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.

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.

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.

Atomic-level quantitative analysis of electronic functional materials by aberration-corrected STEM

The stable sub-angstrom resolution of the aberration-corrected scanning transmission electron microscope(ACSTEM)makes it an advanced and practical characterization technique for all materials.Owing to the prosperous advancement in computational technology,specialized software and programs have emerged as potent facilitators across the entirety of electron microscopy characterization process.Utilizing advanced image processing algorithms promotes the rectification of image distortions,concurrently elevating the overall image quality to superior standards.Extracting high-resolution,pixel-level discrete information and converting it into atomic-scale,followed by performing statistical calculations on the physical matters of interest through quantitative analysis,represent an effective strategy to maximize the value of electron microscope images.The efficacious utilization of quantitative analysis of electron microscope images has become a progressively prominent consideration for materials scientists and electron microscopy researchers.This article offers a concise overview of the pivotal procedures in quantitative analysis and summarizes the computational methodologies involved from three perspectives:contrast,lattice and strain,as well as atomic displacements and polarization.It further elaborates on practical applications of these methods in electronic functional materials,notably in piezoelectrics/ferroelectrics and thermoelectrics.It emphasizes the indispensable role of quantitative analysis in fundamental theoretical research,elucidating the structure–property correlations in high-performance systems,and guiding synthesis strategies.

Rapid and real-time analysis of multi-component dissolved gas in seawater by Raman spectroscopy combined with continuous gas-liquid separator

Rapid and sensitive detection of dissolved gases in seawater is quite essential for the investigation of the global carbon cycle.Large quantities of in situ optical detection techniques showed restricted measurement efficiency,owing to the single gas sensor without the identification ability of multiple gases.In this work,a novel gas-liquid Raman detection method of monitoring the multi-component dissolved gases was proposed based on a continuous gas-liquid separator under a large difference of partial pressure.The limit of detection(LOD)of the gas Raman spectrometer could arrive at about 14 μl·L^(-1)for N_(2)gas.Moreover,based on the continuous gas-liquid separation process,the detection time of the dissolved gases could be largely decreased to about 200 s compared with that of the traditional detection method(30 min).Effect of equilibrium time on gas-liquid separation process indicated that the extracted efficiency and decay time of these dissolved gases was CO_(2)>O_(2)>N_(2).In addition,the analysis of the relationship between equilibrium time and flow speed indicated that the decay time decreased with the increase of the flow speed.The validation and application of the developed system presented its great potential for studying the components and spatiotemporal distribution of dissolved gases in seawater.

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.

Design analysis and its application of M out of N in reactor protection system

The reliability and availability of the reactor protection system （RPS） can be improved by using M out of N judg- ment system. By analyzing two quantitative indicators, the rate of refusal to operate and mal-operation rate, a strict math- ematical formula and an approximate calculation are stated. The differences of a series of judgment systems are discussed on condition that the unsafe failure probability and the security failure probability are both 0.1. Based on given parameters （A, B,P, Q）： A is upper limit of the refusal rate for the RPS, B is upper limit of the real-operation rate, P and Q are basic protection unit rates corresponding to refusal rate and mal-operation rate, respectively. According to these parameters, the values of N and M can be solved.

Qualitative and Quantitative Analysis of Alkaloids in Cortex Phellodendri by HPLC-ESI-MS/MS and HPLC-DAD

A combined method of high performance liquid chromatograph-elecrtrospray-ionization mass spectrometer（HPLC-ESI-MS/MS） coupled with a photodiode array detector（HPLC-DAD） and principal component analysis（PCA） was applied to the qualitative and quantitative analyses of alkaloids in Cortex Phellodendri（CP） samples, and to the differentiation of two species of CP, Cortex Phellodendri Chinensis（CPC） and Cortex Phellodendri Amurensis（CPA）. Twenty-two peaks appeared in the HPLC-MS base peak chromatogram of CP detected by the HPLC-ESI-MS/MS analysis, and the alkaloids were identified according to the MSn data, the known MS fragmentation rules and the literature data. Five alkaloids including berberine, palmatine, jatrorrhizine, phellodendrine and magnoflorine were simultaneously determinated by the HPLC-DAD. Berberine was the primary component in all CP samples, and the contents of berberine and palmatine were exploited to be two critical parameters for effective discrimination between the two species of CP. The average content of berberine in CPC（58.75 mg/g） was higher than that in CPA（9.16 mg/g）, while the content of palmatine was less, only 0.25 mg/g in CPC and 4.19 mg/g in CPA. With the use of PCA, samples datasets were separated successfully into two different clusters corresponding to the two species, and berberine, pahnatine, phellodendrine and magnoflorine contribute most to the above mentioned calssifying . The proposed method oroved to be a useful tool in the aualitv control of Chinese herbal medicines.

