CN107884346B - Overlapping spectral line separation method based on MPT spectral data - Google Patents
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Abstract
An overlapping spectral line separation method based on MPT spectral data comprises the following steps: selecting overlapped spectrum data to be analyzed, estimating characteristic data of a spectral line to be separated in the overlapped spectrum data, wherein the characteristic data comprises a maximum peak value I, a peak value wavelength lambda and a half peak width sigma, and fitting an effective analysis area corresponding to the maximum peak value I; constructing an objective function based on the MPT spectrum mathematical model, and performing optimization matching on the characteristic data of the spectral line to be separated in the effective analysis area by using the objective function to obtain an optimal separation spectral line; and subtracting the spectral data of the optimal separation spectral line from the overlapped spectral data to obtain the overlapped spectral data to be analyzed next. When the MPT spectrometer carries out sample analysis, the data of the overlapped peak-shaped area can be directly used for qualitative and quantitative analysis, so that the analysis performance of the MPT spectrometer, and the detection capability and the detection precision of the MPT spectrometer on complex mixed samples are greatly improved.
Description
Technical Field
The invention relates to the technical field of atomic emission spectroscopy analysis, in particular to an overlapping spectral line separation method based on MPT spectral data.
Background
The MPT spectrometer consists of a light source system and a spectrum data acquisition and analysis system, wherein the light source system is used for exciting a characteristic spectrum of elements in a sample to be tested; the spectrum acquisition and analysis system is used for acquiring element characteristic spectrum information excited by the light source system and then performing qualitative or quantitative analysis on elements in the sample by using the characteristic spectrum information. The separation of each component of the sample to be analyzed on different wavelength positions on the spectrogram is completed by a light splitting system in the spectral data acquisition and analysis system, but due to the limited resolving power of hardware equipment, the spectral peaks of a plurality of element spectral lines with very close wavelengths cannot be separated, and the acquired characteristic spectral data shows a combined peak form formed by overlapping a plurality of spectral peaks, which is not beneficial to the subsequent quantitative analysis of the sample.
Therefore, in general, since the overlapping peak data is formed by combining the peaks of a plurality of element spectral lines and cannot be directly used, when the MPT spectrometer is used for analyzing a sample, the spectral lines in an overlapping peak-shaped area are avoided as much as possible, so that many times, the spectral lines with strong emission intensity of the elements to be detected are abandoned to avoid the overlapping peaks, and the spectral lines with weak emission intensity of the elements are selected, so that the detection precision and accuracy of the instrument for the sample are reduced. Especially, when a complex mixed sample is analyzed, complex sample pretreatment is required to be carried out firstly, and even after pretreatment, the detection precision and accuracy of the instrument on the sample are not enough or even the sample cannot be quantitatively detected due to the fact that selective emission intensity is strong and few or no peak overlapping spectral lines exist.
Disclosure of Invention
The application provides an overlapping spectral line separation method based on MPT spectral data, which comprises the following steps:
overlapping spectral data to be analyzed, denoted as { X, Y }, where X ═ λ, { λ }, is selected0，λ1，λi…λn}，Y＝{I0，I1，Ii…InWhere i is 0, 1, 2 … n, i is the number of the superimposed spectrum data, n is the number of the superimposed spectrum data, λiIs the peak wavelength, I, of the ith lineiThe spectral intensity value of the ith spectral line;
estimating characteristic data of spectral lines to be separated in the overlapped spectral data, wherein the characteristic data comprises a maximum peak value I, a peak value wavelength lambda and a half-peak width sigma, and an effective analysis area corresponding to the fitted maximum peak value I;
constructing a target function based on an MPT (Multi-point Transmission test) spectrum mathematical model, and performing optimization matching on the characteristic data of the spectral line to be separated in an effective analysis area by using the target function to obtain an optimal separation spectral line;
and subtracting the spectral data of the optimal separation spectral line from the overlapped spectral data to obtain the overlapped spectral data to be analyzed next.
In one embodiment, estimating the characteristic data of the spectral line to be separated comprises:
the maximum peak value I is the maximum value of the spectral intensity values in the ribose overlapped spectral data, and I is max { Y };
the peak wavelength lambda is a wavelength value corresponding to the maximum peak value I;
the formula for calculating the half-peak width σ is:
In one embodiment, fitting the effective analysis area corresponding to the maximum peak I includes:
the left boundary l of the effective analysis region satisfies lambdai< lambda, and, Ii-1≥IiAnd min (λ)i- λ) a wavelength value of the condition;
the right boundary r of the effective analysis region is lambdai< λ and, Ii-1≥IiAnd min (λ)i- λ) the wavelength value of the condition.
