includes multispectral light source, the first optical alignment system, the second optics
Colimated light system, microcobjective, motorized subject table, beam splitting system, ccd image acquisition device, data processing equipment and computer；Institute
It states multispectral light source and is issued using ultraviolet, visible and near infrared band wide wavelength light source, the multispectral light source can be covered
Wide wavelength light source directional light is collimated by first optical alignment system；The microcobjective focuses parallel for focusing
The micro- plastic sample placed on light to the motorized subject table；Second optical alignment system is used for unrestrained through micro- plastic sample
The multispectral signal of reflection is collimated；The beam splitting system is used for will be multispectral after second optical alignment system collimation
Signal is divided into ultraviolet spectra, visible spectrum and infrared spectroscopy；The ccd image acquisition device is for acquiring three kinds of spectral signals simultaneously
It is sent to the data processing equipment；The data processing equipment is sent for amplifying the signal of acquisition with after AD conversion
It analyses and compares to the computer, completes the identification of micro- plastic sample.
Further, motorized subject table control module, sample data library and spectral information ratio are provided in the computer
To module: the motorized subject table control module controls the movement of the motorized subject table and records moving rail for sending signal
Mark；The sample data lab setting has common plastics and common plastics additive, antioxidant, UV resistant agent, nucleation
Agent, antistatic agent, the ultraviolet, infrared of plasticizer, visible spectrum information and the spectrum analysis prediction according to database information building
Model；The spectral information comparison module is used to obtain the spectral information to micrometer plastics, according to the sample data of building
Library and spectrum analysis model, which are obtained, modifies condition information to the type of micrometer plastics, pigment, additive, adsorption；And it compares
The similarity of the test sample point and adjacent test sample point, if similarity is greater than the set value, then it is assumed that the test sample point and adjacent test sample point category
The grain to micrometer plastic sample is estimated according to the spacing and motion track information of adjacent test sample point in same micro- plastic grain
Diameter and length information.
Further, the building process of spectrum analysis prediction model are as follows:
1) spectrum of several known samples of selection is pre-processed using Orthogonal Signal Correction Analyze preconditioning technique；
2) modeling sample and forecast sample are chosen using SPXY method；
3) genetic algorithm is selected to carry out characteristic wavelength extraction to the sample of selection；
4) spectrum analysis prediction model is constructed using least square method supporting vector machine；
5) the spectrum analysis prediction model of building is commented using related coefficient, relation analysis error and root-mean-square error
Valence.
Further, the multispectral light source uses tungsten halogen lamp.
Further, the beam splitting system uses flat reflective grating monochromator.
Further, the data processing equipment includes amplifier and AD converter, and the amplifier is used for received
The signal of the ccd image acquisition device amplifies, and the AD converter is used to be AD converted the signal of amplification, and will
Signal after AD conversion is sent to the computer.
The invention adopts the above technical scheme, which has the following advantages: 1, spectral technique is applied to micro- by the present invention
Plastics detection field is compared with the sample spectra library established before, reaches using the difference of different micro- plastic reflective spectrum
The features such as purpose quickly detected has high sensitivity, simple and easy, strong antijamming capability, detection efficiency is high.2, of the invention
Entire detection process, strong antijamming capability, testing result is with a high credibility, and measurement is fast and convenient, at low cost, applied widely, can
With the measurement for outdoor environment.
Detailed description of the invention
Fig. 1 is the principle of device schematic diagram of the invention quickly identified based on micro- multispectral technology to micro- plastics.
Specific embodiment
Come to carry out detailed description to the present invention below in conjunction with attached drawing.It should be appreciated, however, that attached drawing has been provided only more
Understand the present invention well, they should not be interpreted as limitation of the present invention.
As shown in Figure 1, the device provided by the invention quickly identified based on micro- multispectral technology to micro- plastics, packet
Include multispectral light source 1, optical alignment system 2, microcobjective (not shown), motorized subject table 3, beam splitting system 4, CCD figure
As acquisition device 5, data processing equipment 6 and computer 7.