Change of choline compounds in sodium selenite-induced apoptosis of rats used as quantitative analysis by in vitro 9.4T MR spectroscopy

AIM: To study liver cell apoptosis caused by the toxicity of selenium and observe the alteration of choline compounds using in vitro 9.4T high resolution magnetic resonance spectroscopy. METHODS: Twenty male Wistar rats were randomly divided into two groups. The rats in the treatment group were intraperitoneally injected with sodium selenite and the control group with distilled water. All rats were sacrifi ced and the livers were dissected. 1H-MRS data were collected using in vitro 9.4T high resolution magnetic resonance spectrometer. Spectra were processed using XWINNMR and MestRe-c 4.3. HE and TUNEL staining was employed to detect and confi rm the change of liver cells. RESULTS: Good 1H-MR spectra of perchloric acid extract from liver tissue of rats were obtained. The conventional metabolites were detected and assigned. Concentrations of different ingredient choline compounds in treatment group vs control group were as follows: total choline compounds,5.08 ± 0.97 mmol/L vs 3.81 ± 1.16 mmol/L (P = 0.05); and free choline,1.07 ± 0.23 mmol/L vs 0.65 ± 0.20 mmol/L (P = 0.00). However,there was no statistical signif icance between the two groups. The hepatic sinus and cellular structure of hepatic cells in treatmentgroup were abnormal. Apoptosis of hepatic cells was confi rmed by TUNEL assay. CONCLUSION: High dose selenium compounds can cause the rat liver lesion and induce cell apoptosis in vivo. High resolution 1H-MRS in vitro can detect diversified metabolism. The changing trend for different ingredient of choline compounds is not completely the same at early period of apoptosis.

Quantitative Analysis of Moisture Effect on Black Soil Reflectance

Several studies have demonstrated that soil reflectance decreases with increasing soil moisture content, or increases when the soil moisture reaches a certain content; however, there are few analyses on the quantitative relationship between soil reflectance and its moisture, especially in the case of black soils in northeast China. A new moisture adjusting method was developed to obtain soil reflectance with a smaller moisture interval to describe the quantitative relationship between soil reflectance and moisture. For the soil samples with moisture contents ranging from air-dry to saturated, the changes in soil reflectance with soil moisture can be depicted using a cubic equation. Both moisture threshold (MT) and moisture inflexion (MI) of soil reflectance can also be determined by the equation. When the moisture range was smaller than MT, soil reflectance can be simulated with a linear model. However, for samples with different soil organic matter (OM), the parameters of the linear model varied regularly with the OM content. Based on their relationship, the soil moisture can be estimated from soil reflectance in the black soil region.

Texture features analysis on micro-structure of paste backfill based on image analysis technology

The strength of cement-based materials,such as mortar,concrete and cement paste backfill(CPB),depends on its microstructures(e.g.pore structure and arrangement of particles and skeleton).Numerous studies on the relationship between strength and pore structure(e.g.,pore size and its distribution)were performed,but the micro-morphology characteristics have been rarely concerned.Texture describing the surface properties of the sample is a global feature,which is an effective way to quantify the micro-morphological properties.In statistical analysis,GLCM features and Tamura texture are the most representative methods for characterizing the texture features.The mechanical strength and section image of the backfill sample prepared from three different solid concentrations of paste were obtained by uniaxial compressive strength test and scanning electron microscope,respectively.The texture features of different SEM images were calculated based on image analysis technology,and then the correlation between these parameters and the strength was analyzed.It was proved that the method is effective in the quantitative analysis on the micro-morphology characteristics of CPB.There is a significant correlation between the texture features and the unconfined compressive strength,and the prediction of strength is feasible using texture parameters of the CPB microstructure.

