A data selection method for matrix effects and uncertainty reduction for laser-induced breakdown spectroscopy

Severe matrix effects and high signal uncertainty are two key bottlenecks for the quantitative performance and wide applications of laser-induced breakdown spectroscopy(LIBS).Based on the understanding that the superposition of both matrix effects and signal uncertainty directly affects plasma parameters and further influences spectral intensity and LIBS quantification performance,a data selection method based on plasma temperature matching(DSPTM)was proposed to reduce both matrix effects and signal uncertainty.By selecting spectra with smaller plasma temperature differences for all samples,the proposed method was able to build up the quantification model to rely more on spectra with smaller matrix effects and signal uncertainty,therefore improving final quantification performance.When applied to quantitative analysis of the zinc content in brass alloys,it was found that both accuracy and precision were improved using either a univariate model or multiple linear regression(MLR).More specifically,for the univariate model,the root-mean-square error of prediction(RMSEP),the determination coefficients(R^(2))and relative standard derivation(RSD)were improved from 3.30%,0.864 and 18.8%to 1.06%,0.986 and 13.5%,respectively;while for MLR,RMSEP,R^(2)and RSD were improved from 3.22%,0.871 and 26.2%to 1.07%,0.986 and 17.4%,respectively.These results prove that DSPTM can be used as an effective method to reduce matrix effects and improve repeatability by selecting reliable data.

Matrix effect suppressing in the element analysis of soils by laser-induced breakdown spectroscopy with acoustic correction

Laser-induced breakdown spectroscopy(LIBS)has been used for soil analysis,but its measurement accuracy is often influenced by matrix effects of different kinds of soils.In this work,a method for matrix effect suppressing was developed using laser-induced plasma acoustic signals to correct the original spectrum,thereby improving the analysis accuracy of the soil elements.A good linear relationship was investigated firstly between the original spectral intensity and the acoustic signals.The relative standard deviations(RSDs)of Mg,Ca,Sr,and Ba elements were then calculated for both the original spectrum and the spectrum with the acoustic correction,and the RSDs were significantly reduced with the acoustic correction.Finally,calibration curves of MgⅠ285.213 nm,CaⅠ422.673 nm,SrⅠ460.733 nm and BaⅡ455.403 nm were established to assess the analytical performance of the proposed acoustic correction method.The values of the determination coefficient(R~2)of the calibration curves for Mg,Ca,Sr,and Ba elements,corrected by the acoustic amplitude,are improved from 0.9845,0.9588,0.6165,and 0.6490 to 0.9876,0.9677,0.8768,and 0.8209,respectively.The values of R~2 of the calibration curves corrected by the acoustic energy are further improved to 0.9917,0.9827,0.8835,and 0.8694,respectively.These results suggest that the matrix effect of LIBS on soils can be clearly improved by using acoustic correction,and acoustic energy correction works more efficiently than acoustic amplitude correction.This work provides a simple and efficient method for correcting matrix effects in the element analysis of soils by acoustic signals.

Elimination of matrix effects during analysis of perfluorinated acids in solid samples by liquid chromatography tandem mass spectrometry

Matrix effects can significantly hamper the accuracy and precision of the analysis results of perfluorinated acids （PFAs） in environmental solid samples. Several methods, such as standard addition, isotopically labeled internal standards, clean-up of SPE （solid phase extraction） eluents by dispersive graphitized carbon sorbent and substitution of eletrospray ionization （ESI） source by atmosphere pressure photoionization （APPI） source, were demonstrated for elimination of matrix effects in quantitative analysis of PFAs in solid samples. The resuRs indicate that matrix effects can be effectively eliminated by standard addition, but instrumental analysis time will be multiplied. Isotopically labeled internal standards can effectively negate matrix effects of PFAs with the same perfluorocarbon chain length, but is not valid for the other analytes. Although APPI can eliminate matrix effects for all analytes, it is only suitable for analysis of high pollution levels samples. Clean-up of SPE eluents by dispersive graphitized carbon sorbent not only effectively negate the impact of matrix effect, but also avoid frequent clean of the ESI in order to maintain instrumental sensitivity. Therefore, the best method for elimination of matrix effects is the usage of dispersive graphitized carbon sorbent for clean-up of SPE elution.