In one embodiment, the MPT spectral mathematical model is:
where i is the number of the overlapped spectrum data, P (λ)i) At a wavelength λiIntensity value of the overlapped spectrum, M is the number of spectral peaks constituting the overlapped spectrum, j is the number of spectral peaks, Ij(λi) At a wavelength λiThe intensity value of the spectral peak at the j-th position, I is the maximum intensity value of the spectral peak, and lambda is the maximum intensity value of the spectral peakThe wavelength value corresponding to the large intensity value I, sigma is the half-peak width of the spectrum peak, and mu is a proportionality coefficient.
In one embodiment, the objective function is:
wherein i is the serial number of the spectral data, P (lambda)i) At a wavelength λiAt the intensity values of the overlapping spectra, Ij(λi) At a wavelength λiThe intensity value of the spectral peak at the j-th position, and n is the number of the spectral data in the effective analysis area.
In one embodiment, the spectral data of the optimal separation spectral line is subtracted from the overlapped spectral data to obtain the overlapped spectral data to be analyzed, and the calculation formula is:
P(λi)＝P(λi)-Ij(λi)；
wherein, P (lambda)i) At a wavelength λiIntensity value of the overlapping spectral data of the remaining spectral lines, P (lambda)i) At a wavelength λiAt intensity values of the overlapping spectral data, Ij(λi) At a wavelength λiThe intensity value of the separation line data at jth.
According to the method for separating overlapped spectral lines in the embodiment, the overlapped spectral lines are separated, and independent peak shapes and related spectral peak data of the spectral peaks are obtained based on an MPT (Multi-point Transmission test) spectral mathematical model and objective function optimization, so that the method can be used for qualitative and quantitative analysis of each component of a sample, and when an MPT spectrometer performs sample analysis, can directly use the data of the overlapped peak-shaped area to carry out qualitative and quantitative analysis, increases the selection range of the optimal element spectral line in the sample analysis process, reduces the sample pretreatment complexity when the MPT spectrometer carries out complex sample analysis, improves the sample analysis efficiency, saves the sample analysis cost, because the selection limit of the element optimal spectral line in sample analysis is reduced, the analysis performance of the instrument is ensured, and the detection capability and the detection precision of the instrument on the complex mixed sample are greatly improved.
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FIG. 1 is a flow chart of overlapping spectral line separation;
FIG. 2 is a schematic diagram of overlapping peak shapes of overlapping spectral data to be analyzed;
FIG. 3 is a schematic diagram of the separation lines;
FIG. 4 is a schematic illustration of overlapping peak shapes of the remaining overlapping spectral data;
FIG. 5 is a schematic diagram of the separation of overlapping spectral data.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
The invention separates the overlapped spectral lines based on the MPT spectral data to obtain the independent peak shape and the related spectral peak data of each spectral peak, so that the method can be used for qualitative and quantitative analysis of each component of a sample, thereby improving the detection capability and the detection precision of the MPT spectrometer on a complex mixed sample.
The method for separating overlapped spectral lines based on MPT spectral data provided in this example specifically includes the following steps, and a flowchart thereof is shown in fig. 1.
S1: overlapping spectral data to be analyzed are selected.
The overlaid spectral data are represented as { X, Y }, where X ═ λ { (λ } {0，λ1，λi…λn}，Y＝{I0，I1，Ii…InN, i is the number of the overlapped spectrum data, n is the number of the overlapped spectrum data, and λiIs the peak wavelength, I, of the ith lineiThe spectral intensity value of the ith spectral line.
S2: and estimating characteristic data of the spectral lines to be separated in the overlapped spectral data, wherein the characteristic data comprises a maximum peak value/, a peak value wavelength lambda and a half-peak width sigma, and an effective analysis area corresponding to the fitted maximum peak value I.
