CN105486663B - A method of detecting the stable carbon isotope ratio of soil using near infrared spectrum - Google Patents
A method of detecting the stable carbon isotope ratio of soil using near infrared spectrum Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—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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- 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
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—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
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Abstract
The present invention provides a kind of methods for the stable carbon isotope ratio detecting soil using near infrared spectrum, and described method includes following steps：1) the stable carbon isotope ratio of multiple calibration pedotheques is measured；2) the diffusing reflection spectrogram of the near infrared band of acquisition calibration pedotheque, obtains original spectrogram；3) original spectrogram is smoothly pre-processed, spectrogram after being handled；4) Partial Least Squares is used to establish the causes after the processing of calibration pedotheque between spectrogram and stable carbon isotope ratio；5) the diffusing reflection spectrogram for acquiring the near infrared band of pedotheque to be measured, the stable carbon isotope ratio of pedotheque to be measured is calculated according to causes.Method provided by the invention can quickly detect soil stabilization carbon isotope ratio using near-infrared spectra.
Description
Technical field
The present invention relates to field of ecology, more particularly to a kind of method of the stable carbon isotope ratio of detection soil.
Background technology
Stable carbon isotope ratio (δ13C) analysis method can be used to indicate that the source of the soil organism, research soil have
The degree of decomposition of machine matter and its component and turnover, reproduction C3/C4The change histories of vegetation, in soil organism research and ecology
In be increasingly becoming a strong tool.
Measure soil δ13C generally uses stable isotope ratio mass spectrography (IRMS), its working principle is that：Soil passes through height
Temperature burning, organic carbon therein are transformed into gaseous state CO2；After chromatographic column or adsorption column are separated with other gases, in ion source
In be ionized；After ion beam line focus and acceleration, into mass analyzer；Under magnetic fields, ion stream presses certain lotus
Matter ratio (m/z) deflects, and since the quality (m) of various isotopes is different, the degree of ion stream deflection is also different；Each is same
The ion beam of position element reaches ion acceptor by the track of oneself, and the amplified ion intensity of flow for recording each isotope is surveyed
Go out isotopic ratio.Stable isotope ratio mass spectrometer is expensive, and special messenger is needed to operate, and test period is long, corresponding test at
This is also high.Therefore, isotope ratio mass spectrometry (IRMS), which measures soil δ 13C, following deficiency：1, expensive equipment, test at
This height；2, technology requires high, not easy to operate；3, test period is long；4, it is not easy to promote.
Application of the infrared spectrum technology in soil analysis is risen in last century the eighties.Currently near infrared spectrum
(NIR) and middle infrared spectrum (MIR) technology is widely used in point of the various physicochemical properties of soil in conjunction with Chemical Measurement means
Analysis, it is as a result satisfactory.Such as：Total carbon content, total nitrogen content, content of tatal phosphorus, moisture, the soil texture, potassium (K), calcium (Ga),
Content, the Microbials of metals such as iron (Fe), manganese (Mn), magnesium (Mg) etc..NIR, MIR spectroscopic analysis methods are a kind of indirect analyses
Method needs first to be measured the physicochemical property of a large amount of representative pedotheques with reference method, by being associated with sample spectra
Calibration model is built with its physicochemical property；Then the composition and property of unknown pedotheque are predicted with calibration model.Therefore, quilt
The pedotheque of survey will include the range of the type and physicochemical property of predicted pedotheque as far as possible, and to its each component
Physicochemical property carries out Accurate Determining.
Near-infrared (NIR) SPECTRAL REGION refers to electromagnetic wave of the wavelength within the scope of 780~2500nm, spectral information source
In the frequency multiplication and sum of fundamental frequencies of intramolecule vibration, and mainly reflect hydric group (such as C-H, N-H, O-H, S-H etc.) in molecule
Frequency multiplication and sum of fundamental frequencies absorption of vibrations.Many organic matters have characteristic absorption, and the absorption intensity of different-waveband in the SPECTRAL REGION
There are correspondences with the molecular structure and concentration of the substance.In infrared (MIR) SPECTRAL REGION be wavelength in 2500~25000nm
Electromagnetic wave in range, substance are that fundamental frequency, frequency multiplication and sum of fundamental frequencies absorb in the absorption peak of this range.Different compounds have it special
Infrared absorption spectrum, intensity, position, shape and the number of bands of a spectrum are related with compound and its state.MIR and NIR spectra
It is the frequency multiplication of material molecule internal vibration and the absorption of sum of fundamental frequencies difference lies in, near infrared spectrum, different component and functional group
Bands of a spectrum are easier to overlapping and information strength is weaker, cause spectrum elucidation relative difficulty, institute's established model easily to be influenced by extraneous factor, surely
Qualitative difference；And the fundamental frequency that middle infrared spectrum is intramolecule vibration absorbs, information strength is stronger, and information extraction is relatively easy.