Calculation of Ecological Footprint Based on Modified Method and Quantitative Analysis of Its Impact Factors——A Case Study of Shanghai

Ecological footprint （EF） has attracted much attention internationally as a potential indicator for sustainable development. In China, EF has also gained recognition in related fields and disciplines. Moreover, some scholars in these fields have proposed alternative methods to calculate EF and have made some progress. This paper, therefore, begins with the introduction and development of EF in China. However, the established methods of EF calculation hold some limitations, such as indicator variance and result abnormality. In order to resolve those problems, the authors make a further modification considering the demand of EF as a comprehensive indicator： 1） More accurate analysis has been done to divide EF into several parts： imported EF, exported EF, and producible EF, which is the solution to the problem of abnormality in original EF results and can explain abnormal phenomena reasonably. 2） Considering the actual situa- tion of Shanghai, emended equivalence factor is brought forward and a matrix is formed with equivalence factors. The measure can reduce the deviation between the fact and the results. 3） The calculation compares local yield with global average yield to analyze the effects of yields. And based on local yields in different years, the results are more accurate. Finally, the calculation method is applied to calculating EF of Shanghai from 1980 to 2003, and the subsequent detailed analysis is presented. Available data and results suggest a statistically significant correlation coefficient between EF and GDP, population density and urbaniTation level. Through analyzing the process of calculating EF and its results, it can be seen that EF, as a macro-indicator, can not exactly indicate whether development within a region can meet the re- quests of sustainable development, which can be explained by the fact that the result of EF is impacted greatly by sub- jective factors including national policy,available technology, population, etc. Nevertheless, EF can demonstrate, at least to some degree, the regional status in terms of resources and energy consumption, as well as developmental potential. The calculation of EF, therefore, deserves further research to achieve more far-reaching significance in application.

Quantitative analysis of the dynamic change and spatial differences of the ecological security: a case study of Loess Plateau in northern Shaanxi Province

Using the theory and method of the ecological footprint, and combining the changes of regional land use, resource environment, population, society and economy, this paper calculated the ecological footprint, ecological carrying capacity and ecological surplus/loss in 1986-2002 on the Loess Plateau in northern Shaanxi Province. What is more, this paper has put forward the concept of ecological pressure index, set up ecological pressure index models, and ecological security grading systems, and the prediction models of different ecological footprints, ecological carrying capacity, ecological surplus and ecological safety change, and also has assessed the ecological footprint demands of 10,000 yuan GDE The results of this study are as follows： （1） the ecological carrying capacity in northern Shaanxi shows a decreasing trend, the difference of reducing range is the fastest; （2） the ecological footprint appears an increasing trend; （3） ecological pressure index rose to 0.91 from 0.44 during 1986-2002 on the Loess Plateau of northern Shaanxi with an increase of 47%; and （4） the ecological security in the study area is in a critical state, and the ecological oressure index has been increasing rapidlv.

A quantitative analysis method for GPR signals based on optimal biorthogonal wavelet

Due to the disturbances arising from the coherence of reflected waves and from echo noise,problems such as limitations,instability and poor accuracy exist with the current quantitative analysis methods.According to the intrinsic features of GPR signals and wavelet time–frequency analysis,an optimal wavelet basis named GPR3.3 wavelet is constructed via an improved biorthogonal wavelet construction method to quantitatively analyse the GPR signal.A new quantitative analysis method based on the biorthogonal wavelet(the QAGBW method)is proposed and applied in the analysis of analogue and measured signals.The results show that compared with the Bayesian frequency-domain blind deconvolution and with existing wavelet bases,the QAGBW method based on optimal wavelet can limit the disturbance from factors such as the coherence of reflected waves and echo noise,improve the quantitative analytical precision of the GPR signal,and match the minimum thickness for quantitative analysis with the vertical resolution of GPR detection.

MULTI-PEAK MATCH INTENSITY RATIO METHOD OF QUANTI-TATIVE X-RAY DIFFRACTION PHASE ANALYSIS

A new method for quantitative phase analysis is proposed by using X-ray diffraction multi-peak match intensity ratio. This method can obtain the multi-peak match intensity ratio among each phase in the mixture sample by using all diffraction peak data in the mixture sample X-ray diffraction spectrum and combining the relative intensity distribution data of each phase standard peak in JCPDS card to carry on the least square method regression analysis. It is benefit to improve the precision of quantitative phase analysis that the given single line ratio which is usually adopted is taken the place of the multi-peak match intensity ratio and is used in X-ray diffraction quantitative phase analysis of the mixture sample. By analyzing four-group mixture sample, adopting multi-peak match intensity ratio and X-ray diffraction quantitative phase analysis principle of combining the adiabatic and matrix flushing method, it is tested that the experimental results are identical with theory.