Matrix Effects of Fourteen Organophosphorus Pesticides Residues in Nine Kinds of Vegetable Matrices

The matrix effects of 14 organophosphorus pesticides in 9 kinds of vegetables matrices were preliminarily studied by gas chromatography/flame photomet- ric detection（FPD） in the paper. The matrix effects of 14 organophosphoms pesticides in 9 kinds of vegetable matrices at 0.05, 0.1 and 0.2 mg/L were compared, respectively. The results showed that matrix enhancement effect and matrix attenuation effect existed in all cases, while matrix effects did not have strong correlation with concentrations of pesticides, but were related to species of vegetables and structure and polarity of pesticides.

Types and Correction Methods of Matrix Effect during Zircon LA-ICP-MS U-Pb Dating

Matrix effect primarily impacts the accuracy and precision of zircon LA-ICP-MS U-Pb data.This paper describes three types of matrix effect in zircon LA-ICPMS U-Pb dating,i.e.,the element matrix effect,high Ddpa or uranium matrix effect and alpha dose matrix effect,and illustrates the correction of these three effects.In addition,we point out the limitation and possible problems of the existing correction methods.

Advance in Matrix Effect Study of LA-MC-ICPMS U-Pb Dating on U-Bearing Oxide Minerals

Objective With the development of analytic technologies, in-situ dating on U-bearing oxide minerals （e.g., cassiterite, rutile and baddeleyite） has been widely used in geological chronological researches and has attracted remarkable attention to explore evolution of the earth and obtain age information of various geological processes. Matrix effect related studies are especially important during in-situ U- Pb dating based on Laser Ablation Multiple Collector Inductively Coupled Plasma Mass Spectrometry （LA-MC- ICPMS）. However, to our knowledge, only few thorough and systematical matrix effect study of U-bearing oxide minerals has been reported. In this study, we systematically analyzed the matrix effect of U-bearing oxide minerals in order to take place the standards which are difficult to prepare with available standards.

Three-dimensional aspects of formulation excipients in drug discovery:a critical assessment on orphan excipients,matrix effects and drug interactions

Formulation/pharmaceutical excipients play a major role in formulating drug candidates,with the objectives of ease of administration,targeted delivery and complete availability.Many excipients used in pharmaceutical formulations are orphanized in preclinical drug discovery.These orphan excipients could enhance formulatability of highly lipophilic compounds.Additionally,they are safe in preclinical species when used below the LD50 values.However,when the excipients are used in formulating compounds with diverse physico-chemical properties,they pose challenges by modulating study results through their bioanalytical matrix effects.Excipients invariably present in study samples and not in the calibration curve standards cause over-/under-estimation of exposures.Thus,the mechanism by which excipients cause matrix effects and strategies to nullify these effects needs to be revisited.Furthermore,formulation excipients cause drug interactions by moderating the pathways of drug metabolizing enzymes and drug transport proteins.Although it is not possible to get rid of excipient driven interactions,it is always advised to be aware of these interactions and apply the knowledge to draw meaningful conclusions from study results.In this review,we will comprehensively discuss a)orphan excipients that have wider applications in preclinical formulations,b)bioanalytical matrix effects and possible approaches to mitigating these effects,and c)excipient driven drug interactions and strategies to alleviate the impacts of drug interactions.

A preliminary study of isopropyl alcohol matrix effect and correction in ICP-MS

Isopropyl alcohol matrix effect was found to be element specific by using the defined matrix effect factor in ICP-MS, which could not be corrected by using the conventional internal reference method. Unlike the conventional internal reference method, the presented method allows for the analyte to behave differently from the internal reference under the influence of the matrix.

Investigation of matrix effects in the MC-ICP-MS induced by Nb, W, and Cu: Isotopic case studies of iron and copper

Some elements normally occur at trace levels while the majority of natural geological materials may be exceedingly enriched in some special cases, such as the Bayan Obo ore deposit where REE and Nb are extremely enriched. These elements may not be removed completely during purification. Therefore, matrix effects will be caused during stable isotope ratio measurement in the MC-ICP-MS. Experiments have shown that the established methods of chromatographic separation of Cu, Fe, and Zn using AG MP-1 Anion Exchange Resin cannot make ef-fective separation of Nb, W, and Cu from Fe using 20 mL 6 M HCl. It is also observed that the elution curves of W and Cu overlap at working conditions and thus W is present in measurable amounts in some sample solutions. Matrix effects in the MC-ICP-MS induced by Nb, W, and Cu during Fe isotope ratio measurements and by W during Cu isotope ratio measurements were thus investigated by examining their changes in delta values between doped and undoped standards. The results show that the effects of the matrix elements Nb, W, or Cu on Fe isotope ratio measurements are minimal in the case of m(Nb)/m(Fe)<0.005, m(W)/m(Fe)<0.01, or m(Cu)/m(Fe)<0.6. This finding, combined with the extremely low levels of W and Cu, and the fact that nearly 90% of Nb can be removed during purification, demonstrates that the methods of chromatographic separation of Fe established before are suitable for Bayan Obo ore samples and that the methods can be simplified when Cu elution is unnecessary. The effects of the matrix element W on Cu isotope determinations are minimal in the case of m(W)/m(Cu)<0.7. Therefore, W exerts no significant effect on the measurements of Cu isotopes for the majority of natural geological materials.