Diffusing reflection is a kind of common near-infrared acquisition method, and basic principle is：When illumination is mapped to loose solid-like
When the surface of product, in addition to some is reflected by sample surfaces and (is known as mirror reflected light) immediately, remaining incident light exists
Sample surfaces generate unrestrained transmitting, or toss about reflection gradually decaying between sample particle, or to penetrate dissipating of turning back again after internal layer
It penetrates.The light for being diffusely reflected or scattering out after these contact sample microparticle surfaces has absorption-attenuation characteristic, and here it is unrestrained anti-
Penetrate the fundamental cause for generating spectrum.The effect of diffusing reflection device be exactly maximum intensity these diffusion, the luminous energy that scatter out
Pinching gets up to be sent into detector, so as to get the spectral signal with good signal-to noise ratio.The spectral technology that diffuses is fast in the past 20 years
A kind of detection method of speed development, this method is easy to operate, quick, can be carried out fast, accurately to various samples to non-demolition
Analysis, the development of the digitlization of analytical instrument and chemometrics method in addition can be well with chemometrics method
The extraction and the influence in terms of background interference for solving spectral information so that it plays important function in many fields, and takes
Obtained preferable social and economic benefit.
Either NIR or MIR spectrum are done in collected spectral information including some can generate Spectral Signal
The information disturbed, to influence the foundation and prediction of model, it is therefore desirable to carry out Pretreated spectra.Common preprocessing procedures
Have data smoothing, baseline correction, centralization, multiplicative scatter correction, standardization, derivative, Fourier transform and more than several sides
Method is used in combination.In addition, the effective information rate in signal Analysis, main method can be improved in spectrogram compression and information extraction
There are principal component analysis (PCA), wavelet analysis, simulated annealing (SAA), genetic algorithm (GA), moving window (MWPLS) etc..
One of the core technology of NIR and MIR spectrum analyses is to establish function between spectral information and component physicochemical property
Relationship establishes calibration model.The common analysis method of spectrum regression analysis has:Multiple linear regression (MLR), principal component regression
(PCR), Partial Least Squares returns (PLSR), artificial neural network (ANN), support vector machines (SVM) etc..MLR, PCR and
PLSR is chiefly used in solving linear correction problem, and ANN and SVM are chiefly used in solving the problems, such as gamma correction.
It yet there are no and utilize near-infrared (NIR) spectral detection soil δ13The report of C values.
Invention content
In view of the drawbacks described above of the prior art, the present invention provides a kind of new detection soil δ13The method of C values will solve
Certainly the technical issues of is quickly to detect soil δ using near-infrared (NIR) spectrum13C values.
To solve the above problems, the technical solution adopted by the present invention is that：It is a kind of to detect the steady of soil using near infrared spectrum
Determine the method for carbon isotope ratio, described method includes following steps：
1) the stable carbon isotope ratio of multiple calibration pedotheques is measured；
2) the diffusing reflection spectrogram of the near infrared band of acquisition calibration pedotheque, obtains original spectrogram；
3) original spectrogram is smoothly pre-processed, spectrogram after being handled；
4) Partial Least Squares is used to establish after the processing of calibration pedotheque between spectrogram and stable carbon isotope ratio
Causes；
5) the diffusing reflection spectrogram for acquiring the near infrared band of pedotheque to be measured calculates soil to be measured according to causes
The stable carbon isotope ratio of earth sample.
Preferably, in the step 1), the method for measuring the stable carbon isotope ratio of calibration pedotheque is to stablize
Isotope ratio mass spectrography.
Preferably, in the step 1), the specific steps for preparing calibration pedotheque include：After soil sample is removed water, mill
Carefully, 60 mesh sieve is crossed.
Preferably, in the step 1), multiple calibration pedotheques include the sample of Oe and Oa layers of soil.
Preferably, in the step 3), original spectrogram, which is carried out smooth pretreated specific steps, includes：The atmospheric background
Inhibit, absorbance conversion, automatic baseline correction and the processing of Norris first derivative filterings.
