CN106918565B - Heavy metal-polluted soil Cd content Inverse modeling and its spectral response characteristics wave band recognition methods based on indoor standard specimen bloom spectrum signature - Google Patents
Heavy metal-polluted soil Cd content Inverse modeling and its spectral response characteristics wave band recognition methods based on indoor standard specimen bloom spectrum signature Download PDFInfo
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Abstract
The invention discloses a kind of heavy metal-polluted soil Cd content Inverse modeling based on indoor standard specimen bloom spectrum signature and its spectral response characteristics wave band recognition methods, the standard soil sample under different Cd pollution contents is artificially designed first, standard specimen is polluted using Soil Background sample laboratory addition pollutant production Cd, and its physicochemical property is analyzed, obtain standard sample of soil indoor spectral and heavy metal Cd content data;Then, it realizes the pretreatment of spectroscopic data using spectral resampling method-standard normal transformation (SNV)-single order/second-order differential-background sample ratio spectra transform method, while using descriptive statistical analysis heavy metal-polluted soil Cd content;Finally, constructing heavy metal-polluted soil Cd content inverse model using partial least-square regression method, it is based on model extraction spectral response characteristics wave band.This is currently at high cost in soil sampling, low efficiency, it is difficult to meet it is a wide range of, fast implement heavy metal content in soil inverting under the conditions of, method that one kind of invention can accurately, efficiently estimate heavy metal-polluted soil Cd content.
Description
Technical field
The present invention relates to heavy metal content in soil EO-1 hyperion inverting fields, in particular to based on indoor standard specimen bloom spectrum signature
Heavy metal-polluted soil Cd content Inverse modeling and its spectral response characteristics wave band know method for distinguishing.
Background technique
With the development of urbanization, industrialization and intensive agriculture, farming land heavy metal pollution of soil object is because of the residence time
It is long, concealment is strong, migration is small, toxicity is big, is not easy the features such as being degraded by microorganisms, being enriched with by food chain, gradually by
To the common concern of domestic and international researcher.However, because a wide range of highly dense sampling cost consumption is huge, normalization rapidly and efficiently dynamically
Monitoring is difficult to carry out, and a wide range of Heavy Metal Pollution Control of carrying out still has that " heavy metal pollution security risk loses count of, is dirty so far
Contaminate spatial framework it is unknown " two big outstanding problems, it has also become pendulum heavy metal pollution of soil comprehensively with deep treatment in face of together
" theoretical and method " wide gap is unable to satisfy country in wide geographic space and rapidly and efficiently investigates thoroughly heavy metal pollution spatial framework, hair
Existing basin heavy metal pollution temporal and spatial evolution and Forming Mechanism, control pollution range expands and transfer, agriculture life of making rational planning for
Produce, reduce the great demand of polluted product damage national health.
At the same time, emerging remote sensing have can by non-contacting mode to target object carry out quickly,
Dynamically, the feature monitored on a large scale, EO-1 hyperion are even more because its more and continuous spectral band advantage is gradually widely used in soil
Earth monitoring heavy metal pollution research in, new opportunity is provided for quantitative inversion heavy metal content in soil so that on a large scale, Gao Shi
Space division resolution, the content spatial distribution of high-precision quick detection heavy metal pollution of soil target area are possibly realized.
In recent years, a large amount of research work has been carried out around the inverting of heavy metal content in soil EO-1 hyperion both at home and abroad.End mesh
Before, numerous studies are it has been verified that when heavy metal content in soil reaches certain numerical value, visible light, near-infrared and thermal infrared on ground
Apparent heavy metal spectral response characteristics can be found in band spectrum test;When heavy metal content in soil is relatively low, can still pass through
The spectral signature of the violent oxide of surface soil organic matter, iron and clay mineral calculates content of beary metal indirectly.However, soil constituent
Complexity, content of beary metal is little, and a huge sum of money is established in the effectively composition spectrums interference such as exclusion soil moisture, organic matter, iron and manganese oxides
Belong to content inverse model, accurately identify trace heavy metal element spectral response characteristics wave band, is that key technology urgently to be resolved is difficult
Topic.