Neural network-based matrix effect correction in EDXRF analysis

In this paper we discuss neural network-based matrix effect correction in energy dispersive X-ray fluorescence (EDXRF) analysis,with detailed algorithm to classify the samples.The method can correct the matrix effect effectively through classifying the samples automatically,and influence of X-ray absorption and enhancement by major elements of the samples is reduced.Experiments for the complex matrix effect correction in EDXRF analysis of samples in Pangang showed improved accuracy of the elemental analysis result.

Effect of parameter setting and spectral normalization approach on study of matrix effect by laser induced breakdown spectroscopy of Ag–Zn binary composites

The complex nature of laser-material interaction causes non-stoichiometric ablation of alloy samples.This is attributed to matrix effect, which reduces analyzing capability. To address this issue, the analytical performance of three different normalization methods, namely normalization with background, internal normalization and three point smoothing techniques at different parameter settings is studied for quantification of Ag and Zn by Laser induced breakdown spectroscopy(LIBS).The LIBS spectra of five known concentration of silver zinc binary composites have been investigated at various laser irradiances(LIs). Calibration curves for both Ag(I) line(4d^(10)5s^2S_(1/2)→4d^(10)5p^2P_(1/2) at 338.28 nm) and Zn(I) line(4s5s^3S_1→4s4p^3P_2 at 481.053 nm) have been determined at LI of 5.86?×?10^(10)W cm^(-2). Slopes of these calibration curves provide the valuation of matrix effect in the Ag–Zn composites. With careful sample preparation and normalization after smoothing at optimum parameter setting(OPS), the minimization of sample matrix effect has been successfully achieved. A good linearity has been obtained in Ag and Zn calibration curve at OPS when normalized the whole area of spectrum after smoothing and the obtained coefficients of determination values were R^2?=?0.995 and 0.998 closer to 1. The results of matrix effect have been further verified by analysis of plasma parameters. Both plasma parameters showed no change with varying concentration at OPS. However, at high concentration of Ag, the observed significant changes in both plasma parameters at common parameter setting PS-1 and PS-2 were the gesture of matrix effect. In our case, the better analytical results were obtained at smoothing function with optimized parameter setting that indicates it is more efficient than normalization with background and internal normalization method.

A Pragmatic Approach to Coping with Matrix Effects during ICP-MS Analysis of Trace Elements in Silicate Rocks and Calibration of REE Interferences

Operating an Agilent 7700X ICP-MS spectrometer under robust plasma conditions (1550 W) with a He-filled octopole collision cell and analysing solutions (?1 total dissolved solids) still suffered analyte peak suppression due to matrix effects. International reference rocks BCR-1, BHVO-1, AGV-1, G-2 and BCR-2 all showed count rate reductions for 36 elements (mass range 7Li to 238U) averaging ~10% but with no dependence on isotope mass. Use of an internal standard (103Rh) and/or using a ten-fold dilution of sample solutions reduced these effects but problems with reduced count rates combined with larger errors for some elements introduced other problems. The best approach was to normalise the count rates for each element in the other samples against those for BCR-1 as an external standard;thus the count suppression due to the matrix effect is corrected for each individual element. This approach provides standardization “traceability” in line with the ERM ISO/IEC requirement. Experiments are also reported on quantifying the proportions of Ba and selected REE oxide/hydroxide components versus parent isotopes (XO/X and XOH/X). This information is essential for correcting peak interferences on higher mass number REE for the rock samples, and equations are developed to use measured CeO/Ce and CeOH/Ce ratios to predict such values for any other member of the REE suite. Concentrations obtained show excellent agreement with recommended values for the international reference materials especially for the REE. Robust data are also provided for two other standard rocks: nepheline syenite STM-1 and quartz syenite CAAS-1;the latter shows exceptional enrichments of Zr, REE, Th, and U.