Multispectral light source 1 can cover ultraviolet, visible and near infrared band wide wave in 200nm~2500nm using wavelength
Long light source, the wide wavelength light source that multispectral light source 1 issues are collimated into parallel and focus through microcobjective by optical alignment system 2
It is placed with the motorized subject table 3 to micrometer plastic sample, through the irreflexive multispectral signal of micro- plastic sample through optical alignment system
System 2 is collimated into directional light and is emitted to beam splitting system 4, and beam splitting system 4 is used to multispectral signal being divided into ultraviolet spectra, visible light
Spectrum and infrared spectroscopy, three kinds of spectral signals after light splitting acquire through ccd image acquisition device 5 and are sent to data processing equipment 6,
Data processing equipment 6 is used to amplify the signal of acquisition and is sent to computer 7 after AD conversion and analyses and compares, quickly
Identify micro- plastic sample.Wherein, computer 7 is also connected with motorized subject table 3, and computer 7 controls motorized subject table 3 and continuously moved
It moves and is able to record the motion profile of motorized subject table 3, realize the automatically scanning to micro- plastic sample.
In a preferred embodiment, multispectral light source 1 can use tungsten halogen lamp.
In a preferred embodiment, optical alignment system 2 can use the entrance slit of limitation incident beam and make
Incident divergent beams become the lens of collimated light beam.
In a preferred embodiment, beam splitting system 4 can use flat reflective grating monochromator, and being used for will be purple
Outside, visible and infrared three spectral regions complex lights are decomposed into monochromatic light.
In a preferred embodiment, data processing equipment 6 includes amplifier and AD converter, and amplifier is for docking
The signal of the ccd image acquisition device 5 of receipts amplifies, and AD converter is for being AD converted the signal of amplification, and by AD
Signal after conversion is sent to computer 7.
In a preferred embodiment, motorized subject table control module, sample data library and light are provided in computer 7
Spectrum information comparison module:
Motorized subject table control module is used to send the movement of signal control motorized subject table and records motion track；
Sample data lab setting has common plastics such as polyethylene, polypropylene, polycarbonate, polystyrene, nylon modeling
Material, polyethylene terephthalate, polyvinyl chloride, polymethacrylates and PC etc. and common plastics additive, antioxygen
The ultraviolet, infrared of the substances such as agent, UV resistant agent, nucleating agent, antistatic agent, plasticizer, visible spectrum information and according to number
According to the spectrum analysis prediction model of library information architecture.
Spectral information comparison module is used to obtain the spectral information to micrometer plastics, is treated using the preconditioning technique of OSC
It surveys sample spectrum to be pre-processed, the method rejecting abnormalities sample combined using principal component analysis with mahalanobis distance, according to structure
The sample data library built and spectrum analysis model, which are obtained, modifies situation to the type of micrometer plastics, pigment, additive, adsorption
Etc. information；Due to continuous test sample, the similarity of the test sample point and adjacent test sample point is compared, if similarity is greater than 90%, then it is assumed that
The test sample point and adjacent test sample point belong to same micro- plastic grain, according to the spacing and motion track information of adjacent test sample point,
Estimate the information such as partial size and the length of micro- plastics.
In a preferred embodiment, the specific method of spectrum analysis prediction model building:
1) Pretreated spectra
The present embodiment uses the pretreatment skill of OSC (Orthogonal Signal Correction Analyze, Orthogonal Signal Correction)
Art pre-processes the spectrum of 254 known samples, reduces noise, the selection of sample number, can be according to reality as example
It is selected.
2) modeling collection samples selection
In view of the influence of the change of properties of the composition variable to be predicted, modeling sample is chosen using SPXY method, this
Embodiment using SPXY, (choose by (Sample Set Partitioning based on Joint x-y Distances) method
178 samples are left 76 samples as forecast set as modeling collection, this method based on the Euclidean between sample spectrum variable away from
From uniformly choosing modeling sample, the Euclidean distance calculation formula between two samples in sample characteristics space are as follows:
In formula, dx(i, j) is the Euclidean distance between sample spectrum variable；dy(i, j) is the Europe between sample components property
Family name's distance, z are selection modeling collection total number of samples, and i, j are two samples for needing to compare.
