Accurate method based on data filtering for quantitative multi-element analysis of soils using CF-LIBS

To obtain more stable spectral data for accurate quantitative analysis of multi-element,especially for the large-area in-situ elements detection of soils, we propose a method for a multielement quantitative analysis of soils using calibration-free laser-induced breakdown spectroscopy(CF-LIBS) based on data filtering. In this study, we analyze a standard soil sample doped with two heavy metal elements, Cu and Cd, with a specific focus on the line of Cu I324.75 nm for filtering the experimental data of multiple sample sets. Pre-and post-data filtering,the relative standard deviation for Cu decreased from 30% to 10%, The limits of detection(LOD)values for Cu and Cd decreased by 5% and 4%, respectively. Through CF-LIBS, a quantitative analysis was conducted to determine the relative content of elements in soils. Using Cu as a reference, the concentration of Cd was accurately calculated. The results show that post-data filtering, the average relative error of the Cd decreases from 11% to 5%, indicating the effectiveness of data filtering in improving the accuracy of quantitative analysis. Moreover, the content of Si, Fe and other elements can be accurately calculated using this method. To further correct the calculation, the results for Cd was used to provide a more precise calculation. This approach is of great importance for the large-area in-situ heavy metals and trace elements detection in soil, as well as for rapid and accurate quantitative analysis.

Research on batch multielement rapid quantitative analysis based on the standard curve-assisted calibration-free laserinduced breakdown spectroscopy method

This study proposes a batch rapid quantitative analysis method for multiple elements by combining the advantages of standard curve(SC)and calibration-free laser-induced breakdown spectroscopy(CF-LIBS)technology to achieve synchronous,rapid,and accurate measurement of elements in a large number of samples,namely,SC-assisted CF-LIBS.Al alloy standard samples,divided into calibration and test samples,were applied to validate the proposed method.SC was built based on the characteristic line of Pb and Cr in the calibration sample,and the contents of Pb and Cr in the test sample were calculated with relative errors of 6%and 4%,respectively.SC built using Cr with multiple characteristic lines yielded better calculation results.The relative contents of ten elements in the test sample were calculated using CF-LIBS.Subsequently,the SC-assisted CF-LIBS was executed,with the majority of the calculation relative errors falling within the range of 2%-5%.Finally,the Al and Na contents of the Al alloy were predicted.The results demonstrate that it effectively enables the rapid and accurate quantitative analysis of multiple elements after a single-element SC analysis of the tested samples.Furthermore,this quantitative analysis method was successfully applied to soil and Astragalus samples,realizing an accurate calculation of the contents of multiple elements.Thus,it is important to advance the LIBS quantitative analysis and its related applications.

Simplified quantitative analysis method and its application in the insitu synthesized copper-based azide chips

Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ synthesis method,including small size and low dosage,bring about difficulties in quantitative analysis and differences in ignition capabilities of CA chips.The aim of present work is to develop a simplified quantitative analysis method for accurate and safe analysis of components in CA chips to evaluate and investigate the corresponding ignition ability.In this work,Cu(N_(3))2 and CuN_(3)components in CA chips were separated through dissolution and distillation by utilizing the difference in solubility and corresponding content was obtained by measuring N_(3)-concentration through spectrophotometry.The spectrophotometry method was optimized by studying influencing factors and the recovery rate of different separation methods was studied,ensuring the accuracy and reproducibility of test results.The optimized method is linear in range from 1.0-25.0 mg/L,with a correlation coefficient R^(2)=0.9998,which meets the requirements of CA chips with a milligram-level content test.Compared with the existing ICP method,component analysis results of CA chips obtained by spectrophotometry are closer to real component content in samples and have satisfactory accuracy.Moreover,as its application in miniaturized explosive systems,the ignition ability of CA chips with different component contents for direct ink writing CL-20 and the corresponding mechanism was studied.This study provided a basis and idea for the design and performance evaluation of CA chips in miniaturized explosive systems.