Preferably, in the step 4), the specific steps for establishing causes include：With SPXY methods respectively by light
Spectrum information and stable carbon isotope ratio are divided into calibration set and verification collects；Using Partial Least Squares, believe in calibration set spectrum
Principal component is extracted in breath, and 20 folding cross verifications is used in combination to choose best number of principal components, using the spectral information of calibration set as independent variable,
Using calibration set stable carbon isotope ratio as dependent variable, regression model is established；And the precision of regression model is examined using verification collection.
It is highly preferred that the ratio of the sample number of calibration set and verification collection is 3：1.It is highly preferred that the tool of the 20 folding cross verifications
Body step includes：By number of principal components f successively from 1 value to 20, for taking a fixed number of principal components, calibration set is divided into 20
Subset, each subset data is respectively used to do one-time authentication, while other 19 subset datas, for training, cross validation repeats
20 times, average 20 times as a result, finally obtaining the validation-cross root-mean-square error of a correspondence number of principal components.More preferably
Ground, the specific steps that the precision of inspection calibration model is collected with verification include：With the correction coefficient of determination, validation-cross root-mean-square error
Calibration model is evaluated with four prediction related coefficient, predicted root mean square error parameters.
Preferably, in the step 1), the specific steps for preparing pedotheque to be measured include：After soil sample is removed water, mill
Carefully, 60 mesh sieve is crossed.
Beneficial effects of the present invention are：1, this method can quick, accurate, easy, low price measurement soil δ 13C values.2、
Easy to operate, popularization is strong, has a wide range of application.3, it is suitable for the various ecosystems such as forest, farmland, meadow.
The technique effect of the design of the present invention, concrete structure and generation is described further below with reference to attached drawing, with
It is fully understood from the purpose of the present invention, feature and effect.
Description of the drawings
Fig. 1 be in the embodiment of the present invention 1 and 2 sample 6, Pinggu different depth soil near infrared absorption spectrogram.
Fig. 2 is that spectral model in the embodiment of the present invention 1 (including Oe and Oa) validation-cross difference number of principal components is corresponding
The schematic diagram of RMSECV values.
Fig. 3 is the schematic diagram of spectral model in the embodiment of the present invention 1 (including Oe and Oa) predicted value and actual value correlation.
Fig. 4 is that spectral model in the embodiment of the present invention 2 (not including Oe and Oa) validation-cross difference number of principal components is corresponding
RMSECV values.
Fig. 5 is the signal of spectral model in the embodiment of the present invention 2 (not including Oe and Oa) predicted value and actual value correlation
Figure.
Specific implementation mode
Specific implementation mode as one preferred, it is provided by the present invention quickly to detect soil using near infrared spectrum
The method of stable carbon isotope ratio includes the following steps.
(1) standby soil sample to be checked
It by the impurity elimination of mineral layer soil, air-dries, crushing, crosses 60 mesh sieve, drier saves backup；By Oe and Oa layers of soil (two
The different degrees of Litter leaf not decomposed completely of kind) 48h are dried in 60 DEG C to eliminate moisture, it crushes, crosses 60 mesh and sieve, drier preserves
It is spare.Totally 200 samples come from seven different regions (Pinggu, Hong Yashan, Bai An, Huang Zangyu, Xinyang, Mount Huang, the Yunshan Mountain)
The pedotheque of different depth (Oe, Oa, 0-2,2-5,5-10,10-20cm) in cork oak forest.
Sample preparation details：Forest soil sample is solid particle in irregular shape, size, shape and the uniformity coefficient of particle
All spectroscopic data is had a huge impact；By pulverizing and sieving, it can get smaller soil particle degree, increase the uniform of sample
Degree, reduce particle scattering effect as far as possible influences caused by spectra collection.
Two innovative points of the present invention：One, depth, general soil test will not all be added Oe and Oa layers, but more and more
Studies have shown that the Oe and Oa layers of important component because containing a large amount of soil organism and forest soil；Two, it adopts
Sample region, the sample that the present invention acquires come from 5 provinces on a latitudinal gradient, at a distance of 1500 kilometers from north to south, from north
The warm temperate zone in portion is gradually transitions the subtropical zone in south.
