CN107167446A - A kind of heavy metal-polluted soil is visible and near-infrared spectral reflectance feature diagnostic method - Google Patents
A kind of heavy metal-polluted soil is visible and near-infrared spectral reflectance feature diagnostic method Download PDFInfo
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- CN107167446A CN107167446A CN201710345306.4A CN201710345306A CN107167446A CN 107167446 A CN107167446 A CN 107167446A CN 201710345306 A CN201710345306 A CN 201710345306A CN 107167446 A CN107167446 A CN 107167446A
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- 239000002689 soil Substances 0.000 title claims abstract description 105
- 230000003595 spectral effect Effects 0.000 title claims abstract description 37
- 238000002405 diagnostic procedure Methods 0.000 title claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 88
- 238000001228 spectrum Methods 0.000 claims abstract description 57
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 29
- 238000000985 reflectance spectrum Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 7
- 238000005090 crystal field Methods 0.000 claims abstract description 5
- 238000012937 correction Methods 0.000 claims description 10
- 238000009499 grossing Methods 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 9
- 238000009795 derivation Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 4
- 238000003745 diagnosis Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000004471 energy level splitting Methods 0.000 claims description 2
- 238000010606 normalization Methods 0.000 claims description 2
- 125000003636 chemical group Chemical group 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 16
- 230000007246 mechanism Effects 0.000 abstract description 6
- 238000004445 quantitative analysis Methods 0.000 abstract description 4
- 238000004856 soil analysis Methods 0.000 abstract description 3
- 230000002596 correlated effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 30
- 238000005516 engineering process Methods 0.000 description 12
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 235000012721 chromium Nutrition 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000013178 mathematical model Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- -1 50W Halogen Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- 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
Abstract
The invention discloses a kind of heavy metal-polluted soil is visible and near-infrared spectral reflectance feature diagnostic method, the visible near-infrared reflectance spectrum of first choice measurement heavy metal compound；The configuration of extra-nuclear electron formula of heavy metal reflectance spectrum and heavy metal element is connected, the reflection spectrum characteristic of heavy metal compound is observed；Band po sition and reason that the feature reflection peak of binding crystal field theory analysis heavy metal occurs；The heavy metal compound of various concentrations gradient is added into pedotheque, influence of the heavy metal of variety classes various concentrations to soil reflective spectrum is studied；Different Pretreated spectras are carried out to sample reflection spectrum；The linear relationship probed between heavy metal concentration and soil reflective spectrum and significantly correlated（p<0.05）Position and potential mechanism that wave band occurs.This research method is that the qualitative of heavy metal-polluted soil and quantitative Analysis of Reflective Spectrum provide theoretical foundation and laboratory reference.
Description
Technical field
The present invention relates to the research method of heavy metal-polluted soil, and in particular to one kind utilizes visible and near-infrared spectral reflectance skill
The method that art is studied heavy metal-polluted soil.
Background technology
Soil is one of important natural resources that the mankind depend on for existence and development, is also the important composition of human ecological environment
Part.With the fast development of modern industrial or agricultural, a large amount of pollutants enter soil environment, and wherein heavy metal is important pollutant
One of, and heavy metal in soil is easy to accumulation, accumulation can be caused by approach such as food chains to health to a certain extent
Threaten.
Chemical analysis being used conventional soil heavy metal analysis, although this method precision is high, detection limit is low more, but analysis week
Phase length, cost are high, waste time and energy.The reflectance spectrum of soil includes abundant soil information, is the concentrated expression of soil property
(document 1).With the appearance and development of Visible-to-Near InfaRed reflectance spectrum technology, the composition in soil is carried out using this technology
One of the problem of quick detection is paid close attention to as scientific research.It has now been found that, content of beary metal is obvious with having in soil
The components such as organic matter, carbonate, ferriferous oxide, the clay mineral of spectral signature are relevant, can by the spectral information of these components
With indirect inverting heavy metal in soil content (document 2).However, heavy metal in soil content is extremely low, its spectral signature is possible to
It can be sheltered by the spectral signature of soil key component, the spectral information of heavy metal-polluted soil is directly obtained very using prior art
Difficulty, generally by the contents of heavy metal elements after field acquisition pedotheque using chemical analysis method acquisition reality, has
The soil key component content such as machine matter or organic carbon, then by between actual soil constitution content and soil spectrum data
Inherent dependency relation founding mathematical models analysis prediction this area's contents of heavy metal elements and distributed intelligence.Such as Liu (documents
3) Cu constituent contents in visible ray near infrared light spectrum estimation Lean River flood plain soil are utilized.Yang Yana etc. (document 4) profits
The Zn contents in the agricultural land soil of Pearl River Delta near infrared spectrum combination PLS success prediction.(the documents such as Wu Mingzhu
5) Optimized model of subtropical zone total Chromium in Soil-EO-1 hyperion inverting has been obtained using near-infrared spectrum technique, the model can be with
The fast slowdown monitoring of spectrum for the full chromium of Fuzhou area soil (Cr).Though Visible-to-Near InfaRed reflectance spectrum technology is gradually applied to
The research of heavy metal content in soil, but its quantitative inversion mechanism and modeling method are still in the exploratory stage.