Quantitative analysis and prediction of the sound field convergence zone in mesoscale eddy environment based on data mining methods

The mesoscale eddy(ME)has a significant influence on the convergence effect in deep-sea acoustic propagation.This paper use statistical approaches to express quantitative relationships between the ME conditions and convergence zone(CZ)characteristics.Based on the Gaussian vortex model,we construct various sound propagation scenarios under different eddy conditions,and carry out sound propagation experiments to obtain simulation samples.With a large number of samples,we first adopt the unified regression to set up analytic relationships between eddy conditions and CZ parameters.The sensitivity of eddy indicators to the CZ is quantitatively analyzed.Then,we adopt the machine learning(ML)algorithms to establish prediction models of CZ parameters by exploring the nonlinear relationships between multiple ME indicators and CZ parameters.Through the research,we can express the influence of ME on the CZ quantitatively,and achieve the rapid prediction of CZ parameters in ocean eddies.The prediction accuracy(R)of the CZ distance(mean R:0.9815)is obviously better than that of the CZ width(mean R:0.8728).Among the three ML algorithms,Gradient Boosting Decision Tree has the best prediction ability(root mean square error(RMSE):0.136),followed by Random Forest(RMSE:0.441)and Extreme Learning Machine(RMSE:0.518).

Incorporating empirical knowledge into data-driven variable selection for quantitative analysis of coal ash content by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy(LIBS)has become a widely used atomic spectroscopic technique for rapid coal analysis.However,the vast amount of spectral information in LIBS contains signal uncertainty,which can affect its quantification performance.In this work,we propose a hybrid variable selection method to improve the performance of LIBS quantification.Important variables are first identified using Pearson's correlation coefficient,mutual information,least absolute shrinkage and selection operator(LASSO)and random forest,and then filtered and combined with empirical variables related to fingerprint elements of coal ash content.Subsequently,these variables are fed into a partial least squares regression(PLSR).Additionally,in some models,certain variables unrelated to ash content are removed manually to study the impact of variable deselection on model performance.The proposed hybrid strategy was tested on three LIBS datasets for quantitative analysis of coal ash content and compared with the corresponding data-driven baseline method.It is significantly better than the variable selection only method based on empirical knowledge and in most cases outperforms the baseline method.The results showed that on all three datasets the hybrid strategy for variable selection combining empirical knowledge and data-driven algorithms achieved the lowest root mean square error of prediction(RMSEP)values of 1.605,3.478 and 1.647,respectively,which were significantly lower than those obtained from multiple linear regression using only 12 empirical variables,which are 1.959,3.718 and 2.181,respectively.The LASSO-PLSR model with empirical support and 20 selected variables exhibited a significantly improved performance after variable deselection,with RMSEP values dropping from 1.635,3.962 and 1.647 to 1.483,3.086 and 1.567,respectively.Such results demonstrate that using empirical knowledge as a support for datadriven variable selection can be a viable approach to improve the accuracy and reliability of LIBS quantification.

Energy-dispersive X-ray Spectroscopy for the Quantitative Analysis of Pyrite Thin Specimens

To explore ways to improve the accuracy of quantitative analysis of samples in the micrometer to nanometer range of magnitudes,we adopted analytical transmission electron microscopy(AEM/EDS)for qualitative and quantitative analysis of pyrite materials.Additionally,the k factor of pyrite is calculated experimentally.To develop an appropriate non-standard quantitative analysis model for pyrite materials,the experimentally calculated k factor is compared with that estimated from the non-standard quantitative analytical model of the instrument software.The experimental findings demonstrate that the EDS attached to a TEM can be employed for precise quantitative analysis of micro-and nanoscale regions of pyrite materials.Furthermore,it serves as a reference for improving the results of the EDS quantitative analysis of other sulfides.

Spectra-assisted laser focusing in quantitative analysis of laser-induced breakdown spectroscopy for copper alloys

Laser-induced breakdown spectroscopy(LIBS)is a capable technique for elementary analysis,while LIBS quantitation is still under development.In quantitation,precise laser focusing plays an important role because it ensures the distance between the laser and samples.In the present work,we employed spectral intensity as a direct way to assist laser focusing in LIBS quantitation for copper alloys.It is found that both the air emission and the copper line could be used to determine the position of the sample surface by referencing the intensity maximum.Nevertheless,the fine quantitation was only realized at the position where the air emission(e.g.O(I)777.4 nm)reached intensity maximum,and also in this way,a repeatable quantitation was successfully achieved even after 120 days.The results suggested that the LIBS quantitation was highly dependent on the focusing position of the laser,and spectra-assisted focusing could be a simple way to find the identical condition for different samples’detection.In the future,this method might be applicable in field measurements for LIBS analysis of solids.