(2) δ of soil sample to be checked is measured using stable isotope ratio mass spectrography13C values
(3) spectra collection
The cross section that an internal diameter 11mm is placed on low-hydroxy-group squartz glass is the stainless steel cylinder of annular, to bottom
The white light penetrated up is unobstructed, and the 200mg soil samples accurately weighed are placed in it, then by a weight be 4g, diameter is also
The bottle of 11mm, is gently placed in soil sample, can make that thickness of sample is uniform, has enough dress sample depth and will not press too tight
Generate mirror-reflection.Using designed, designed of the present invention and the sample stage built, the diffusing reflection spectrogram of infrared band, instrument in acquisition
It is configured to：Fourier transformation infrared spectrometer, attachment are near-infrared integrating sphere, white light source, CaF2Beam splitter, InGaAs detections
Device；Acquisition parameter is：Using Jin Jing as background, scanning range 10000-4000cm-1, resolution ratio 4cm-1, scan 64 times.
Innovation about harvester：General extensive acquisition soil sample has fixed-size automatic sampling apparatus, but its
Instrument price and testing cost can be improved, and uses underaction.Based on practical angle, designed, designed of the present invention is simultaneously built
The irreflexive sample stage of pedotheque, purpose are mainly to maintain that thickness of sample is uniform, has enough dress sample depth and will not press
Tightly generate very much mirror-reflection.
(4) data prediction
Software Omnic 8.2 is carried by original spectrogram whole wave band (i.e. 10000-4000cm with instrument-1) carry out the air back of the body
Scape inhibits, and changes into absorption spectrum, then carry out automatic baseline correction.After spectroscopic data is imported software matlab7.8, Norris is used
(7,7,1) derivation exponential smoothing is handled, and first 7 indicates 7 points of smooth, second 7 expression, 7 differential widths, 1 expression one in bracket
Order derivative.Norris derivations smoothing processing can eliminate noise, be eliminated as much as unrelated information variable.
The pretreatment of pedotheque near infrared spectrum can efficiently reduce system deviation, noise, granularity and wave crest mistake
The influence of point etc..In some common preprocessing procedures, baseline drift is mainly eliminated in baseline correction；Smoothing processing master
If eliminating noise information；Derivative processing (first derivation or second order derivation) can effectively eliminate needle position misalignment, reduce peak and peak it
Between overlapping, obtain more effective informations；Multiplicative scatter correction is to eliminate solid particle size, surface scattering and light
Influences of the Cheng Bianhua to solid diffusing reflection spectrum.
The cross-reference of preprocess method not of the same race has its corresponding prediction model different improvement and influence, so,
The modelling effect for comparing Norris first derivatives filtering and Norris second dervative filterings herein also compares and adds
The modelling effect of multiplicative scatter correction and Norris first derivative filterings when being not added with multiplicative scatter correction.
(5) soil near infrared spectrum and δ are established using Partial Least Squares13Quantitative relationship between C values
By soil δ13C values are also introduced into matlab softwares.Test sample is pressed 3 with SPXY algorithms:1 ratio is respectively by light
Spectrum information and δ13C values are divided into calibration set and verification collects, and are respectively used to model foundation and verification.
The innovative point that the present invention is divided about sample set：Many researchs are all pre- around how to choose best spectrum when modeling
Processing method, the division methods of less relatively calibration set and verification collection, but the selection of calibration set and verification collection sample is more to spectrum
Meta analysis correction is most important.Common Method of Sample Selection includes mainly randomized (RS) and K-S (Kennard-Stone) at present
Method and SPXY (sample set partitioning based on joint x-y distance) method.Randomized randomness
Greatly, do not ensure that selected sample there are enough representativenesses；The big sample of SPECTRAL DIVERSITY is selected into calibration set by K-S methods,
Remaining sample is included into verification collection, but for the range that content is low or concentration is low, spectrum change very little between sample is often selected
Sample also do not have representativeness；SPXY algorithms are a kind of sample set selection methods based on statistical basis, with spectrum-physics and chemistry value
Symbiosis distance is used as foundation to ensure utmostly to characterize sample distribution, to improve model stability.The present invention is based on Norris
The spectrum of first derivative filtering processing, compares the effect of SPXY methods and K-S methods institute established model.