Summary of the invention
In order to effectively exclude the interference of the composition spectrums such as soil moisture, organic matter, iron and manganese oxides, a micro huge sum of money is accurately identified
Belong to component spectrum response characteristic wave band, the present invention provides a kind of heavy metal-polluted soil Cd content based on indoor standard specimen bloom spectrum signature
Inverse modeling and its spectral response characteristics wave band know method for distinguishing.
In order to achieve the above technical purposes, the technical scheme is that, it is a kind of based on indoor standard specimen bloom spectrum signature
Heavy metal-polluted soil Cd content Inverse modeling and its spectral response characteristics wave band know method for distinguishing, comprising the following steps:
Step 1: standard sample of soil production and its accurate heavy metal Cd content and soil spectrum data acquisition;
Step 2: heavy metal-polluted soil Cd content analysis and spectroscopic data pre-process;
Step 3: the heavy metal-polluted soil Cd content Inverse modeling based on the spectroscopic data that step 2 is converted to realizes spectrum
The identification of response characteristic wave band.
The method, the production of standard sample of soil described in step 1 and the acquisition of its accurate heavy metal Cd content, including
Following steps:
Step 1): heavy metal-polluted soil Cd pollution content actual change range and its spectral response effect are fully considered, artificially
Design the standard soil sample under different Cd pollutions content (> 50 grade) (unit: mg/kg);
Step 2): background soil of the grid acquisition mode with 1m × 1m resolution acquisition research area without heavy metal pollution is used
Earth sample is several (> 50 parts), gives over to standard specimen addition soil original pattern;
Step 3): by the collected Soil Background of step 2) through laboratory drying, milled processed, precise obtains standard specimen
Add soil original pattern, every part of 100g;
Step 4): taking step 3) treated that original pattern is a, is digested using three acid --- and atomic absorption spectrophotometry is real
Test room chemical analysis measurement Soil Background heavy metal Cd content (unit: mg/kg);
Step 5): the 1000mg/ that the Cd pollution content value for reaching and setting in step 1) need to be added into 100g original pattern is calculated
The Cd standard solution of kg, calculation formula are as follows:
C=100 (A-S)/ρ
In formula, C represents the Cd standard solution amount (unit: ml) being added in 100g original pattern soil, and A is represented in step 1) and designed
Standard sample of soil heavy metal Cd content (unit: mg/kg), S represents the heavy metal of the Soil Background sample measured in step 4)
Cd content, ρ represent the density (unit: kg/m of Cd standard solution3)。
Particularly, after artificially adding Cd standard solution into 100g soil original pattern, soil weight need to be measured after air-drying processing
Metal Cd content, standard specimen Cd content not more than 0.1mg are the 10 of original pattern-4The order of magnitude can be neglected, therefore soil is total
Amount is based on 100g.
Step 6): laboratory is successively added to the soil of step 3) acquisition by the Cd standard solution amount being calculated in step 5)
In earth original pattern, Soil standard sample is made;
Step 7): using three acid digestion one, atomic absorption spectrophotometry laboratory chemical analyzes determination step 6 one by one) in
Standard sample of soil obtained is accurate to obtain standard sample of soil heavy metal Cd content.