DecodeSTORM:A user-friendly ImageJ plug-in for quantitative data analysis in single-molecule localization microscopy

Quantitative data analysis in single-molecule localization microscopy(SMLM)is crucial for studying cellular functions at the biomolecular level.In the past decade,several quantitative methods were developed for analyzing SMLM data;however,imaging artifacts in SMLM experiments reduce the accuracy of these methods,and these methods were seldom designed as user-friendly tools.Researchers are now trying to overcome these di±culties by developing easyto-use SMLM data analysis software for certain image analysis tasks.But,this kind of software did not pay su±cient attention to the impact of imaging artifacts on the analysis accuracy,and usually contained only one type of analysis task.Therefore,users are still facing di±culties when they want to have the combined use of different types of analysis methods according to the characteristics of their data and their own needs.In this paper,we report an ImageJ plug-in called DecodeSTORM,which not only has a simple GUI for human–computer interaction,but also combines artifact correction with several quantitative analysis methods.DecodeSTORM includes format conversion,channel registration,artifact correction(drift correction and localization¯ltering),quantitative analysis(segmentation and clustering,spatial distribution statistics and colocalization)and visualization.Importantly,these data analysis methods can be combined freely,thus improving the accuracy of quantitative analysis and allowing users to have an optimal combination of methods.We believe DecodeSTORM is a user-friendly and powerful ImageJ plug-in,which provides an easy and accurate data analysis tool for adventurous biologists who are looking for new imaging tools for studying important questions in cell biology.

Quantitative morphometric analysis of a deep-water channel in the Taranaki Basin, New Zealand

The morphological changes of deep-water channels have an important influence on the distributions of channel sand reservoirs,so it is important to explore the morphological change process of deep-water channel for the exploration and development of deep-water oil and gas.Based on a typical sinuous Quaternary channel(Channel I)in the Taranaki Basin,New Zealand,a variety of seismic interpretation techniques were applied to quantitatively characterize the morphological characteristics of the Channel I,and the relationships between the quantitative parameters and the morphological changes of the Channel I,as well as the controlling factors affecting those morphological changes,were discussed.The results are as follows:(1)in the quantitative analysis,six parameters were selected:the channel depth,width,sinuosity,and aspect ratio(width/depth),the channel swing amplitude(λ)and the channel bend frequency(ω);(2)according to the quantitative morphological parameters of the channel(mainly including three parameters such as channel sinuosity,ωandλ),the Channel I was divided into three types:the low-sinuous channel(LSC),the high-sinuous channel(HSC),the moderate-sinuous channel(MSC).U-shaped channel cross-sections developed in the LSC,V-shaped channel cross-sections developed in the HSC,including inclined-V and symmetric-V cross-sections,and dish-shaped channel cross-sections developed in the MSC;(3)the morphological characteristics of the LSC and MSC were related to their widths and depths,while the morphology of the HSC was greatly affected by the channel width,a change in depth did not affect the HSC morphology;(4)the morphological changes of the Channel I were controlled mainly by the slope gradient,the restricted capacity of the channel and the differential in fluid properties.

Consequences of Insufficient Selectivity in Quantitative and Qualitative Chemical Analysis

A problem in chemical analysis in connection with measurements of a substance normally occurring in a sample, or identification of a substance which should not exist in a sample, is insufficient selectivity. In this article, we analyze this problem and propose remedies. We use a real doping case to illustrate how chemical noise causes a serious selectivity problem, probably causing a false positive outcome.

Quantitative energy-dispersive X-ray fluorescence analysis for unknown samples using full-spectrum least-squares regression

The full-spectrum least-squares(FSLS) method is introduced to perform quantitative energy-dispersive X-ray fluorescence analysis for unknown solid samples.Based on the conventional least-squares principle, this spectrum evaluation method is able to obtain the background-corrected and interference-free net peaks, which is significant for quantization analyses. A variety of analytical parameters and functions to describe the features of the fluorescence spectra of pure elements are used and established, such as the mass absorption coefficient, the Gi factor, and fundamental fluorescence formulas. The FSLS iterative program was compiled in the C language. The content of each component should reach the convergence criterion at the end of the calculations. After a basic theory analysis and experimental preparation, 13 national standard soil samples were detected using a spectrometer to test the feasibility of using the algorithm. The results show that the calculated contents of Ti, Fe, Ni, Cu, and Zn have the same changing tendency as the corresponding standard content in the 13 reference samples. Accuracies of 0.35% and 14.03% are obtained, respectively, for Fe and Ti, whose standard concentrations are 8.82% and 0.578%, respectively. However, the calculated results of trace elements (only tens of lg/g) deviate from the standard values. This may be because of measurement accuracy and mutual effects between the elements.