1. utilizing single dependent variable (δ in calibration set13C values) minimum two partially is carried out to more independents variable (mid-infrared light spectrum information)
Multiply (partial least squares method, PLS) regression modeling, basic process is：Master is extracted in spectral information
Ingredient t1 (t1 is the linear combination of spectral information), t 1 should carry the variation information in spectroscopic data as much as possible, and t1 and
δ13The degree of correlation of C values can reach maximum.After first principal component t1 is extracted, Partial Least Squares Regression implements spectrum letter
The recurrence to t 1 is ceased, if regression equation has reached satisfied precision, algorithm terminates；Otherwise, spectral information quilt will be utilized
Residual, information after t1 explanations and δ13Residual, information after C values are explained by t1 carries out the second Principle component extraction taken turns.It is so past
It is multiple, until can reach a relatively satisfactory precision.If being finally extracted m principal component t1, t2 ... altogether to spectral information,
Tm, Partial Least Squares Regression will be by implementing δ13Then C values are expressed as δ again to t1, the recurrence of t2 ..., tm13C values are about original
The regression equation of variable (i.e. spectral information).
2. in the analysis process, the present invention (ensures that model is preferable with the best number of principal components of 20 folding cross verifications selection
The quantity of principal component needed for precision).The parameter of " 20 folding method " is set as：To a certain number of principal components f (getting 20 from 1 successively),
Calibration set is divided into 20 groups (usually dividing equally), an individual subsample is kept as the data of verification model, other 19
A sample is used for training.Validation-cross is repeated 20 times, and the verification of each subsample and only verification are primary, average 20 results or
Using other combinations, the validation-cross root-mean-square error (RMSECV) of this corresponding number of principal components is finally obtained.RMSECV
It is worth smaller, illustrates that the predictive ability of model is better.RMSECV values are generally used to establish the method that principal component number is mapped best
Number of principal components, the corresponding number of principal components of RMSECV minimum points are usually best number of principal components.
Include spectrum as far as possible by Partial Least Squares extraction 3. using the infrared spectrum in calibration set as independent variable more
Information while and and δ13The principal component (number is determined by above-mentioned validation-cross) for the certain amount that C values are closely related, with δ13C
Value is dependent variable, establishes soil middle infrared spectrum and δ13Calibration model between C values.And the spectral information of individual authentication collection is substituted into
The model calculates δ13C values, by collecting actual measurement δ with verification13C values compare, testing model precision of prediction.
Model prediction ability and stability are by the correction coefficient of determination (R2), validation-cross root-mean-square error (RMSECV) and pre-
4 survey related coefficient (R), predicted root mean square error (RMSEP) parameters are evaluated, and good model should have two coefficient height
The feature low with two errors.In addition, it is possible to use prediction relation analysis error (Residual predictive
Deviation, RPD) model is carried out to go deep into evaluation；Think that model has preferable predictive ability when RPD values are more than 3, it can
With into the quantitative control of row index.Can substitute into the infrared information of the similar soil of unknown, property after model foundation is good should
In model, its δ is calculated13C values.
Determination about best number of principal components.The minimum point of RMSECV is not conventionally chosen, but is tried one by one
It tests, considers 4 parameters (paying close attention to RMSEP values).
The present invention acquires the atlas of near infrared spectra of cork oak forest soil (from different places and depth), to initial data
After carrying out series of preprocessing, in conjunction with the PLSR in Chemical Measurement, can it is accurate, quickly, it is easy, detect various soil at low cost
δ in earth13C values.
It is an advantage of the invention that：
(1) accurate.Correct coefficient of determination R2It is all higher than 0.96 with prediction related coefficient R, corrects root-mean-square error and prediction
Root-mean-square error is respectively less than 1.05, RPD and is more than 3.
(2) quickly.One sample collection only needs 3min, can acquire within one day at least 200 infrared spectrums, at subsequent data
Reason can be completed in 1h.
(3) easy to operate.Sample pre-treatments are simple, and instrumentation is simple.
(4) testing cost is low.Compared to stable isotope ratio mass spectrometer, infrared spectrometer is cheap.
(5) popularization is strong, easy to spread.Instrumentation is simple, and price is relatively cheap.
(6) applied widely, it cannot be only used for the detection of forest soil, it can also be used to other ecosystems such as farmland, grassland
System.