3) characteristic wavelength extracts
Model is established using all-wave length, the complexity and computation burden of model can be greatly increased, while reducing the pre- of model
Precision is surveyed, irrelevant variable and synteny variable are introduced.Therefore, the present invention selects genetic algorithm to carry out characteristic wavelength extraction.It loses
Propagation algorithm is a kind of adaptive global probability search method, has used for reference living nature natural selection and genetic mechanism, by selecting,
Intersect and be mutated, constantly eliminates poor variable, retain preferable variable, be finally reached optimal result.
4) spectrum analysis prediction model is established
The present invention uses least square method supporting vector machine (Least Squares-Support Vector Machine, LS-
SVM spectrum analysis prediction model) is constructed, principle is data while Function Fitting from low-dimensional to High Dimensional Mapping, then
According to loss function solution is minimized in the higher dimensional space for having equality constraint, linear fit function, detailed process are finally obtained
Are as follows:
Assuming that training sample set D={ (xk, yk) | k=1,2 ..., N }, xk∈Rn, yk∈R,xkIt is input data, ykIt is defeated
Data out.Function Estimation problem in the power space ω is converted to following equation derivation:
Constraint condition are as follows:
Wherein,For nuclear space mapping function, γ is penalty coefficient, ekFor error variance, b is deviation
Amount, loss function J is the sum of SSE error and regularization amount.
According to above formula, Lagrangian can define:
In formula, Lagrangian multiplier ak∈ R is referred to as supported value.Ask L to ω, b, ek, akPartial derivative be equal to 0, disappear
Except ω, e, matrix equation can be obtained:
Wherein
According to Mercer condition, exist:
Kernel function Ψ (xk, xl) polynomial kernel, Multilayer Perception core, B-spline core, RBF core etc. can be used, least square is supported
The Function Estimation of vector machine are as follows:
5) model evaluation
Performance is carried out using the spectrum analysis prediction model of related coefficient, relation analysis error and root-mean-square error to foundation
Evaluation, this is the prior art, and this will not be repeated here.
It is quickly identified below by specific embodiment micro- plastics based on micro- multispectral technology that the present invention will be described in detail
The using effect of device, detailed process are as follows:
Prepare polyethylene, polypropylene, polycarbonate, polystyrene, nylon plastic(s) respectively, carries out sample data library and establish in fact
It tests.
Then it is tested using known micro- plastic sample, the stability of verifying attachment, retest 10 times, it is correct to know
Rate is not 95%, illustrates that device has good stability.
The different plastic grain sample of 10g is mixed, 1g sample is taken to be detected, repeats test 3 times, it is overall to identify
Rate is up to 90%.
Micro- plastic sample in surrounding medium is subjected to device detection, identifies vinyon, polyvinyl chloride plastic magazine
Polypropylene plastics, testing result is consistent with the result detected with Fourier transform infrared spectroscopy, further illustrates apparatus of the present invention
Reliability.
The various embodiments described above are merely to illustrate the present invention, wherein the structure of each component, connection type and manufacture craft etc. are all
It can be varied, all equivalents and improvement carried out based on the technical solution of the present invention should not exclude
Except protection scope of the present invention.
Claims (6)
1. a kind of device quickly identified based on micro- multispectral technology to micro- plastics, which is characterized in that the device includes
Multispectral light source, the first optical alignment system, the second optical alignment system, microcobjective, motorized subject table, beam splitting system, CCD
Image collecting device, data processing equipment and computer；
The multispectral light source use can cover ultraviolet, visible and near infrared band wide wavelength light source, the multispectral light
The wide wavelength light source that source issues is collimated into directional light by first optical alignment system；
The microcobjective is focused for focusing the micro- plastic sample placed on directional light to the motorized subject table；
Second optical alignment system to through the irreflexive multispectral signal of micro- plastic sample for collimating；
The beam splitting system is used to the multispectral signal after second optical alignment system collimation being divided into ultraviolet spectra, visible
Spectrum and infrared spectroscopy；
The ccd image acquisition device is for acquiring three kinds of spectral signals and being sent to the data processing equipment；
The data processing equipment is used to amplify the signal of acquisition and is sent to the computer after AD conversion and is divided
Analysis compares, and completes the identification of micro- plastic sample.