Bibliography：
Reflectance spectrum research [J] soil of [document 1] Xu Binbin soil profiles, 2000,32 (6):281-287.
[document 2] He Junliang, Zhang Shuyuan, looks into brave, waits high-spectrum remote-sensings inverting heavy metal content in soil progress [J]
Remote sensing technology and application, 2015,30 (3):407-412.
[document 3] Yaolin Liu, Yiyun Chen.Feasibility of Estimating Cu
Contamination in Floodplain Soils using VNIR Spectroscopy—A Case Study in
the Le’an River Floodplain,China[J].2012,21(8):951.
[document 4] Yang Yana, Pan Tao, Li Minmiao, waits near infrared spectrums to be used for quick analysis and its stability of zinc in soil
[J] science and technology and engineering, 2014,14 (4):150.
The EO-1 hyperion response of the bright subtropical soils chromiums of [document 5] Wu Mingzhu, Li little Mei, Sha Jin and inverse model
[J] spectroscopy and spectrum analysis, 2014,34 (6):1660.
The content of the invention
It is an object of the invention to from research heavy metal-polluted soil itself reflectance spectrum angle, binding crystal field theory point
Band po sition and reason that the feature reflection peak of heavy metal occurs are analysed, then by the way that artificially design addition is different into pedotheque
Species various concentrations heavy metal compound, studies the influence of the type and concentration of heavy metal to pedotheque reflectance spectrum, is soil
The qualitative and quantitative Analysis of Reflective Spectrum of earth heavy metal provides theory support.
The technical solution adopted in the present invention is：A kind of heavy metal-polluted soil is visible and near-infrared spectral reflectance feature diagnosis side
Method, it is characterised in that comprise the following steps：
Step 1：Measure the Visible-to-Near InfaRed reflectance spectrum of heavy metal compound；
Step 2：The configuration of extra-nuclear electron formula of heavy metal reflectance spectrum and heavy metal element is connected, heavy metal is observed
Reflection spectrum characteristic；
Step 3：Band po sition and reason that the feature reflection peak of binding crystal field theory analysis heavy metal occurs；
Step 4：Soil sample is gathered, the heavy metal compound of various concentrations gradient is added into pedotheque, grinding is mixed
Its Visible-to-Near InfaRed reflected spectrum data is measured after closing uniformly；
Step 5：Different Pretreated spectras are carried out to sample reflection spectrum；
Step 6：Make the Pearson correlation coefficient curve for the heavy metal pedotheque that different Pretreated spectras are crossed.
The beneficial effects of the invention are as follows：
The present invention proposes a kind of method of heavy metal-polluted soil Visible-to-Near InfaRed reflection spectrum characteristic diagnosis, the research side
Method is compared with the research method of in the past traditional heavy metal-polluted soil, and traditional Visible-to-Near InfaRed reflectance spectrum technology is applied to
The experimental study of heavy metal-polluted soil is usually that the pedotheque of field acquisition is obtained to actual heavy metal through chemical analysis method
The soil key component content such as constituent content, organic matter or organic carbon, then passes through actual soil constitution content and soil
Inherent dependency relation founding mathematical models between spectroscopic data are believed to analyze prediction this area's contents of heavy metal elements with distribution
Breath.In order to carry out inexpensive, effective research, the present invention to heavy metal-polluted soil it will be seen that-near-infrared spectral reflectance technology application
To the basic research of heavy metal-polluted soil, and related experiment is designed, explore heavy metal-polluted soil compound reflective spectral response
Feature and mechanism, explore practicality of the visible-near-infrared spectrum technology to type identification and the content estimation of heavy metal in soil
And inherent mechanism, it is that the qualitative of heavy metal-polluted soil and quantitative Analysis of Reflective Spectrum provide theoretical foundation and laboratory reference, is soil
Earth monitoring heavy metal pollution and prevention and control research are offered reference and directive significance.