Soil of the embodiment 1 including Oe and Oa
(1) soil sample to be checked is prepared.It by the impurity elimination of mineral layer soil, air-dries, crushing, crosses 60 mesh sieve, drier saves backup；It will
Oe and Oa layers of soil dries 48h in 60 DEG C to eliminate moisture, crushes, and crosses 60 mesh sieve, and drier saves backup.Totally 199 samples come
It is different deep from the cork oak forest in seven different regions (Pinggu, Hong Yashan, Bai An, Huang Zangyu, Xinyang, Mount Huang, the Yunshan Mountain)
Spend the pedotheque of (Oe, Oa, 0-2,2-5,5-10,10-20cm), wherein 139, mineral layer soil, Oe and Oa layers of soil totally 60
It is a.
It is not improved using spectral model precision after multiplicative scatter correction pretreatment by table 1, it was demonstrated that sample preparation obtains
Preferably, reduce particle scattering effect as far as possible influences caused by spectra collection.
(2) δ of soil sample to be checked is measured using stable isotope ratio mass spectrography13C values.
(3) spectra collection.200mg soil samples are weighed, the cross section for being placed in 11mm is in the stainless steel column body of annular, and bottom is
Low-hydroxy-group squartz glass, sample top flatten.The diffusing reflection spectrogram of near infrared band is acquired, instrument configuration is：Fourier transform
Infrared spectrometer, attachment are near-infrared integrating sphere, white light source, CaF2Beam splitter, InGaAs detectors；Acquisition parameter is：With
Jin Jing is background, scanning range 10000-4000cm-1, resolution ratio 4cm-1, scan 64 times.By sample for Pinggu, attached drawing 1 is aobvious
The near-infrared spectrogram of 6 depth of soil is shown.
(4) data prediction.Software Omnic 8.2 is carried by original spectrogram whole wave band (i.e. 10000- with instrument
4000cm-1) the atmospheric background inhibition is carried out, absorption spectrum is changed into, then carry out automatic baseline correction.By the spectrum number of 199 samples
After importing software matlab7.8, the processing such as 7 points of smooth, first derivatives are carried out with Norris methods.
The embodiment has attempted 4 kinds of common pretreatments to the near infrared spectrum of pedotheque：1. Norris first derivatives
Filtering+SPXY methods divide calibration set and verification collects；2. multiplicative scatter correction+Norris first derivative filterings+SPXY
Method divides calibration set and verification collects；3. Norris second dervative filtering+SPXY methods divide calibration set and verification collects；④
Norris first derivative filtering+K-S methods divide calibration set and verification collects, and reapply offset minimum binary (PLS) method and establish soil
Earth δ13The quantitative estimation model of C values.As a result (table 1) shows that different pretreatments method is to built soil δ13C value estimation models
Precision of prediction has certain influence, and with preprocess method used by this patent, (Norris first derivative filtering+SPXY methods are drawn
Point calibration set and verification collect) spectrum modeling accuracy highest.
1 model preprocessing method of table and the common processing method prediction soil δ of partial least square model13C (including Oe and
Oa precision) compares
(5) soil near infrared spectrum and δ are established using Partial Least Squares13Quantitative relationship between C values.By corresponding 199
A soil δ13C values are also introduced into matlab softwares.Test sample is pressed 3 with SPXY algorithms:1 ratio respectively by spectral information and
δ13C values are divided into calibration set and verification collects, and calibration set contains 150 samples, and verification collection contains 49 samples.Using offset minimum binary
Method, it is that 11, RMSECV values are shown in attached drawing 2 to the mapping of principal component number to choose best number of principal components with 20 folding cross verifications.Complete
In spectral range soil near infrared spectrum and δ are established with training set13Regression model between C values, and by the spectrum of individual authentication collection
Information substitutes into the model and calculates δ13C values, by collecting actual measurement δ with verification13C values compare, testing model precision of prediction.Correction determines
Coefficient (R2) it is 0.9684, validation-cross root-mean-square error (RMSECV) is 0.9311；Prediction related coefficient (R) is 0.9631
(attached drawing 3), predicted root mean square error (RMSEP) are 0.5965.Predict that relation analysis error (RPD) is 3.74.
Pay attention to：By attached drawing 2 as it can be seen that when number of principal components is 12, root-mean-square error (RMSECV) minimum is mutually verified, is
0.9276；But corresponding prediction related coefficient (R) is 0.9536, predicted root mean square error (RMSEP) is 0.6691.And it is of the invention
By one by one experiment of the number of principal components from 1 to 20, it is best number of principal components to consider selection 11, its RMSECV is in all masters
Ranking is second from the bottom in ingredient, only bigger than 12, is 0.9311；But corresponding R is 0.9631, is maximum in all principal components,
And RMSEP is 0.5965, is minimum in all principal components.