2. the device according to claim 1 quickly identified based on micro- multispectral technology to micro- plastics, feature
It is, motorized subject table control module, sample data library and spectral information comparison module is provided in the computer:
The motorized subject table control module controls the movement of the motorized subject table and records motion track for sending signal；
The sample data lab setting has common plastics and common plastics additive, antioxidant, UV resistant agent, nucleation
Agent, antistatic agent, the ultraviolet, infrared of plasticizer, visible spectrum information and the spectrum analysis prediction according to database information building
Model；
The spectral information comparison module is used to obtain the spectral information to micrometer plastics, according to the sample data library of building
It is obtained with spectrum analysis model and modifies condition information to the type of micrometer plastics, pigment, additive, adsorption；And it compares and is somebody's turn to do
The similarity of test sample point and adjacent test sample point, if similarity is greater than the set value, then it is assumed that the test sample point belongs to adjacent test sample point
Same micro- plastic grain estimates the partial size to micrometer plastic sample according to the spacing and motion track information of adjacent test sample point
And length information.
3. the device according to claim 2 quickly identified based on micro- multispectral technology to micro- plastics, feature
It is, the building process of spectrum analysis prediction model are as follows:
1) spectrum of several known samples of selection is pre-processed using Orthogonal Signal Correction Analyze preconditioning technique；
2) modeling sample and forecast sample are chosen using SPXY method；
3) genetic algorithm is selected to carry out characteristic wavelength extraction to the sample of selection；
4) spectrum analysis prediction model is constructed using least square method supporting vector machine；
5) the spectrum analysis prediction model of building is evaluated using related coefficient, relation analysis error and root-mean-square error.
4. described in any item dresses quickly identified based on micro- multispectral technology to micro- plastics according to claim 1~3
It sets, which is characterized in that the multispectral light source uses tungsten halogen lamp.
5. described in any item dresses quickly identified based on micro- multispectral technology to micro- plastics according to claim 1~3
It sets, which is characterized in that the beam splitting system uses flat reflective grating monochromator.
6. described in any item dresses quickly identified based on micro- multispectral technology to micro- plastics according to claim 1~3
It sets, which is characterized in that the data processing equipment includes amplifier and AD converter, and the amplifier is used for received described
The signal of ccd image acquisition device amplifies, and the AD converter turns for being AD converted to the signal of amplification, and by AD
Signal after changing is sent to the computer.
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| CN109211803B (en) * | 2018-09-17 | 2020-10-09 | 中国科学院生态环境研究中心 | Device for rapidly identifying micro plastic based on microscopic multispectral technology |
| CN112611566A (en) * | 2020-11-27 | 2021-04-06 | 中国航发四川燃气涡轮研究院 | Online particle detection method and device in high-temperature and high-speed airflow based on spectrum identification |
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| CN110261346A (en) * | 2019-06-27 | 2019-09-20 | 浙江大学 | A method of quickly detecting PVC content in soil based near infrared spectrum |
| CN110197486A (en) * | 2019-07-02 | 2019-09-03 | 清华大学 | X-ray grating integrated imaging information extracting method, system and storage medium |
| EP3842788A1 (en) * | 2019-12-23 | 2021-06-30 | Sick Ag | Spectral sensor |
| CN112611566A (en) * | 2020-11-27 | 2021-04-06 | 中国航发四川燃气涡轮研究院 | Online particle detection method and device in high-temperature and high-speed airflow based on spectrum identification |
| CN113484261A (en) * | 2021-06-18 | 2021-10-08 | 北京市农林科学院 | Ultraviolet detection method for polyethylene terephthalate micro-plastic |
| IT202100029888A1 (en) * | 2021-11-25 | 2023-05-25 | Univ Degli Studi Di Firenze | METHOD OF IDENTIFICATION OF MICROPARTICLES, PARTICULARLY MICROPLASTICS, IN ENVIRONMENTAL MATRIX |
| CN114998664A (en) * | 2022-07-18 | 2022-09-02 | 中国科学院烟台海岸带研究所 | Rapid detection method and device for micro-plastic in seawater by multiple optical platforms |
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