<i>In Situ</i>Analysis of Copper Alloys by Femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry: Constrains on Matrix Effects

Direct analysis of copper-base alloys using laser ablation techniques is an increasingly common procedure in cultural heritage studies. However, main discussions remain focused on the possibility of using non-matrix matched external reference materials. To evaluate the occurrence of matrix effects during in situ microanalysis of copper-base materials, using near infrared femtosecond laser ablation techniques (NIR fs-LA-ICP-MS), two bronzes, i.e., (Sn-Zn)-ternary and (Sn)-binary copper-matrix reference materials, as well as a reference synthetic glass (NIST-SRM-610) have been analyzed. The results have been compared to data obtained on a sulfide-matrix reference material. Similar values in relative sensitivity averages of 63Cu, 118Sn and 66Zn, as well as in 118Sn/63Cu and 66Zn/63Cu ratios were obtained, for all analyzed matrix types, i.e., copper-base-, silicate-, and sulfide-reference materials. Consequently, it is possible to determinate major and minor element concentrations in copper alloys, i.e., Cu, Sn and Zn, using silicate and sulfide reference materials as external calibrators, without any matrix effect and over a wide range of concentrations (from wt.% to ppm). Equally, Cu, Sn and Zn concentrations can be precisely determined in sulfides using homogeneous alloys (reference) materials as an external calibrator. Thus, it is possible to determine Cu, Sn and Zn in copper-base materials and their ore minerals, mostly sulfides, in a single analytical session, without requiring specific external calibrators for each matrix type. In contrast, immiscible elements in copper matrix, such as Pb and Fe show notable differences in their relative sensitivity values and ratios for different matrix-materials analyzed, implying that matrix-matched external calibrations remain to be applied for their trace quantification.

Effect of matrix thermal properties on laser-induced plasma

The matrix thermal properties have an important impact on laser-induced plasma,as the thermal effect dominates the interaction between ns-pulsed laser and matter,especially in metals.We used a series of pure metals and aluminum alloys to measure plasma temperature and electron density through laser-induced breakdown spectroscopy,in order to investigate the effect of matrix thermal properties on laser-induced plasma.In pure metals,a significant negative linear correlation was observed between the matrix thermal storage coefficient and plasma temperature,while a weak correlation was observed with electron density.The results indicate that metals with low thermal conductivity or specific heat capacity require less laser energy for thermal diffusion or melting and evaporation,resulting in higher ablation rates and higher plasma temperatures.However,considering ionization energy,thermal effects may be a secondary factor affecting electron density.The experiment of aluminum alloy further confirms the influence of thermal conductivity on plasma temperature and its mechanism explanation.

Matrix Effect on Polydiarylfluorenes Electrospun Hybrid Microfibers: From Morphology Tuning to High Explosive Detection Efficiency

Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.

Flatness Control Based on Dynamic Effective Matrix for Cold Strip Mills

Steel strips are the main of steel products and flatness is an important quality indicator of steel strips. Flatness control is the key and highly difficult technique of strip mills. The bottle-neck restricting the improvement of flatness control techniques is that the research on flatness theories and control mathematic models is not in accordance with the requirement of technique developments. To build a simple, rapid and accurate explicit formulation control model has become an urgent need for the development of flatness control technique. This paper puts forward the conception of dynamic effective matrix based on the effective matrix method for flatness control proposed by the authors under the consideration of the influence of the change of parameters in roiling processes on the effective matrix, and the concept is validated by industrial productions. Three methods of the effective matrix generation are induced： the calculation method based on the flatness prediction model; the calculation method based on the data excavation in rolling processes and the direct calculation method based on the network model. A fuzzy neural network effective matrix model is built based on the clusters, and then the network structure is optimized and the high-speed-calculation problem of the dynamic effective matrix is solved. The flatness control scheme for cold strip mills is proposed based on the dynamic effective matrix. On stand 5 of the 1 220 mm five-stand 4-high cold strip tandem mill, the industrial experiment with the control methods of tilting roll and bending roll is done by the control scheme of the static effective matrix and the dynamic effective matrix, respectively. The experiment result proves that the control effect of the dynamic effective matrix is much better than that of the static effective matrix. This paper proposes a new idea and method for the dynamic flatness control in the rolling processes of cold strip mills and develops the theory and model of the flatness control effective matrix method.