The method, soil pollution standard specimen spectrum described in step 2 and the spectrum that background sample spectrum makees ratio are pre-
Processing method, comprising the following steps:
Step 1): laboratory is artificially added to the standard sample of soil spectrum of Cd pollution standard specimen production and without artificially adding a huge sum of money
Belong to Cd standard solution Soil Background sample spectrum do simultaneously the interval 10nm resampling-standard normal transformation (SNV)-single order/
Second-order differential processing, the spectroscopic data after being converted;
Step 2): the soil pollution standard specimen spectrum after step 1) spectrum transform is made into ratio with background sample spectrum, is obtained
To spectrum characteristic data, calculation formula is as follows:
Ri=Ai/Bi(i=1,2 ..., n)
In formula, n represents spectral band number, and i represents i-th of wave band, AiAfter step 1) the spectrum conversion for representing i-th of wave band
Soil pollution sample spectrum reflectivity, BiSoil spectrum reflectivity after representing step 1) the spectrum conversion of i-th of wave band, Ri
The spectral reflectivity that i-th of wave band obtains after ratio transformation is represented, as heavy metal-polluted soil Cd content EO-1 hyperion Inverse modeling
Input variable spectrum characteristic data.
Detailed description of the invention
Fig. 1 is laboratory standard specimen production method process;
Fig. 2 is spectrum transform example effects of the spectrum based on all kinds of preprocessing procedures;
Fig. 3 is the basic principle of Partial Least Squares modeling factors extraction process;
Fig. 4 is that Partial Least Squares models least squares error theoretical principle.
Specific embodiment
Here is to a preferred embodiment of the invention, in conjunction with the detailed description of attached drawing progress.
1, as shown in Fig. 1 flow chart, standard sample of soil production and its accurately heavy metal Cd content and soil spectrum data acquisition,
Concrete principle method is as follows:
Step 1): heavy metal-polluted soil Cd pollution content actual change range and its spectral response effect are fully considered, artificially
Design the standard soil sample under different Cd pollutions content (> 50 grade) (unit: mg/kg);
Step 2): background soil of the grid acquisition mode with 1m × 1m resolution acquisition research area without heavy metal pollution is used
Earth sample is several (> 50 parts), gives over to standard specimen addition soil original pattern;
Step 3): by the collected Soil Background of step 2) through laboratory drying, milled processed, precise obtains standard specimen
Add soil original pattern, every part of 100g;
Step 4): taking step 3) treated that original pattern is a, is digested using three acid --- and atomic absorption spectrophotometry is real
Test room chemical analysis measurement Soil Background heavy metal Cd content (unit: mg/kg);
Step 5): the 1000mg/ that the Cd pollution content value for reaching and setting in step 1) need to be added into 100g original pattern is calculated
The Cd standard solution of kg, calculation formula are as follows:
C=100 (A-S)/ρ
In formula, C represents the Cd standard solution amount (unit: ml) being added in 100g original pattern soil, and A is represented in step 1) and designed
Standard sample of soil heavy metal Cd content (unit: mg/kg), S represents the heavy metal of the Soil Background sample measured in step 4)
Cd content, ρ represent the density (unit: kg/m of Cd standard solution3)。
Particularly, after artificially adding Cd standard solution into 100g soil original pattern, soil weight need to be measured after air-drying processing
Metal Cd content, standard specimen Cd content not more than 0.1mg are the 10 of original pattern-4The order of magnitude can be neglected, therefore soil is total
Amount is based on 100g.
Step 6): laboratory is successively added to the soil of step 3) acquisition by the Cd standard solution amount being calculated in step 5)
In earth original pattern, Soil standard sample is made;
Step 7): using three acid digestion one, atomic absorption spectrophotometry laboratory chemical analyzes determination step 6 one by one) in
Standard sample of soil obtained is accurate to obtain standard sample of soil heavy metal Cd content.
2, (SNV)-single order/second-order differential-background sample ratio series light is converted using spectral resampling method-standard normal
Spectral transformation method carries out spectroscopic data pretreatment, and concrete principle method is as follows:
Step 1): to eliminate data redundancy, noise is reduced, smooth waveform obtains smoothly changing wave spectrum, between being with 10nm
Every the resampling for carrying out spectroscopic data, calculation formula is as follows:
R=(R1+R2+…+Rn)/n
In formula, R represents the spectral reflectivity after resampling;N represents wave band number in the interval 10nm, RnRepresent n-th of wave
The spectral reflectivity of section.