Brief description of the drawings
Fig. 1 is heavy metal compound CrCl during the present invention is implemented3、CuCl2、ZnCl2Visible-to-Near InfaRed reflected light set a song to music
Line；
Fig. 2 a are CrCl during the present invention is implemented3The reflectance spectrum of powder and the CrCl of various concentrations3The reflected light of pedotheque
Spectral curve；
Fig. 2 b are spectral reflectance and CrCl during the present invention is implemented3The Pearson correlation coefficient curve of concentration；
Fig. 3 a are CuCl during the present invention is implemented2The reflectance spectrum of powder and the CuCl of various concentrations2The reflected light of pedotheque
Spectral curve；
Fig. 3 b are spectral reflectance and CuCl during the present invention is implemented2The Pearson correlation coefficient curve of concentration；
Fig. 4 a are ZnCl during the present invention is implemented2The reflectance spectrum of powder and the ZnCl of various concentrations2The reflected light of pedotheque
Spectral curve；
Fig. 4 b are spectral reflectance and ZnCl during the present invention is implemented2The Pearson correlation coefficient curve of concentration；
Fig. 5 is the CrCl that different Pretreated spectras are crossed during the present invention is implemented3The Pearson correlation coefficient curve of pedotheque；
Fig. 6 is the CuCl that different Pretreated spectras are crossed during the present invention is implemented2The Pearson correlation coefficient curve of pedotheque；
Fig. 7 is the ZnCl that different Pretreated spectras are crossed during the present invention is implemented2The Pearson correlation coefficient curve of pedotheque.
Embodiment
Understand for the ease of those of ordinary skill in the art and implement the present invention, below in conjunction with the accompanying drawings and embodiment is to this hair
It is bright to be described in further detail, it will be appreciated that implementation example described herein is merely to illustrate and explain the present invention, not
For limiting the present invention.
A kind of heavy metal-polluted soil that the present invention is provided is visible and near-infrared spectral reflectance feature diagnostic method, including following step
Suddenly：
Step 1：Measure heavy metal compound CrCl3、CuCl2、ZnCl2Visible-to-Near InfaRed reflectance spectrum, such as Fig. 1 institutes
Show；
Heavy metal compound, because metallic element spectral signature is relevant with its coordination ion type, according to experiment needs, be
Coordination ion is avoided to produce interference to spectral signature, the present embodiment is research object from chloride-based heavy metal.
It is to the specific method of the Visible-to-Near InfaRed reflective spectral measure of sample：
The FieldSpec3 type ground-object spectrum instrument for using ASD companies of the U.S. to produce is unique using 50W Halogen lamp LEDs in darkroom
Light source carries out soil spectrum measure (350~2500nm wave bands).Sampling interval is 1nm, 45 ° of light source incidence angle, away from soil sample surface
30cm, probe is located at the vertical direction 12cm of soil sample surface, 10 ° of the angle of visual field, soil sample area coverage about 44cm2, the average thickness of soil sample
Spend nearly 1cm.First corrected before determining with blank, each 10 curves of spectrum of sample collection, removal 350~399nm and 2451~
2500nm edges wave band, retains 400~2400nm wave bands, obtained after arithmetic average the actual reflectance spectrum number of each soil sample
According to.
Step 2：The configuration of extra-nuclear electron formula of heavy metal reflectance spectrum and heavy metal element is connected, heavy metal is observed
Reflection spectrum characteristic；
The configuration of extra-nuclear electron formula of heavy metal element, the electronics referred mainly on (n-1) d tracks of heavy metal central ion is filled out
Fill state (n is energy fluence subnumber, and d is classification of track, and d tracks most multipotency accommodates 10 electronics).
Step 3：Band po sition and its reason that the feature reflection peak of binding crystal field theory analysis heavy metal occurs；
The feature reflection peak of heavy metal compound is curve of the heavy metal in the reflectivity formation of visible region, in " peak
Shape ".