Fitting Full X-Ray Diffraction Patterns for Quantitative Analysis: A Method for Readily Quantifying Crystalline and Disordered Phases

Fitting of full X-ray diffraction patterns is an effective method for quantifying abundances during X-ray diffraction (XRD) analyses. The method is based on the principal that the observed diffraction pattern is the sum of the individual phases that compose the sample. By adding an internal standard (usually corundum) to both the observed patterns and to those for individual pure phases (standards), all patterns can all be normalized to an equivalent intensity based on the internal standard intensity. Using least-squares refinement, the individual phase proportions are varied until an optimal match is reached. As the fitting of full patterns uses the entire pattern, including background, disordered and amorphous phases are explicitly considered as individual phases, with their individual intensity profiles or “amorphous humps” included in the refinement. The method can be applied not only to samples that contain well-ordered materials, but it is particularly well suited for samples containing amorphous and/or disordered materials. In cases with extremely disordered materials where no crystal structure is available for Rietveld refinement or there is no unique intensity area that can be measured for a traditional RIR analysis, full-pattern fitting may be the best or only way to readily obtain quantitative results. This approach is also applicable in cases where there are several coexisting highly disordered phases. As all phases are considered as discrete individual components, abundances are not constrained to sum to 100%.

AN INCREMENTAL METHOD OF X-RAY DIFFRACTION QUANTITATIVE PHASE ANALYSIS OF SAMPLESCONTAINING AMORPHOUS MATERIAL

A new method for quantitative X-ray diffraction phase analysis of a powder misture has been developed according to Popovic's doping method. The weight fraction of amorphous material in the analysed sample is obtained. For a multicomponent system in which (n-2) pure phases are added into an n-phase compnent sample and theweight fractions of all n phases can be determined by the method. The test results of confirmation agree well with the theory.

A SOLUTION OF MINIMUM NORM FOR QUANTITATIVE PHASE ANALYSIS BY STANDARDLESS X-RAY DIFFRACTION

A new expression of quantitative phase analysis by standardless X-ray diffraction has been derived using intensity matrix of vector modulus.The criterion of standardless X-ray diffraction analysis was suggested,so as to separate the diffraction pattern of every phase from that of sample.The optimal solution could be obtained by the least squares regression.

A SOLUTION OF MINIMUM NORM FOR QUANTITATIVE PHASE ANALYSIS BY STANDARDLESS X-RAY DIFFRACTION

A new expression of quantitative phase analysis by standardless X-ray diffraction has been derived using intensity matrix of vector modulus,The criterion of standardless X-ray diffraction analysis was suggested,so as to separate the diffraction pattern of every phase from that of sample.The optimal solution could be obtained by the least squares regression.

DATA PROCESSING OF UNIVERSAL QUANTITATIVE METHOD IN STANDARDLESS X-RAY PHASE ANALYSIS

Accuracy of coeffcient A_(isp) is related to the reference phase chosen during analysis. The cri- terion of choosing reference phase which may minimize the error of A_(isp) was deduced. The optimum results could be obtained by using the method of least squares if the number of sam- pies for analysis is more than the phase in samples. The procedure presented here is satisfacto- ryfor ordinary phase analysis.

Quantitative Analysis of Land Use Landscape Pattern in Shihezi Desert Oasis

Based on the land use status map of Shihezi City,the land use landscape map of Shihezi City was made with the support of GIS then many landscape indices were selected to quantitatively analyze the landscape pattern characteristics of Shihezi Oasis from three aspects of landscape diversity index,landscape space configuration index and plaque characteristics index. The results showed that the main plaque types of the landscape in Shihezi reclamation area are arable land and water areas,which totally account for 58% of the total area; farmland,gardens,woodland,urban sites,industrial and mining land use were embedded in this oasis landscape in the form of mosaics,and their fractal index was high due to the strong impact of human activities; arable land and mining land distribution was scattered,but marshes and other uncultivated land were relatively concentrated. The dominance degree of the landscape was low because there was no advantageous type in this landscape and all patches distributed equably which was easily to be disturbed so that the whole landscape was unstable. Comprehensively speaking,the landscape in Shihezi region was rather complicate,and its diversity index,fragmentation degree and heterogeneity were high.