The estimation method of each parameter in this example is as follows:
the maximum peak value I is the maximum value of the spectrum intensity value in the overlapped spectrum data, wherein I is max { Y }, and Y is the spectrum intensity value set in the overlapped spectrum data to be analyzed;
the peak wavelength lambda is a wavelength value corresponding to the maximum peak value I;
the formula for calculating the half-peak width σ is:
Fitting an effective analysis area corresponding to the maximum peak value I, specifically:
the left boundary l of the effective analysis region satisfies lambdai< lambda, and, Ii-1≥IiAnd min (λ)i- λ) a wavelength value of the condition;
the right boundary r of the effective analysis region is lambdai< λ and, Ii-1≥IiAnd min (λ)i- λ) a wavelength value of the condition;
and determining an effective analysis area according to the left boundary l and the right boundary r.
S3: and constructing an objective function based on the MPT spectrum mathematical model, and performing optimization matching on the characteristic data of the spectral line to be separated in the effective analysis area by using the objective function to obtain the optimal separation spectral line.
Specifically, the MPT spectral mathematical model is as follows:
where i is the number of the overlapped spectrum data, P (λ)i) At a wavelength λiIntensity value of the overlapped spectrum, M is the number of spectral peaks constituting the overlapped spectrum, j is the number of spectral peaks, Ij(λi) At a wavelength λiAnd the intensity value of the spectral peak at the j is shown as I, the wavelength value corresponding to the maximum intensity value I of the spectral peak is shown as lambda, the half-peak width of the spectral peak is shown as sigma, and mu is a proportionality coefficient.
The optimized objective function is as follows:
wherein i is the serial number of the spectral data, P (lambda)i) At a wavelength λiAt the intensity values of the overlapping spectra, Ij(λi) At a wavelength λiThe intensity value of the spectral peak at the j-th position, and n is the number of the spectral data in the effective analysis area.
The target function is utilized to carry out optimization matching on the characteristic data of the spectral line to be separated in the effective analysis area to obtain the optimal separation spectral line
S4: and subtracting the spectral data of the optimal separation spectral line from the overlapped spectral data to obtain the overlapped spectral data to be analyzed next.
The specific calculation formula is as follows:
P(λi)′＝P(λi)-Ij(λi)；
wherein, P (lambda)i) ' is at a wavelength of λiIntensity value of the overlapping spectral data of the remaining spectral lines, P (lambda)i) At a wavelength λiAt intensity values of the overlapping spectral data, Ij(λi) At a wavelength λiThe intensity value of the separation line data at jth.
S4: and repeating the steps S2-S4 until the maximum intensity value of the overlapped spectral data to be analyzed is lower than the preset lower peak limit, and terminating the continuous spectral line separation.
The line separation process of the above steps S2-S4 will be explained below with the overlapping peak shapes in the overlapping spectral data to be analyzed as shown in fig. 2.
1) Preliminarily estimating the overlapped spectral data to be analyzed in fig. 2 according to the step S2 to obtain a maximum peak value I, a peak wavelength λ, and a half-peak width σ, and fitting a left boundary l and a right boundary r of an effective analysis region corresponding to the maximum peak value I, specifically:
the maximum peak value I is the maximum value of the spectral intensity values in the overlapped spectral data, I ═ max { Y }, and is calculated as 109262;
the peak wavelength lambda is the wavelength value corresponding to the maximum peak value I, and the calculated lambda is 228.8012 nm;
the half-peak width is calculated according to the calculation formula to obtain the sigma of 0.0024 nm;
calculating to obtain l of 228.7508nm according to the condition met by the left boundary l;
according to the condition satisfied by the right boundary r, r is calculated to be 228.8156 nm.
2) Performing optimization matching on the parameters estimated in step 1) according to the objective function in step S3, wherein the result of the optimization is as follows:
I＝109262；
λ＝228.8016nm；
σ＝0.0013nm；
μ＝0.1995；
the spectral lines separated according to the above optimization results are shown in fig. 3.
3) Separating the spectral line data obtained in step 2) from the overlapping spectral data to be analyzed according to step S4, the resulting overlapping spectrum of the remaining spectral lines being shown in fig. 4.