Electronics occupied state of the feature reflection peak of heavy metal on central ion (n-1) d tracks of heavy metal compound
Determine, when (n-1) d tracks are not filled up by electronics, the electronics on (n-1) d tracks is obtained after luminous energy, in the presence of crystalline field
Generation energy level splitting, produces the electron transition (d-d transition) from low energy d tracks to high energy d tracks, heavy metal optionally absorbs
The light of this wave band of visible region, remaining unabsorbed light is then reflected, and forms reflection peak；When (n-1) d track quilts
When electronics is filled up, will not occur orbital energy level division after absorbing luminous energy, will not also occur d-d transition, will not go out in visible region
Existing feature reflection peak.Wherein,
Step 4：Soil sample is gathered, the heavy metal compound of various concentrations gradient is added into pedotheque, grinding is mixed
Close uniform rear measurement Visible-to-Near InfaRed reflected spectrum data；
During sampling, after sample point rejects plant residue, chip and stone etc., in about 10m2In the range of gather
0-20cm 10 parts of about 1.5kg of topsoil soil, is then homogenously mixed together, and takes the soil sample no less than 500g to fill
Enter and laboratory is taken back after valve bag, soil sample is under field conditions (factors) through air-drying, grinding, cross 2mm hole sizers.By the soil of a certain sampled point
It is divided into 24 parts, every part of 10g, addition and spectrum measuring for heavy metal.
The heavy metal compound of various concentrations gradient is added into pedotheque, it is comprised the following steps that：
Step 4.1：Soil sample is gathered, is necessarily handled, the pedotheque is divided into by the difference of sampled point
Several pieces, the soil sample of each sampled point is divided into one big group, is used to the addition of heavy metal compound；
Step 4.2：Add the heavy metal compound of 8 concentration gradients respectively into soil sample, ground and mixed is uniform, and
Blank control group is set；
Add the CrCl of 8 concentration gradients respectively into 24 parts of pedotheques3、CuCl2、ZnCl2(referring to table 1), measures it
Visible-to-Near InfaRed reflectance spectrum (as shown in Figure 2,3, 4), studies reflected light of the heavy metal to soil of variety classes various concentrations
The influence of spectrum；
The heavy metal concentration of table 1 is designed
Step 4.3：Measurement with the addition of the Visible-to-Near InfaRed reflectance spectrum of the pedotheque of heavy metal compound respectively.
Step 5：Different Pretreated spectras are carried out to sample reflection spectrum；
Preprocess method is：
Absorbance conversion (Transmission to Absorbance Log (1/T)), Savitzky-Golay convolution are put down
Sliding method, standard normal variable conversion (Standard nomal variate transformation, SNV), multiplicative scatter correction
(Multiplicative scatter correction, MSC), Savitzky-Golay convolution method of derivation, derivation pattern are 2
Order polynomial type, 15 smooth points, 1 order derivative (1st Derivative, FD) is smooth, 2 order derivatives (2ndDerivative,
SD it is) smooth.
(1) absorbance is converted；
Absorbance conversion (Transmission to Absorbance Log (1/T)) is to be based on Kubelka-Munk (K-
M) the relation of function and sample concentration, when sample concentration is not high, absorption coefficient is directly proportional to sample concentration, and its expression formula is such as
Under：
In formula, R∞For the relative diffusing reflection rate of practical measurement；K is diffusing reflection absorption coefficient, depending on the change of unrestrained emitter
Learn composition；S is scattering coefficient, depending on the physical characteristic of diffuse reflector；B is light path；C is sample concentration.
(2) Savitzky-Golay convolution exponential smoothing；
Savitzky-Golay convolution exponential smoothing (S-G is smooth) is also known as moving-polynomial smoother, is come to movement by multinomial
Data in window carry out polynomial least mean square fitting, its essence is a kind of weighted mean method, more emphasize the center of central point
Effect.At wavelength k it is smoothed after average value be：
In formula, x is sample spectra (sample number n × wavelength points m), hiFor smoothing factor, w is wavelength points, and i represents the
I smooth window, xk+iRepresent that the centre wavelength point of i-th of window moves the spectrum at k successively from left to right, H for normalization because
Son,Each measured value is multiplied by smoothing factor hiPurpose be to reduce the smooth influence to useful information as far as possible；
hi/ H can be based on the principle of least square, be tried to achieve with fitting of a polynomial.
(3) standard normal variable converter technique；
Standard normal variable conversion (standard nomal variate transformation, SNV) is primarily used to
Eliminate solid particle size, the influence of surface scattering and change in optical path length to NIR diffusing reflection spectrums.To the spectrum for needing SNV to convert
Calculating formula is as follows：
Wherein, sample spectra x (sample number n × wavelength points m), the averaged spectrum of samplexkRepresent wavelength
Spectrum at point k, m counts for wavelength, k=1,2,3, m.