Observation and Analysis of VLF Nocturnal Multimode Interference Phenomenon based on Waveguide Mode Theory

Very low frequency(VLF)signals are propagated between the ground-ionosphere.Multimode interference will cause the phase to show oscillatory changes with distance while propagating at night,leading to abnormalities in the received VLF signal.This study uses the VLF signal received in Qingdao City,Shandong Province,from the Russian Alpha navigation system to explore the multimode interference problem of VLF signal propagation.The characteristics of the effect of multimode interference phenomena on the phase are analyzed according to the variation of the phase of the VLF signal.However,the phase of VLF signals will also be affected by the X-ray and energetic particles that are released during the eruption of solar flares,therefore the two phenomena are studied in this work.It is concluded that the X-ray will not affect the phase of VLF signals at night,but the energetic particles will affect the phase change,and the influence of energetic particles should be excluded in the study of multimode interference phenomena.Using VLF signals for navigation positioning in degraded or unavailable GPS conditions is of great practical significance for VLF navigation systems as it can avoid the influence of multimode interference and improve positioning accuracy.

CORRELATION OF THE COMPONENTS OF PORTLAND CEMENT CLINKER AND SINTERING PROCESS BY MEANS OF XRD QUANTITATIVE ANALYSIS

In this paper, the cement clinkers from various industrial Kilns were investigated by a superposing peaks method for X-ray quantitative analysis (XRQA) of clinker minerals, the results show that the clinker mineral contents measured by XRQA method better accord with the reality of clinkers made in different conditions than theoretic contents calculated by Bouge formula do. The measured contents of C3S of clinkers manufactured in rotary kilns are higher than theoretically calculated values,whereas, the results of clinker man manufactured in shaft kilns are contrary to that. This is because in rotary kiln, the raw meals are fully pre-heated and have high sintering temperature, the clinkers are well solid-solutioned and rapidly cooled,on the contrary,owing to the struetural defects, it is easy to exist reducing atmosphere and lower temperature in shaft kiln,moreover the cooling rate is slower, all these can evidently Lead to worse clinker quality. Adding CaF2-Ca-SO4 complex mineralizer can remarkably modify the sintering situation in shaft kiln ,especially can evidently increase C3S content and make it well crystallized, therefore, im prove the sintered quality of clinker.

Numerical analysis of matrix swelling and its effect on microstructure of digital coal and its associated permeability during CO_(2)-ECBM process based on X-ray CT data

Matrix swelling effect will cause the change of microstructure of coal reservoir and its permeability,which is the key factor affecting the engineering effect of CO_(2)-ECBM technology.The Sihe and Yuwu collieries are taken as research objects.Firstly,visualization reconstruction of coal reservoir is realized.Secondly,the evolution of the pore/fracture structures under different swelling contents is discussed.Then,the influence of matrix phase with different swelling contents on permeability is discussed.Finally,the mechanism of swelling effect during the CO_(2)-ECBM process is further discussed.The results show that the intra-matrix pores and matrix-edge fractures are the focus of this study,and the contacting area between matrix and pore/fracture is the core area of matrix swelling.The number of matrix particles decreases with the increase of size,and the distribution of which is isolated with small size and interconnected with large size.The swelling effect of matrix particles with larger size has a great influence on the pore/fracture structures.The number of connected pores/fractures is limited and only interconnected in a certain direction.With the increase of matrix swelling content,the number,porosity,width,fractal dimension,surface area and volume of pores/fractures decrease,and their negative contribution to absolute permeability increases from 0.368% to 0.633% and 0.868%-1.404%,respectively.With the increase of swelling content,the number of intra-matrix pores gradually decreases and the pore radius becomes shorter during the CO_(2)-ECBM process.The matrix continuously expands to the connected fractures,and the width of connected fractures gradually shorten.Under the influence of matrix swelling,the bending degree of fluid flow increases gradually,so the resistance of fluid migration increases and the permeability gradually decreases.This study shows that the matrix swelling effect is the key factor affecting CBM recovery,and the application of this effect in CO_(2)-ECBM process can be discussed.