Should the result shows that, this method is suitable for forest soil different depth (Oe, Oa, 0-2cm, 2-5cm, 5-10cm, 10-
δ in 20cm)13The detection of C values can quickly detect soil δ within a short period of time13C values, and satisfied accuracy of detection can be reached.
Meanwhile Norris first derivatives filtering and SPXY methods divide the preprocess methods such as data set and in PLS modelings how
Best number of principal components is chosen all to utilizing near-infrared diffusing reflection technology harmless quantitative detection soil δ13C plays an important role.Test mould
Nearly 200 samples in type are from the cork oak forest soil across two climate zones and five provinces, different weather conditions
Spectrum can be had an impact with soil property.But the model exactly established in such complex condition just has wider array of be applicable in
Range, therefore, the near-infrared spectrum technique based on Partial Least Squares are to be suitble to soil δ13The efficient detection technology of C detections.
Mineral layer soil of the embodiment 2 not including Oe and Oa
(1) soil sample to be checked is prepared.It by the impurity elimination of mineral layer soil, air-dries, crushing, crosses 60 mesh sieve, drier saves backup.Altogether
The cork oak that 139 samples come from seven different regions (Pinggu, Hong Yashan, Bai An, Huang Zangyu, Xinyang, Mount Huang, the Yunshan Mountain) is gloomy
The mineral layer pedotheque of different depth (0-2,2-5,5-10,10-20cm) in woods.
It is not improved using spectral model precision after multiplicative scatter correction pretreatment by table 2, it was demonstrated that sample preparation obtains
Preferably, reduce particle scattering effect as far as possible influences caused by spectra collection.
(2) δ of soil sample to be checked is measured using stable isotope ratio mass spectrography13C values.
(3) spectra collection.200mg soil samples are weighed, the cross section for being placed in 11mm is in the stainless steel column body of annular, and bottom is
Low-hydroxy-group squartz glass, sample top flatten.The diffusing reflection spectrogram of near infrared band is acquired, instrument configuration is：Fourier transform
Infrared spectrometer, attachment are near-infrared integrating sphere, white light source, CaF2Beam splitter, InGaAs detectors；Acquisition parameter is：With
Jin Jing is background, scanning range 10000-4000cm-1, resolution ratio 4cm-1, scan 64 times.By sample for Pinggu, attached drawing 1 is aobvious
The near-infrared spectrogram of 4 depth of soil is shown.
(4) data prediction.Software Omnic 8.2 is carried by original spectrogram whole wave band (i.e. 10000- with instrument
4000cm-1) the atmospheric background inhibition is carried out, absorption spectrum is changed into, then carry out automatic baseline correction.By the spectrum number of 139 samples
After importing software matlab7.8, the processing such as 7 points of smooth, first derivatives are carried out with Norris methods.
The embodiment has attempted 4 kinds of common pretreatments to the near infrared spectrum of pedotheque：1. Norris first derivatives
Filtering+SPXY methods divide calibration set and verify collection, 2. multiplicative scatter correction+Norris first derivatives filtering+SPXY
Method divides calibration set and verification collection, 3. Norris second dervatives filtering+SPXY methods divide calibration set and verification collects, 4.
Norris first derivative filtering+K-S methods divide calibration set and verification collects, and reapply offset minimum binary (PLS) method and establish soil
Earth δ13The quantitative estimation model of C values.As a result (table 2) shows that different pretreatments method is to built soil δ13C value estimation models
Precision of prediction has certain influence, and with preprocess method used by this patent, (Norris first derivative filtering+SPXY methods are drawn
Point calibration set and verification collect) spectrum modeling accuracy highest.
2 model preprocessing methods of table and the common processing method prediction soil δ of partial least square model13C (does not include Oe
And Oa) precision compare
(5) soil near infrared spectrum and δ are established using Partial Least Squares13Quantitative relationship between C values.By corresponding 139
A soil δ13C values are also introduced into matlab softwares.Test sample is pressed 3 with SPXY algorithms:1 ratio respectively by spectral information and
δ13C values are divided into calibration set and verification collects, and calibration set contains 105 samples, and verification collection contains 34 samples.Using offset minimum binary
Method, it is that 12, RMSECV values are shown in attached drawing 4 to the mapping of principal component number to choose best number of principal components with 20 folding cross verifications.Complete
In spectral range soil near infrared spectrum and δ are established with calibration set13Regression model between C values, and by the spectrum of individual authentication collection
Information substitutes into the model and calculates δ13C values, by collecting actual measurement δ with verification13C values compare, testing model precision of prediction.Correction determines
Coefficient (R2) it is 0.9866, validation-cross root-mean-square error (RMSECV) is 1.0213；Prediction related coefficient (R) is 0.9753
(attached drawing 5), predicted root mean square error (RMSEP) are 0.5705.Predict that relation analysis error (RPD) is 4.38.