Step 2): standard normal variable transformation (SNV) is carried out using weighted averageization method to the spectrum after resampling.It is right
In given sample, SNV calculates the standard deviation of all variables, and entire sample passes through the value again and is normalized, calculation formula
It is as follows:
In formula, n is the number of variable;xi,jIt is the value of j-th of variable of i-th of sample;δ is customized offset.
Step 3): it is interfered using single order/second-order differential processing removal partial linear or close to linear background value, i.e. noise
Influence of the spectrum to target optical spectrum, enhanced spectrum feature difference extract spectral signature absorption band, Spectroscopy differential calculation formula are as follows:
R′(λi)=[R (λi)-R(λi-1)]/2Δλ
R″(λi)=[R (λi)-2R(λi-1)+R(λi-2)]/(2Δλ)2
In formula, λiFor the spectral reflectivity of each wave band, R ' (λi) and R " (λi) it is respectively wavelength XiSingle order and second order it is micro-
Spectral, Δ λ are wavelength Xsi-1To λiInterval, this research interval through resampling transformation be 10nm.
Step 4): will be through the soil pollution standard specimen spectrum and back after resampling-SNV-single order/second-order differential spectrum transform
Scape sample spectrum makees ratio, obtains spectrum characteristic data, and calculation formula is as follows:
Ri=Ai/Bi(i=1,2 ..., n)
In formula, n represents spectral band number, and i represents i-th of wave band, AiAfter step 1) the spectrum conversion for representing i-th of wave band
Soil pollution sample spectrum reflectivity, BiSoil spectrum reflectivity after representing step 1) the spectrum conversion of i-th of wave band, Ri
The spectral reflectivity that i-th of wave band obtains after ratio transformation is represented, as heavy metal-polluted soil Cd content EO-1 hyperion Inverse modeling
Input variable spectrum characteristic data.
3, Partial Least Squares Regression (PLSR) method structure is used based on the spectroscopic data that data prediction spectrum is converted to
Heavy metal content in soil inverse model is built, tentatively identifies that the characteristic wave bands heavy metal-polluted soil Cd of heavy metal content in soil inverting contains
Measure EO-1 hyperion Inverse modeling the step of include:
Step 1): setting the wave band number obtained after spectrum transform as m, and soil sample quantity is n, and t, u are respectively from independent variable
With the factor extracted in dependent variable, referred to as the offset minimum binary factor.Each band spectrum reflectivity (x obtained after transformation1,
x2,…,xm) in extract mutually independent ingredient th(h=1,2 ...), from each soil sample heavy metal Cd content value (y1,y2,…,
yn) in extract mutually independent ingredient uj(j=1,2 ...), it is desirable that thAnd ujBetween degree of correlation reach maximum.From original variable
It concentrates and extracts first pair of factor t1And u1Linear combination are as follows:
In formula, w1'=(w1,1,w1,2,…,w1,m) ' be model effect weight;v1'=(v1,1,v1,2,…,v1,m) ' for because becoming
Measure weight.
Step 2): initializaing variable is established to t1Equation.
Wherein, α '1=(α1,1,α1,2,…,α1,m)′;β1'=(β1,1,β1,2,…,β1,m) ' be an only independent variable t1When
Parameter vector, wherein α '1For model effect load capacity.E1And F1Respectively residual error battle array.It can be acquired according to common least square method
Parameter vector α1, β1。
Step 3): returning between the ingredient extracted and dependent variable heavy metal content in soil value is established using multiple regression procedure
Return equation.If the factor I extracted cannot reach the required precision of regression model, residual error battle array E is utilized1And F1It is corresponding to replace x0
And y0, step 2) is repeated, step 3) continues extraction factor, and so on.Assuming that being finally extracted the r factor, x0And y0To r
The regression equation of the factor are as follows:
The first step is analyzed extraction factor t in resulting independent variableh(h=1,2 ... dependent variable is brought in linear combination r) into
To the r factor establish regression equation to get the regression equation of dependent variable, as heavy metal content in soil inverse model, specifically
Formula are as follows:
Y=α1x1+α2x2+···+αmxm
Step 3): extract that above-mentioned model obtains to the significant relevant wave band (x of heavy metal content in soils1,xs2,…,
xsm), as spectral response characteristics wave band.
