CN107884346A - A kind of Overlapped spectral line separation method based on MPT spectroscopic datas - Google Patents
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Abstract
A kind of Overlapped spectral line separation method based on MPT spectroscopic datas, including step：Overlapped spectra data to be analyzed are selected, the characteristic of spectral line to be separated is estimated in overlapped spectra data, characteristic includes peak-peak I, peak wavelength λ and half-peak breadth σ, and effective analyzed area corresponding to the fitting peak-peak I；Object function is built based on MPT spectrum mathematical modeling, and matching is optimized in the characteristic that separation spectral line is effectively treated in analyzed area using object function, obtains optimal separation spectral line；The spectroscopic data that overlapped spectra data are subtracted to optimal separation spectral line obtains next overlapped spectra data to be analyzed.During so that MPT spectrometers carrying out sample analysis, directly qualitative and quantitative analysis can be carried out using the data in overlapping peak shape region, so that the analytical performance of MPT spectrometers, and MPT spectrometers have obtained significantly being lifted to the detectability and accuracy of detection of COMPLEX MIXED sample.
Description
Technical field
The present invention relates to Atomic Emission Spectral Analysis technical field, and in particular to a kind of based on the overlapping of MPT spectroscopic datas
Spectral line separation method.
Background technology
MPT spectrometers are made up of light-source system and spectrum data gathering analysis system, and light-source system is to be measured for inspiring
The characteristic spectrum of element in sample；Spectra collection analysis system is used to gather the elemental characteristic spectrum letter that light-source system inspires
Breath, the qualitative or quantitative analysis of element in sample is then carried out using characteristic spectrum information.Each component of sample to be analysed exists
The separation on different wave length position on spectrogram is completed by the beam splitting system in spectrum data gathering analysis system, but by
It is limited in the resolution capability of hardware device, cause the spectral peak of the very close element spectral line of many wavelength can not complete to separate,
The resultant peak form that multiple peak overlaps are formed is shown as in the characteristic spectrum data collected, is unfavorable for follow-up sample size
Change analysis.
Therefore, it is generally the case that, can not be direct because overlapping peak data is combined by the spectral peak of a plurality of element spectral line
Use, so when carrying out sample analysis using MPT spectrometers, the spectral line using overlapping peak shape region can be avoided as far as possible, this is just
So that many times, the spectral line for selecting element emissive porwer to be measured stronger is abandoned to avoid overlap peak, and it have selected element
The weaker spectral line of emissive porwer, cause accuracy of detection and accuracy of the instrument to sample.Especially COMPLEX MIXED sample is entered
During row analysis, the sample pre-treatments of complexity are first carried out, even if after pre-treatment, also usually because selectable emissive porwer is stronger
And spectral line without overlap of peaks is less or does not have, and causes instrument inadequate to the accuracy of detection of sample and the degree of accuracy, or even can not be to sample
Product carry out quantitative detection.
The content of the invention
The application provides a kind of Overlapped spectral line separation method based on MPT spectroscopic datas, including step：
Overlapped spectra data to be analyzed are selected, the overlapped spectra data are expressed as { X, Y }, wherein X={ λ0, λ1,
λi…λn, Y={ I0, I1, Ii…In, i=0,1,2 ... n, i are the sequence number of overlapping spectroscopic data, and n is of overlapping spectroscopic data
Number, λiFor the peak wavelength of i-th of spectral line, IiFor the spectral intensity values of i-th of spectral line；
The characteristic of spectral line to be separated is estimated in overlapped spectra data, characteristic includes peak-peak I, peak value ripple
Long λ and half-peak breadth σ, and effective analyzed area corresponding to fitting peak-peak I；
Object function is built based on MPT spectrum mathematical modeling, and treated in effective analyzed area using object function point
The characteristic of line of going against accepted conventions optimizes matching, obtains optimal separation spectral line；
The spectroscopic data that overlapped spectra data are subtracted to the optimal separation spectral line obtains next overlapping light to be analyzed
Modal data.