Nondestructive Quantitative Analysis of Cofrel Medicines by Double ANN-NIR Spectroscopy

In this paper, a double artificial neural network （DANN） algorithm was used to parse near infrared （NIR） reflectance spectrum of Cofrel medicines. The contents of benproperine phosphate, which is the effective ingredient in Cofrel medicines, were accurately nondestructive quantitatively predicted. Compared the results with those of HPLC, the relative errors （RE %） were less than 0.18%. The analytical results could be applied to qualitative control of Cofrel medicines.

A feature selection method combined with ridge regression and recursive feature elimination in quantitative analysis of laser induced breakdown spectroscopy

In the spectral analysis of laser-induced breakdown spectroscopy,abundant characteristic spectral lines and severe interference information exist simultaneously in the original spectral data.Here,a feature selection method called recursive feature elimination based on ridge regression(Ridge-RFE)for the original spectral data is recommended to make full use of the valid information of spectra.In the Ridge-RFE method,the absolute value of the ridge regression coefficient was used as a criterion to screen spectral characteristic,the feature with the absolute value of minimum weight in the input subset features was removed by recursive feature elimination(RFE),and the selected features were used as inputs of the partial least squares regression(PLS)model.The Ridge-RFE method based PLS model was used to measure the Fe,Si,Mg,Cu,Zn and Mn for 51 aluminum alloy samples,and the results showed that the root mean square error of prediction decreased greatly compared to the PLS model with full spectrum as input.The overall results demonstrate that the Ridge-RFE method is more efficient to extract the redundant features,make PLS model for better quantitative analysis results and improve model generalization ability.

A New Method for Clay Mineral Analysis and Its Application in Geology

X-ray diffraction (XRD) peaks in a low-angle diffraction section of clayminerals, especially those of authigenic origin, have broadening and tailing features in shape.Using the five basic parameters, peak position, peak height, width, shape coefficient and asymmetry,to describe an XRD peak is more accurate, comprehensive and integrated than using only 3 of them,position, height and width. Following the concept of the five basic parameters of an XRD peak, theprogram Decoform proposed in this study provides more information in mineralogical analyses byfitting actual XRD profiles. In combination with the HW-IR plot, Decoform can he systematically andaccurately used in the comprehensive analyses of crystallinity, domain size, lattice strain andquantitative phase. It is also of value for the geological investigations of diagenesis,metamorphism, basin maturity, structural stress field and so on.

Mathematic Models for Analysis of Quality Components in Sugarcane Juice with Fourier Transform Near Infrared Spectroscopy

With the technique of Fourier transform near infrared (FT-NIR) spectroscopy, the calibration models for quantitative analysis of sucrose and polarization in sugarcane juice were developed by using transmission mode and calibrating with partial least square (PLS) algorithm. The determination coefficients (R2) of the predicted models for sucrose and polarization in juice were 0. 9980 and 0. 9979 respectively; the root mean square errors of cross validation (RMSECV) were 0. 143 and 0. 155% for sucrose and polarization in juice respectively. The predictive errors measured by FT-NIR were close to those by routine laboratory methods. The results demonstrated that the FT-NIR methods had high accuracy and they were able to replace the routine laboratory analysis. It was also demonstrated that as a rapid and accurate measurement, the FT-NIR technique had potential applications in quality control of mill sugarcane, establishment of payment system based on sugarcane quality, and selection of clones in sugarcane breeding.

Computer Management of Quantitative Analysis Chemistry Experiment

The application of computer in the quantitative analysis chemistry experiment is a chemistry experiment teaching applications software, developed by Visual Basic （6.0）, based on the content of quantitative analysis chemistry experiment of chemistry major in higher institute. This software has the function of the automatic processing the experimental data, the automatic generation of test report copies, and the automatic evaluation of students＇ experimental results, which solve the reliability, objectivity and accuracy problems of the students＇ experiment data processing and evaluation, and avoid interference with human factors. The software has the characteristic of the easy installation, the easy operation, the strong practicability, pertinence, the systematicness and the running stability, so it provides a platform in the quantitative analysis chemistry experiment for the students＇ assessment system of automatic processing, and it has a high popularization value. The project＇s technical route design is reasonable, the research method is correct, and the experimental data processing results are reliable, which has reached the leading domestic level in the quantitative analysis chemistry experiment teaching field of computer data processing. And this project has been through the achievements appraisal of Gansu Provincial Sci. ＆ Tech. Department.