Claims (3)
1. a kind of heavy metal-polluted soil Cd content Inverse modeling and its spectral response characteristics wave based on indoor standard specimen bloom spectrum signature
Section knows method for distinguishing, which comprises the following steps:
Step 1: production standard sample of soil;
Step 2: obtaining heavy metal Cd content and soil spectrum data from standard sample of soil, heavy metal-polluted soil Cd content is divided
Analysis, and spectroscopic data is pre-processed;
Step 3: the heavy metal-polluted soil Cd content Inverse modeling based on the spectroscopic data that step 2 is converted to realizes spectral response
Characteristic wave bands identification;
Production standard sample of soil described in step 1, comprising the following steps:
Step 1): the standard soil sample under multiple and different Cd pollution contents is made;
Step 2): acquisition research Soil Background sample of the area without heavy metal pollution several, and weighed, obtained after treatment
Standard specimen to more parts of standard qualities adds soil original pattern;
Step 3): taking step 2) treated that standard specimen addition soil original pattern is a, is digested using three acid --- atomic absorption spectrophotometries
Photometry laboratory chemical analysis measurement Soil Background heavy metal Cd content;
Step 4): the 1000mg/ that the Cd pollution content value for reaching and setting in step 1) need to be added into standard quality original pattern is calculated
The Cd standard solution amount of kg;
Step 5): being successively added in the soil original pattern of step 2) acquisition by the Cd standard solution amount being calculated in step 4),
Soil standard sample is made;
Step 6): using three, acid digestion --- atomic absorption spectrophotometry laboratory chemical analyzes determination step 5) in it is obtained
Standard sample of soil is accurate to obtain standard sample of soil heavy metal Cd content.
2. the method according to claim 1, wherein pretreatment described in step 2, comprising the following steps:
Step (1): laboratory is artificially added to the standard sample of soil spectrum of Cd pollution standard specimen production and without artificially adding heavy metal
The Soil Background sample spectrum of Cd standard solution does the interval 10nm resampling-standard normal transformation (SNV)-single order/second order simultaneously
Differential process, the spectroscopic data after being converted;
Step (2): the soil pollution standard specimen spectrum after step (1) spectrum transform is made into ratio with background sample spectrum, is obtained
Spectrum characteristic data, calculation formula are as follows:
Ri=Ai/Bi(i=1,2 ..., n)
In formula, n represents spectral band number, and i represents i-th of wave band, AiSoil after the conversion of the step of representing i-th of wave band (1) spectrum
Earth pollutes sample spectrum reflectivity, BiSoil spectrum reflectivity after the conversion of the step of representing i-th of wave band (1) spectrum, RiIt represents
The spectral reflectivity that i-th of wave band obtains after ratio transformation is inputted as heavy metal-polluted soil Cd content EO-1 hyperion Inverse modeling
Variable spectrum characteristic data.
3. the method according to claim 1, wherein according to the soil of a spectroscopic data huge sum of money described in step 3
Belong to the expression formula of Cd content Inverse modeling are as follows:
Y=α1x1+α2x2+…+αmxm+β
Wherein x1, x2..., xmIt is characterized band spectrum reflectivity, α1, α2..., αmFor parameter vector, β is constant coefficient, and Y is represented
Heavy metal-polluted soil Cd content.
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CN110991064B (en) * | 2019-12-11 | 2021-07-20 | 广州城建职业学院 | Soil heavy metal content inversion model generation method, system and inversion method |
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