In a kind of embodiment, the characteristic of spectral line to be separated is estimated, including：
Peak-peak I is the maximum of spectral intensity values in institute's ribose overlapped spectra data, I=max { Y }；
Peak wavelength λ is wavelength value corresponding to the peak-peak I；
Half-peak breadth σ calculation formula is：
Wherein, Δ λ1=| λi- λ |, Δ λ2=| λ2- λ |, I1It is left for peak-peak I
Side, meetAnd min (λ-λi) condition intensity level；I2On the right side of peak-peak I, to meetAnd min
(λi- λ) condition intensity level, λ1For I1Corresponding wavelength value；λ2For I2Corresponding wavelength value.
In a kind of embodiment, effective analyzed area corresponding to peak-peak I is fitted, including：
Effective analyzed area left margin l is to meet λi＜ λ, and, Ii-1≥Ii, and min (λi- λ) condition wavelength value；
Effective analyzed area right margin r is to meet λi＜ λ and, Ii-1≥Ii, and min (λi- λ) condition wavelength value.
In a kind of embodiment, MPT spectrum mathematical modelings are：
Wherein, i be overlapping spectroscopic data sequence number, P (λi) it is in wavelength XiLocate the intensity level of overlapped spectra, M is composition weight
The spectral peak number of folded spectrum, j are spectral peak sequence number, Ij(λi) it is in wavelength XiLocate the intensity level of the spectral peak of jth, I is that the maximum of spectral peak is strong
Angle value, λ are wavelength value corresponding to spectral peak maximum intensity value I, and σ is the half-peak breadth of spectral peak, and μ is proportionality coefficient.
In a kind of embodiment, object function is：
Wherein, i be spectroscopic data sequence number, P (λi) it is in wavelength XiLocate the intensity level of overlapped spectra, Ij(λi) it is in ripple
Long λiLocate the intensity level of the spectral peak of jth, n is the number of spectroscopic data in effective analyzed area.
In a kind of embodiment, the spectroscopic data acquisition that the overlapped spectra data are subtracted to the optimal separation spectral line is next
Individual overlapped spectra data to be analyzed, calculation formula are：
P(λi)=P (λi)-Ij(λi)；
Wherein, P (λi) it is in wavelength XiLocate the intensity level of the overlapped spectra data of remaining spectral line, P (λi) it is in wavelength XiPlace
The intensity level of overlapped spectra data, Ij(λi) it is in wavelength XiLocate the intensity level of the separation spectral line data of jth.
According to the Overlapped spectral line separation method of above-described embodiment, each spectral peak to overlap is separated, based on MPT
Spectrum mathematical modeling and objective function optimization obtain the independent peak shape and Correlated Spectroscopy peak data of each spectral peak, it is can be used for sample
Each component qualitative and quantitative analysis so that MPT spectrometers carry out sample analysis when, can directly use overlapping peak shape area
The data in domain carry out qualitative and quantitative analysis, increase the range of choice of the optimal spectral line of element during sample analysis, reduce
MPT spectrometers carry out sample pre-treatments complexity during complex sample analysis, improve sample analysis efficiency, save sample point
Cost is analysed, due to which reducing the selectional restriction of the optimal spectral line of element in sample analysis so that the analytical performance of instrument, Yi Jiyi
Device has obtained significantly being lifted to the detectability and accuracy of detection of COMPLEX MIXED sample.
Brief description of the drawings
Fig. 1 is Overlapped spectral line separation process figure；
Fig. 2 is the overlapping peak shape schematic diagram of overlapped spectra data to be analyzed；
Fig. 3 is separation spectral line schematic diagram；
Fig. 4 is the overlapping peak shape schematic diagram of remaining overlapped spectra data；
Fig. 5 is that overlapping spectroscopic data separates schematic diagram.
Embodiment
The present invention is described in further detail below by embodiment combination accompanying drawing.
The present invention obtains the independent peak shape and phase of each spectral peak by being separated Overlapped spectral line based on MPT spectroscopic datas
Spectral peak data are closed, it is can be used for the qualitative and quantitative analysis of each component of sample, so as to improve MPT spectrometers to complexity
The detectability and accuracy of detection of biased sample.