Effect of Sample Matrix on Radial and Axial Profiles of Ion Abundance in Inductively Coupled Plasma Mass Spectrometry

In inductively coupled plasma mass spectrometry (ICP-MS) analysis, only a few options are available to deal with non-spectroscopic interferences. Considering that diluting the sample is impractical for traces analysis, other alternatives must be employed. Traditionally, the method of standard additions is used to correct the matrix effect but it is a time consuming method. Others methods involves separation techniques. Another way to overcome matrix interferences is to understand the mechanism involved and adjust plasma viewing conditions to reduce or eliminate the effect. In this study, the effect of various concomitant elements in ICP-MS was assessed by measuring the distribution of selected singly charged analyte ions (Al, V, Cr, Mn, Ni, Co, Cu, Zn, As, In, Ba, La, Ce, Pb), doubly charged ions (La, Ce, Ba and Pb) and oxides ions (BaO) in the presence of concomitant elements spanning a mass range from 23 (Na) to 133 (Cs) u.m.a. and different ionization energies. Concomitant elements are alkali metals, alkaline earth metals and Si. Analyte ion suppression was observed while moving the ICP across and away from the sampling interface with or without a single concomitant element. Matrix effect measures were realised, firstly, to highlight the relation between the signal extinction of an analyte and the masse of the concomitant element, and secondly to highlight the relation between the removal of the analyte signal and the first ionization energy of the element of matrix. A dependence upon both the mass of the matrix element and the mass of the analyte was observed. The suppression seems increased with increasing matrix element mass and decreased with increasing analyte mass. The effect of the mass of the matrix element was the more significant of the two factors. If space-charge effects were found to be significant for matrix elements of much lower mass, it seems diffusion also played an active part for heavier matrix elements. Finally, some evidence was found for a shift in ion-atom equilibrium for dications and for energy demand regarding oxides.

Thermal resistance matrix representation of thermal effects and thermal design of microwave power HBTs with two-dimensional array layout

Based on the thermal network of the two-dimensional heterojunction bipolar transistors(HBTs) array, the thermal resistance matrix is presented, including the self-heating thermal resistance and thermal coupling resistance to describe the self-heating and thermal coupling effects, respectively.For HBT cells along the emitter length direction, the thermal coupling resistance is far smaller than the self-heating thermal resistance, and the peak junction temperature is mainly determined by the self-heating thermal resistance.However, the thermal coupling resistance is in the same order with the self-heating thermal resistance for HBT cells along the emitter width direction.Furthermore, the dependence of the thermal resistance matrix on cell spacing along the emitter length direction and cell spacing along the emitter width direction is also investigated, respectively.It is shown that the moderate increase of cell spacings along the emitter length direction and the emitter width direction could effectively lower the self-heating thermal resistance and thermal coupling resistance,and hence the peak junction temperature is decreased, which sheds light on adopting a two-dimensional non-uniform cell spacing layout to improve the uneven temperature distribution.By taking a 2 × 6 HBTs array for example, a twodimensional non-uniform cell spacing layout is designed, which can effectively lower the peak junction temperature and reduce the non-uniformity of the dissipated power.For the HBTs array with optimized layout, the high power-handling capability and thermal dissipation capability are kept when the bias voltage increases.

Effects of Solid Matrix and Porosity of Porous Medium on Heat Transfer of Marangoni Boundary Layer Flow Saturated with Power-Law Nanofluids

The effect of the solid matrix and porosity of the porous medium are first introduced to the study of power-law nanofluids, and the Marangoni boundary layer flow with heat generation is investigated. Two cases of solid matrix of porous medium including glass balls and aluminum foam are considered. The governing partial differential equations are simplified by dimensionless variables and similarity transformations, and are solved numerically by using a shooting method with the fourth-fifth-order Runge-Kutta integration technique. It is indicated that the increase of the porosity leads to the enhancement of heat transfer in the surface of the Marangoni boundary layer flow.

Preparation and Compressive Stress Effect of Polymer Matrix RE-Fe Giant Magnetostrictive Composite

Polymer matrix RE-Fe giant magnetostrictire composite （GMPC） was prepared using bonding and magnetic field forming technique, and magnetostriction of samples was measured for different compressive stress. The experimental results show thai there is certain compressive effect in GMPC. And the influence of compressive stress on magnetostriction of sample was investigated. It offers essential reference for application and device design of GMPC.