(4) multiplicative scatter correction；
The purpose and the basic phases of SNV of multiplicative scatter correction (multiplicative scatter correction, MSC)
Together, the scattering influence that distribution of particles is uneven and granular size is produced mainly is eliminated.
(5) Savitzky-Golay convolution method of derivation；
The single order (1 of spectrumstDerivative, FD) and second dervative (2nd, DerivativeSD) and it is spectrum analysis
Conventional baseline correction and spectrally resolved preprocess method.
The present embodiment uses the PLS_Toolbox in Matlab to carry out absorbance conversion to obtained sample reflection spectrum
(Transmission to Absorbance Log (1/T)), Savitzky-Golay convolution exponential smoothing, standard normal variable become
Change (Standard nomal variate transformation, SNV), multiplicative scatter correction (Multiplicative
Scatter correction, MSC), Savitzky-Golay convolution method of derivation, derivation pattern be 2 order polynomial types, 15 is flat
Sliding points, 1 order derivative (1st Derivative, FD) is smooth, 2 order derivatives (2nd Derivative, SD) are smoothly waited and do not shared the same light
Spectrum pretreatment；
Step 6：Make Pearson correlation coefficient curve (as shown in Fig. 5,6,7) to pretreated sample reflectance spectrum, visit
Study carefully the linear relationship and significantly correlated (p between heavy metal concentration and soil reflective spectrum<0.05) position that wave band occurs
With potential mechanism.
In step 6, when carrying out Pearson correlation coefficient calculating, due to contents of heavy metal elements in initial soil sample
Soil background is compared to concentration 1000mg/kg~20000mg/kg of the heavy metal compound of addition, and the two differs greatly, right
Experimental result influences very little, can be neglected.Table 2 is Daye Area heavy metal-polluted soil background value；
The Daye Area heavy metal-polluted soil background value * mgkg of table 2-1
The data source of table 2 is in bibliography：Hu Xueyu, Sun Hongfa, Chen De woods Daye mining soil Accumulation of heavy metals are to soil
Influence [J] ecological environment journals of Soil enzyme, 2007,16 (5):1421-1423.
The present invention relates to a kind of method of heavy metal-polluted soil Visible-to-Near InfaRed reflection spectrum characteristic diagnosis, i.e., from research
Heavy metal itself reflection spectrum characteristic sets out, and designs the experiment of the heavy-metal contaminated soil of different type various concentrations gradient, carries
Characteristic wave bands are taken, the potential mechanism of heavy-metal contaminated soil, low cost, the reflectance spectrum for reliably carrying out heavy metal-polluted soil is explored
Research, the present invention is that the qualitative of heavy metal-polluted soil and quantitative Analysis of Reflective Spectrum provide theoretical foundation and laboratory reference, is had
Significance.
Above-mentioned embodiment is used for explaining the present invention, and the present invention relates to utilize Visible-to-Near InfaRed reflectance spectrum
A kind of specific method that technology is studied heavy metal-polluted soil, rather than say Visible-to-Near InfaRed reflectance spectrum technology to soil
Heavy metal carries out research and is only limited to the method, nor saying that all experiment parameters of the present invention immobilize, of the invention is important
Meaning be to heavy metal-polluted soil reflectance spectrum research provide a kind of new approaches, i.e., from heavy metal compound in itself and to
Artificial design adds heavy metal to study in pedotheque, is that Visible-to-Near InfaRed reflectance spectrum technology is used for heavy metal in soil
Type identification and content estimation laboratory reference and inspiration are provided.
It should be appreciated that the part that this specification is not elaborated belongs to prior art.
It should be appreciated that the above-mentioned description for preferred embodiment is more detailed, therefore it can not be considered to this
The limitation of invention patent protection scope, one of ordinary skill in the art is not departing from power of the present invention under the enlightenment of the present invention
Profit is required under protected ambit, can also be made replacement or be deformed, each fall within protection scope of the present invention, this hair
It is bright scope is claimed to be determined by the appended claims.