The Overlapped spectral line separation method based on MPT spectroscopic datas that this example provides specifically includes following steps, its flow chart
As shown in Figure 1.
S1：Select overlapped spectra data to be analyzed.
Overlapped spectra data are expressed as { X, Y }, wherein X={ λ0, λ1, λi…λn, Y={ I0, I1, Ii…In, i=0,1,
2...n, i be overlapping spectroscopic data sequence number, n be overlapping spectroscopic data number, λiFor the peak wavelength of i-th of spectral line, IiFor
The spectral intensity values of i-th of spectral line.
S2：Estimate the characteristic of spectral line to be separated in overlapped spectra data, characteristic include peak-peak/, peak
It is worth wavelength X and half-peak breadth σ, and effective analyzed area corresponding to fitting peak-peak I.
The evaluation method of each parameter is as follows in this example：
Peak-peak I is the maximum of spectral intensity values in overlapping spectroscopic data, and I=max { Y }, Y are overlapping light to be analyzed
Spectral intensity value set in modal data；
Peak wavelength λ is wavelength value corresponding to peak-peak I；
Half-peak breadth σ calculation formula is：
Wherein, Δ λ1=| λ1- λ |, Δ λ2=| λ2- λ |, I1It is left for peak-peak I
Side (refers to λi＜ λ spectroscopic data section), meetAnd min (λ-λi) condition intensity level；I2It is right for peak-peak I
Side (refers to λi＞ λ spectroscopic data section), meetAnd min (λi- λ) condition intensity level, λ1For I1Corresponding ripple
Long value；λ2For I2Corresponding wavelength value.
Effective analyzed area corresponding to peak-peak I is fitted, is specially：
Effective analyzed area left margin l is to meet λi＜ λ, and, Ii-1≥Ii, and min (λi- λ) condition wavelength value；
Effective analyzed area right margin r is to meet λi＜ λ and, Ii-1≥Ii, and min (λi- λ) condition wavelength value；
Effective analyzed area is determined according to left margin l and right margin r.
S3：Object function is built based on MPT spectrum mathematical modeling, and treated using object function in effective analyzed area
The characteristic of separation spectral line optimizes matching, obtains optimal separation spectral line.
Specifically, MPT spectrum mathematical modelings are as follows：
Wherein, i be overlapping spectroscopic data sequence number, P (λi) it is in wavelength XiLocate the intensity level of overlapped spectra, M is composition weight
The spectral peak number of folded spectrum, j are spectral peak sequence number, Ij(λi) it is in wavelength XiLocate the intensity level of the spectral peak of jth, I is that the maximum of spectral peak is strong
Angle value, λ are wavelength value corresponding to spectral peak maximum intensity value I, and σ is the half-peak breadth of spectral peak, and μ is proportionality coefficient.
The object function of optimization is as follows：
Wherein, i be spectroscopic data sequence number, P (λi) it is in wavelength XiLocate the intensity level of overlapped spectra, Ij(λi) it is in ripple
Long λiLocate the intensity level of the spectral peak of jth, n is the number of spectroscopic data in effective analyzed area.
The characteristic for treating separation spectral line in effective analyzed area using the object function optimizes matching, obtains
Optimal separation spectral line
S4：The spectroscopic data that overlapped spectra data are subtracted to optimal separation spectral line obtains next overlapped spectra to be analyzed
Data.
Specific formula for calculation is as follows：
P(λi) '=P (λi)-Ij(λi)；
Wherein, P (λi) ' be is in wavelength XiLocate the intensity level of the overlapped spectra data of remaining spectral line, P (λi) it is in wavelength Xi
Locate the intensity level of overlapped spectra data, Ij(λi) it is in wavelength XiLocate the intensity level of the separation spectral line data of jth.
S4：Repeat step S2-S4, until the maximum intensity value of overlapped spectra data to be analyzed is less than under presetting peak value
It is limited to stop, terminates and continue spectral line separation.
Below with the overlap peak shape in overlapped spectra data to be analyzed as shown in Fig. 2 dividing above-mentioned steps S2-S4 spectral line
Illustrated from process.