4) Repeating 1) -3) until the maximum intensity value of the overlapped spectral data to be analyzed is lower than a preset peak lower limit, the peak lower limit of the example is 2500, the overlapped spectral data to be analyzed in the side graph 2 is finally separated into 4 spectral line peaks, and the optimization results of the 4 spectral line peaks are shown in the following table:
the peak shapes of the 4 spectral lines are shown in fig. 5, and by querying the MPT spectral line library, it can be determined that the elements corresponding to the 4 spectral line peaks are: 228.8016nm is Cd element, 228.8694nm is W element, 228.8375nm is Ni element, 228.9067nm is Zn element, and the contents of the four elements in the sample can be accurately analyzed by utilizing the MPT mathematical model information obtained by the separation.
The overlapping spectral line separation method of the embodiment enables the MPT spectrometer to directly use the data of the overlapping peak-shaped area for qualitative and quantitative analysis when analyzing the sample, and increases the selection range of the optimal spectral line of the element in the sample analysis process. The sample pretreatment complexity of the MPT spectrometer in complex sample analysis is reduced, the sample analysis efficiency is improved, and the sample analysis cost is saved. Due to the fact that the selection limit of the optimal element spectral line in sample analysis is reduced, the analysis performance of the MPT spectrometer, and the detection capability and detection precision of the MPT spectrometer on complex mixed samples are greatly improved.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (3)
1. An overlapping spectral line separation method based on MPT spectral data is characterized by comprising the following steps:
overlapping spectral data to be analyzed, denoted as { X, Y }, where X ═ λ, { λ }, is selected0，λ1，λi...λn}，Y＝{I0，I1，Ii...InWhere i is 0, 1, 2 … n, i is the number of the superimposed spectrum data, n is the number of the superimposed spectrum data, λiIs the ithPeak wavelength of the spectral line,/iThe spectral intensity value of the ith spectral line;
estimating characteristic data of spectral lines to be separated in the overlapped spectral data, wherein the characteristic data comprise a maximum peak value I, a peak value wavelength lambda and a half peak width sigma, and an effective analysis area corresponding to the maximum peak value I is fitted; wherein the estimating the characteristic data of the spectral line to be separated comprises:
the maximum peak value I is the maximum value of the spectral intensity value in the overlapped spectral data, and is max { Y };
the peak wavelength lambda is a wavelength value corresponding to the maximum peak value I;
the calculation formula of the half-peak width sigma is as follows:
constructing an objective function based on an MPT (Multi-point Transmission test) spectrum mathematical model, and performing optimization matching on the characteristic data of the spectral line to be separated in the effective analysis region by using the objective function to obtain an optimal separation spectral line; wherein the MPT spectrum mathematical model is as follows:
where i is the number of the overlapped spectrum data, P (λ)i) At a wavelength λiIntensity value of the overlapped spectrum, M is the number of spectral peaks constituting the overlapped spectrum, j is the number of spectral peaks, Ij(λi) At a wavelength λiThe intensity value of the jth spectral peak is determined, I is the maximum intensity value of the spectral peak, lambda is the wavelength value corresponding to the maximum intensity value I of the spectral peak, sigma is the half-peak width of the spectral peak, and mu is a proportionality coefficient;
the objective function is:
wherein i is the serial number of the spectral data, P (lambda)i) At a wavelength λiAt the intensity values of the overlapping spectra, Ij(λi) At a wavelength λiThe intensity value of the jth spectral peak is positioned, and n is the number of the spectral data in the effective analysis area;
and subtracting the spectral data of the optimal separation spectral line from the overlapped spectral data to obtain the overlapped spectral data to be analyzed next.
2. The method of overlapping line separation of claim 1 wherein fitting the effective analysis area corresponding to the largest peak I comprises:
the left boundary l of the effective analysis region satisfies lambdai< lambda, and, Ii-1≥IiAnd min (λ)i- λ) a wavelength value of the condition;
the right boundary r of the effective analysis region is lambdai< λ and, Ii-1≥IiAnd min (λ)i- λ) the wavelength value of the condition.
3. The method for separating overlapped spectral lines according to claim 1, wherein the spectral data of the optimal separation spectral line is subtracted from the overlapped spectral data to obtain the overlapped spectral data to be analyzed, and the calculation formula is:
P(λi)′＝P(λi)-Ij(λi)；
wherein, P (lambda)i) ' is at a wavelength of λiIntensity value of the overlapping spectral data of the remaining spectral lines, P (lambda)i) At a wavelength λiAt intensity values of the overlapping spectral data, Ij(λi) At a wavelength λiThe intensity value of the separation line data at jth.
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