Claims (13)
1. a kind of heavy metal-polluted soil is visible and near-infrared spectral reflectance feature diagnostic method, it is characterised in that comprise the following steps：
Step 1：Measure the Visible-to-Near InfaRed reflectance spectrum of heavy metal compound；
Step 2：The configuration of extra-nuclear electron formula of heavy metal reflectance spectrum and heavy metal element is connected, the anti-of heavy metal is observed
Penetrate spectral signature；
Step 3：Band po sition and reason that the feature reflection peak of binding crystal field theory analysis heavy metal occurs；
Step 4：Soil sample is gathered, the heavy metal compound of various concentrations gradient is added into pedotheque, ground and mixed is equal
Its Visible-to-Near InfaRed reflected spectrum data is measured after even；
Step 5：Different Pretreated spectras are carried out to sample reflection spectrum；
Step 6：Make the Pearson correlation coefficient curve for the heavy metal pedotheque that different Pretreated spectras are crossed.
2. heavy metal-polluted soil according to claim 1 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In：In step 1, the Visible-to-Near InfaRed reflectance spectrum of heavy metal compound is measured, blank correction is first carried out before determining, during measure
10 curves of spectrum of each sample collection, remove 350~399nm and 2451~2500nm edges wave band, retain 400~2400nm
Wave band, obtained after arithmetic average the actual reflected spectrum data of each soil sample.
3. heavy metal-polluted soil according to claim 1 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In：In step 2, the configuration of extra-nuclear electron formula of heavy metal element refers mainly to (n-1) d tracks of heavy metal compound central ion
On electronics occupied state；Wherein, n is energy fluence subnumber, and d is classification of track, and d tracks most multipotency accommodates 10 electronics.
4. heavy metal-polluted soil according to claim 1 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In：In step 3, the electronics filling shape of the feature reflection peak of heavy metal on (n-1) d tracks of heavy metal compound central ion
State is determined, when (n-1) d tracks are not filled up by electronics, and the electronics on (n-1) d tracks is obtained after luminous energy, in the effect of crystalline field
Lower generation energy level splitting, is produced from low energy d tracks to the electron transition of high energy d tracks, i.e. d-d transition；Heavy metal is optionally
The light of this wave band of visible region is absorbed, remaining unabsorbed light is then reflected, form reflection peak；When (n-1) d rails
When road is filled up by electronics, will not occur orbital energy level division after absorbing luminous energy, will not also occur d-d transition, in visible region not
Feature reflection peak occurs；Wherein, n is energy fluence subnumber, and d is classification of track, and d tracks most multipotency accommodates 10 electronics.
5. heavy metal-polluted soil according to claim 1 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In：The heavy metal compound of various concentrations gradient is added described in step 4 into pedotheque, it is comprised the following steps that：
Step 4.1：Soil sample is gathered, is necessarily handled, the pedotheque is divided into by the difference of sampled point some
Part, the soil sample of each sampled point is divided into one big group, is used to the addition of heavy metal compound；
Step 4.2：Add the heavy metal compound of 8 concentration gradients respectively into soil sample, ground and mixed is uniform, and sets
Blank control group；
Step 4.3：Measurement with the addition of the Visible-to-Near InfaRed reflectance spectrum of the pedotheque of heavy metal compound respectively.
6. heavy metal-polluted soil according to claim 5 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In：In step 4.1, during sampling, after sample point rejects debris, in about 10m2In the range of gather 0-20cm topsoil
10 parts of about 1.5kg of earth soil, is then homogenously mixed together, and takes the soil sample no less than 500g to be taken back after loading valve bag
Laboratory, soil sample is under field conditions (factors) through air-drying, grinding, cross 2mm hole sizers, addition and spectral measurement for Heavy Metal Reagent.
7. heavy metal-polluted soil according to claim 5 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In in step 4.2,8 concentration gradients design of heavy metal compound is shown in Table 1：
The heavy metal concentration of table 1 is designed
Wherein, X represents different types of heavy metal compound.
8. heavy metal-polluted soil according to claim 1 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In：Sample reflection spectrum is carried out in step 5 preprocess method of different Pretreated spectra uses include absorbance conversion method,
Savitzky-Golay convolution exponential smoothing, standard normal variable conversion, multiplicative scatter correction, Savitzky-Golay convolution derivations
Method.