1) peak-peak I, peak value ripple are obtained to overlapped spectra data preresearch estimates to be analyzed in Fig. 2 according to above-mentioned steps S2
Long λ and half-peak breadth σ, and the left margin l and right margin r of effective analyzed area corresponding to fitting peak-peak I, specifically：
Peak-peak I is the maximum of spectral intensity values in overlapping spectroscopic data, I=max { Y }, is computed, peak-peak
I=109262；
Peak wavelength λ is wavelength value corresponding to peak-peak I, and it is 228.8012nm to be computed λ；
It is 0.0024nm that ingeniously σ, which is calculated, according to above-mentioned calculation formula in half-peak breadth；
The condition met according to left margin l, it is 228.7508nm that l, which is calculated,；
The condition met according to right margin r, it is 228.8156nm that r, which is calculated,.
2) object function in above-mentioned steps S3 optimizes matching to the parameter estimated in 1), optimizes obtained knot
Fruit is as follows：
I=109262；
λ=228.8016nm；
σ=0.0013nm；
μ=0.1995；
The spectral line that this is separated according to above-mentioned optimum results is as shown in Figure 3.
3) spectral line data obtained in 2) is separated from overlapped spectra data to be analyzed according to step S4, obtained
The overlapped spectra of remaining spectral line is as shown in Figure 4.
4) 1) -3 are repeated), until the maximum intensity value of overlapped spectra data to be analyzed is less than presetting peak value lower limit
Only, the peak value lower limit of this example is set to 2500, and overlapped spectra data to be analyzed are finally separating as 4 spectral line peaks, 4 spectrums in the Fig. 2 of side
The optimum results at line peak are as shown in the table：
The peak shape of 4 spectral lines is as shown in figure 5, by inquiring about MPT spectral lines storehouse, it may be determined that element corresponding to 4 spectral line peaks
Respectively：228.8016nm is Cd elements, and 228.8694nm is W elements, and 228.8375nm is Ni elements, 228.9067nm Zn
Element, essence is carried out to the content of these four elements in sample using above-mentioned isolated each MPT mathematical modelings information can
Really analysis.
When the Overlapped spectral line separation method of this example make it that MPT spectrometers carry out sample analysis, overlap peak can be directly used
The data in shape region carry out qualitative and quantitative analysis, increase the range of choice of the optimal spectral line of element during sample analysis.Drop
Low MPT spectrometers carry out sample pre-treatments complexity during complex sample analysis, improve sample analysis efficiency, save sample
Product analysis cost.Due to which reducing the selectional restriction of the optimal spectral line of element in sample analysis so that MPT spectrometers it is analytical
Energy, and MPT spectrometers have obtained significantly being lifted to the detectability and accuracy of detection of COMPLEX MIXED sample.
Use above specific case is illustrated to the present invention, is only intended to help and is understood the present invention, not limiting
The system present invention.For those skilled in the art, according to the thought of the present invention, can also make some simple
Deduce, deform or replace.
Claims (6)
1. a kind of Overlapped spectral line separation method based on MPT spectroscopic datas, it is characterised in that including step：
Overlapped spectra data to be analyzed are selected, the overlapped spectra data are expressed as { X, Y }, wherein X={ λ0, λ1, λi…λn,
Y={ I0, I1, Ii…In, i=0,1,2 ... n, i be overlapping spectroscopic data sequence number, n be overlapping spectroscopic data number, λiFor
The peak wavelength of i-th of spectral line, IiFor the spectral intensity values of i-th of spectral line；
The characteristic of spectral line to be separated is estimated in the overlapped spectra data, the characteristic includes peak-peak I, peak
It is worth wavelength X and half-peak breadth σ, and effective analyzed area corresponding to the fitting peak-peak I；
Object function is built based on MPT spectrum mathematical modeling, and utilizes the object function right in effective analyzed area
The characteristic of the spectral line to be separated optimizes matching, obtains optimal separation spectral line；
The spectroscopic data that the overlapped spectra data are subtracted to the optimal separation spectral line obtains next overlapping light to be analyzed
Modal data.