Should the result shows that, this method is suitable for the forest soil of different depth (0-2cm, 2-5cm, 5-10cm, 10-20cm)
Middle δ13The detection of C values can quickly detect soil δ within a short period of time13C values, and satisfied accuracy of detection can be reached.This hair
It is bright that near infrared band modeling is acquired by homemade sample stage, achieve extraordinary effect.Meanwhile Norris first derivatives
Filtering and SPXY methods divide the preprocess methods such as data set and how to choose best number of principal components in PLS modelings all right
Utilize near-infrared diffusing reflection technology harmless quantitative detection soil δ13C plays an important role.139 samples in test model come from across
The more cork oak forest soil of two climate zones and five provinces, different weather conditions and soil property can generate spectrum
It influences.But the model exactly established in such complex condition just has the wider array of scope of application, therefore, is based on offset minimum binary
The near-infrared spectrum technique of method is to be suitble to soil δ13The efficient detection technology of C detections.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be in the protection domain being defined in the patent claims.
Claims (6)
1. a kind of method for the stable carbon isotope ratio detecting soil using near infrared spectrum, which is characterized in that the method
Include the following steps：
1) the stable carbon isotope ratio of multiple calibration pedotheques is measured；
2) the diffusing reflection spectrogram of the near infrared band of acquisition calibration pedotheque, obtains original spectrogram；
3) original spectrogram is smoothly pre-processed, spectrogram after being handled；
4) Partial Least Squares is used to establish quantifying between spectrogram and stable carbon isotope ratio after the processing of calibration pedotheque
Relational model；
5) the diffusing reflection spectrogram for acquiring the near infrared band of pedotheque to be measured calculates soil-like to be measured according to causes
The stable carbon isotope ratio of product；
Wherein,
In step 4), the specific steps for establishing the causes include：With SPXY methods respectively by spectral information and institute
It states stable carbon isotope ratio and is divided into calibration set and verification collection；Using Partial Least Squares, in the calibration set spectral information
Middle extraction principal component is used in combination 20 folding cross verifications to choose best number of principal components, is with the spectral information of the calibration set
Independent variable establishes regression model using the stable carbon isotope ratio of the calibration set as dependent variable；And utilize the verification
Collection examines the precision of regression model；
The ratio of the sample number of the calibration set and the verification collection is 3：1；
The specific steps of the 20 folding cross verification include：By number of principal components f successively from 1 value to 20, for taking fixed one
The calibration set is divided into 20 subsets by a number of principal components, and each subset data is respectively used to do one-time authentication, while its
For training, cross validation is repeated 20 times for his 19 subset datas, average 20 times as a result, finally obtaining a corresponding institute
State the validation-cross root-mean-square error of number of principal components；
Include with the specific steps for verifying the precision that collection inspection corrects the regression model：With the correction coefficient of determination, interaction
Verification root-mean-square error and four prediction related coefficient, predicted root mean square error parameters evaluate calibration model.
2. the method as described in claim 1, which is characterized in that in the step 1), measure the stabilization of calibration pedotheque
The method of carbon isotope ratio is stable isotope ratio mass spectrography.
3. the method as described in claim 1, which is characterized in that in the step 1), prepare the specific of calibration pedotheque
Step includes：It is levigate after soil sample is removed water, cross 60 mesh sieve.
4. the method as described in claim 1, which is characterized in that in the step 1), multiple calibration pedotheques
Include the sample of Oe and Oa layers of soil.
5. the method as described in claim 1, which is characterized in that in the step 3), original spectrogram is carried out smooth pre- place
The specific steps of reason include：The atmospheric background inhibits, absorbance conversion, automatic baseline correction and Norris first derivative filterings
Processing.
6. the method as described in claim 1, which is characterized in that in the step 1), prepare the specific of pedotheque to be measured
Step includes：It is levigate after soil sample is removed water, cross 60 mesh sieve.
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