9. heavy metal-polluted soil according to claim 8 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In the absorbance converts exponential smoothing, and calculating formula is as follows：
<mrow>
<mi>F</mi>
<mrow>
<mo>(</mo>
<msub>
<mi>R</mi>
<mi>&infin;</mi>
</msub>
<mo>)</mo>
</mrow>
<mo>=</mo>
<mfrac>
<mi>K</mi>
<mi>S</mi>
</mfrac>
<mo>=</mo>
<mfrac>
<mrow>
<mi>b</mi>
<mi>c</mi>
</mrow>
<mi>S</mi>
</mfrac>
<mo>=</mo>
<msup>
<mi>b</mi>
<mo>,</mo>
</msup>
<mi>c</mi>
<mo>;</mo>
</mrow>
In formula, R∞For the relative diffusing reflection rate of practical measurement；K is diffusing reflection absorption coefficient, depending on the chemical group of unrestrained emitter
Into；S is scattering coefficient, depending on the physical characteristic of diffuse reflector；B is light path；C is sample concentration.
10. heavy metal-polluted soil according to claim 8 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
At, the Savitzky-Golay convolution exponential smoothing, wavelength k it is smoothed after average value be：
<mrow>
<msub>
<mi>x</mi>
<mrow>
<mi>k</mi>
<mo>,</mo>
<mi>s</mi>
<mi>m</mi>
<mi>o</mi>
<mi>o</mi>
<mi>t</mi>
<mi>h</mi>
</mrow>
</msub>
<mo>=</mo>
<mover>
<msub>
<mi>x</mi>
<mi>k</mi>
</msub>
<mo>&OverBar;</mo>
</mover>
<mo>=</mo>
<mfrac>
<mn>1</mn>
<mi>H</mi>
</mfrac>
<munderover>
<mo>&Sigma;</mo>
<mrow>
<mi>i</mi>
<mo>=</mo>
<mo>-</mo>
<mi>w</mi>
</mrow>
<mrow>
<mo>+</mo>
<mi>w</mi>
</mrow>
</munderover>
<msub>
<mi>x</mi>
<mrow>
<mi>k</mi>
<mo>+</mo>
<mi>i</mi>
</mrow>
</msub>
<msub>
<mi>h</mi>
<mi>i</mi>
</msub>
</mrow>
In formula, x is sample spectra, sample number n × wavelength points m；hiFor smoothing factor, w is wavelength points, i represent i-th it is flat
Sliding window mouthful, xk+iRepresent that the centre wavelength point of i-th of window moves the spectrum at k successively from left to right, H is normalization factor,Each measured value is multiplied by smoothing factor hiPurpose be to reduce the smooth influence to useful information as far as possible；hi/H
The principle of least square can be based on, is tried to achieve with fitting of a polynomial.
11. heavy metal-polluted soil according to claim 8 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In the standard normal variable converter technique, calculating formula is as follows：
<mrow>
<mi>x</mi>
<mo>=</mo>
<mfrac>
<mrow>
<mi>x</mi>
<mo>-</mo>
<mover>
<mi>x</mi>
<mo>&OverBar;</mo>
</mover>
</mrow>
<msqrt>
<mfrac>
<mrow>
<munderover>
<mo>&Sigma;</mo>
<mrow>
<mi>k</mi>
<mo>=</mo>
<mn>1</mn>
</mrow>
<mi>m</mi>
</munderover>
<msup>
<mrow>
<mo>(</mo>
<msub>
<mi>x</mi>
<mi>k</mi>
</msub>
<mo>-</mo>
<mover>
<mi>x</mi>
<mo>&OverBar;</mo>
</mover>
<mo>)</mo>
</mrow>
<mn>2</mn>
</msup>
</mrow>
<mrow>
<mi>m</mi>
<mo>-</mo>
<mn>1</mn>
</mrow>
</mfrac>
</msqrt>
</mfrac>
<mo>;</mo>
</mrow>
Wherein, sample spectra x, sample number n × wavelength points m；The averaged spectrum of samplexkRepresent at wavelength points k
Spectrum, m be wavelength points, k=1,2,3, m.
12. heavy metal-polluted soil according to claim 8 is visible and near-infrared spectral reflectance feature diagnostic method, its feature exists
In the Savitzky-Golay convolution method of derivation, derivation pattern is 2 order polynomial types, and 15 smooth points, 1 order derivative is put down
Sliding, 2 order derivatives are smooth.
13. the heavy metal-polluted soil according to claim 1-12 any one is visible and near-infrared spectral reflectance feature diagnosis side
Method, it is characterised in that：In step 6, when carrying out Pearson correlation coefficient calculating, contents of heavy metal elements in initial soil sample
Ignore.
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