2. Overlapped spectral line separation method as claimed in claim 1, it is characterised in that the characteristic of the estimation spectral line to be separated
According to, including：
The peak-peak I be the overlapped spectra data in spectral intensity values maximum, I=max { Y }；
The peak wavelength λ is wavelength value corresponding to the peak-peak I；
The calculation formula of the half-peak breadth σ is：
Wherein, Δ λ1=| λ1- λ |, Δ λ2=| λ2- λ |, I1For on the left of peak-peak I,
MeetAnd min (λ-λi) condition intensity level；I2On the right side of peak-peak I, to meetAnd min (λi-
λ) the intensity level of condition, λ1For I1Corresponding wavelength value；λ2For I2Corresponding wavelength value.
3. Overlapped spectral line separation method as claimed in claim 1, it is characterised in that corresponding to the fitting peak-peak I
Effective analyzed area, including：
Effective analyzed area left margin l is to meet λi＜ λ, and, Ii-1≥Ii, and min (λi- λ) condition wavelength value；
Effective analyzed area right margin r is to meet λi＜ λ and, Ii-1≥Ii, and min (λi- λ) condition wavelength value.
4. Overlapped spectral line separation method as claimed in claim 1, it is characterised in that the MPT spectrum mathematical modeling is：
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Wherein, i be overlapping spectroscopic data sequence number, P (λi) it is in wavelength XiLocate the intensity level of overlapped spectra, M is the overlapping light of composition
The spectral peak number of spectrum, j are spectral peak sequence number, Ij(λi) it is in wavelength XiLocate the intensity level of the spectral peak of jth, I is the maximum intensity of spectral peak
Value, λ are wavelength value corresponding to spectral peak maximum intensity value I, and σ is the half-peak breadth of spectral peak, and μ is proportionality coefficient.
5. Overlapped spectral line separation method as claimed in claim 4, it is characterised in that the object function is：
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Wherein, i be spectroscopic data sequence number, P (λi) it is in wavelength XiLocate the intensity level of overlapped spectra, Ij(λi) it is in wavelength XiPlace
The intensity level of the spectral peak of jth, n are the number of spectroscopic data in effective analyzed area.
6. Overlapped spectral line separation method as claimed in claim 5, it is characterised in that subtract the overlapped spectra data described
The spectroscopic data of optimal separation spectral line obtains next overlapped spectra data to be analyzed, and calculation formula is：
P(λi) '=P (λi)-Ij(λi)；
Wherein, P (λi) ' be is in wavelength XiLocate the intensity level of the overlapped spectra data of remaining spectral line, P (λi) it is in wavelength XiLocate overlapping
The intensity level of spectroscopic data, Ij(λi) it is in wavelength XiLocate the intensity level of the separation spectral line data of jth.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112461770A (en) * | 2020-11-17 | 2021-03-09 | 山东省科学院海洋仪器仪表研究所 | Method for acquiring performance of spectrometer |
| CN113607867A (en) * | 2021-07-23 | 2021-11-05 | 清华大学合肥公共安全研究院 | Dual-fold-spectrum peak analysis method based on peak body mapping |
| CN113607867B (en) * | 2021-07-23 | 2024-06-11 | 清华大学合肥公共安全研究院 | Double-overlap spectrum peak analysis method based on peak body mapping |
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| CN112461770A (en) * | 2020-11-17 | 2021-03-09 | 山东省科学院海洋仪器仪表研究所 | Method for acquiring performance of spectrometer |
| CN112461770B (en) * | 2020-11-17 | 2022-11-29 | 山东省科学院海洋仪器仪表研究所 | Method for acquiring performance of spectrometer |
| CN113607867A (en) * | 2021-07-23 | 2021-11-05 | 清华大学合肥公共安全研究院 | Dual-fold-spectrum peak analysis method based on peak body mapping |
| CN113607867B (en) * | 2021-07-23 | 2024-06-11 | 清华大学合肥公共安全研究院 | Double-overlap spectrum peak analysis method based on peak body mapping |
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