Substitution–dilution method to correct the matrix effect in multi-element quantitative analysis by X-ray fluorescence

A mathematical model based on the dilution–addition method (DAM) for multi-elemental analysis using an X-ray fluorescence technique is proposed. The conditions for sample preparation do not require both the unknown and standard samples to be similar in composition and mineralogy, and the unknown sample is replaced quantitatively by the standard sample, hence the denomination substitution–dilution method (SDM). This method makes it possible to correct the matrix effect in multi-elemental quantitative analysis by X-ray fluorescence for each analyte. The proposed model presents hyperbolic behaviour of the experimental data when the X-ray fluorescence intensities are represented versus the substitution factor (h) for each analyte. After calculating the A/B parameter relations, which depend on the X-ray fluorescence intensity of each analyte (I_i^ns) and the substitution factor (h) and determining the analyte concentration in the multi-element standard sample (C_i^p), it is possible to calculate the analyte concentration in the multi-element unknown using an algorithm suggested for this purpose. This work studies the substitution–dilution phase proposed in the method, and the factors arising from incorporation of the standard and diluent are established according to the nature of the samples and the modifications. These factors make it possible to establish the experimental interval of analyte concentration, generally narrow, which corresponds to a section of the hyperbolic function which is so short that it can be accepted as linear. This linear model can be accepted for a wide variety of samples with a diluent/sample ratio greater than 10. The proposed linear method provides satisfactory results which are comparable to those calculated by applying the hyperbolic method. The proposed method (SDM) has been applied to two different types of matrices, a binary alloy (without diluent, using the hyperbolic model) and a geological sample (with diluent, using both hyperbolic and linear models). In all cases the results were satisfactory.     

Evaluation of the interelemental effect in X-ray fluorescence analysis by the total addition method

Summary An algorithm for quantifying interelemental effects in X-ray fluorescence techniques is developed. By applying an addition process, the ratio between the mass absorption coefficients of the analyte and the unknown sample ( _i ^* / _s ^* ) is calculated to correct the fluorescence intensity of the element to be determined and linearize the I-c calibration plot. This coefficient can be calculated graphically and numerically. The method is applied to the determination of tin in lead alloys with good results over wide concentration ranges.Notation used Q Constant of proportionality in Eq. (4) X-ray fluorescence intensity of the I _i ^o standard - I _i ^s unknown sample - I _i ^ns dilute unknown sample - I _i ^ms unknown sample after addition of i analyte Corrected fluorescence intensity of the I _i ^cs unknown sample - I _i ^msc unknown sample after addition of i analyte Relationship of fluorescence intensity between R_i sample and standard - R _i dilute sample and standard Factor of f_m addition - f_x addition equivalent to the mass fraction of the i analyte in the unknown sample Mass absorption coefficient of _i ^* analyte - _s ^* unknown sample - _ms ^* unknown sample after addition Mass fraction of c _i ^s analyte - c _i ^ms unknown sample after addition     

Influence of X-ray tube spectral distribution on uncertainty of calculated fluorescent radiation intensity

The relative radiation intensity (R_i) defined as fluorescent radiation intensity of analyte in specimen to fluorescent radiation intensity of pure element or compound, e.g., oxide is used in calculation in both fundamental parameter methods and in theoretical influence coefficient algorithms. Accuracy of calculated R_i is determined by uncertainties of atomic parameters, spectrometer geometry and also by X-ray tube spectral distribution. This paper presents the differences between R_i calculated using experimental and theoretical X-ray tube spectra evaluated by three different algorithms proposed by Pella et al., Ebel, and Finkelshtein–Pavlova. The calculations are performed for the most common targets, i.e., Cr, Mo, Rh and W. In this study, R_i is calculated for V, Cr, Mn, Fe, Co, Ni, Cu and Mo in steels as an example. The differences between R_i calculated using different X-ray tube spectrum algorithms are presented when pure element standard, multielement standard similar to the analyzed material and one pure element standard for all analytes is used in X-ray fluorescence analysis. The differences between R_i for intermediate-thickness samples (and also for thin films) and for X-ray tube, which ran for many hours, are also evaluated.     

A review and tutorial discussion of noise and signal-to-noise ratios in analytical spectrometry—III. Multiplicative noises

In this review, signal-to-noise ratios are discussed in a tutorial fashion for the case of multiplicative noise. Multiplicative noise is introduced simultaneously with the analyte signal and is therefore much more difficult to reduce than additive noise. The sources of noise, the mathematical representation of noise, and the major types of noises in emission and luminescence spectrometry are discussed. If the limiting source of noise is multiplicative white noise, the signal-to-noise ratio for optimal sampling time τ_s increases as the square root of the response or integration time of the readout and is independent of the rate at which sample and reference are measured. The variation of multiplicative flicker noise with variation in sampling time, τ_s, time interval between sample and reference measurements, T, and response (τ_r) or integration (τ_i) time is discussed in some detail. The optimal system for the case of multiplicative noise is a dual channel approach in which the sample and reference are measured simultaneously and a ratio of signals is taken. Although the best reference in most cases of interest to analytical chemists is a calibration standard, it is often impossible to measure a sample and a calibration standard simultaneously and so an internal standard, a detector monitoring the source intensity, etc., may be useful.     

Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)2

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO₃)₂. The correlation coefficient of the graph plotted from the normalized absorbance signals of Bi versus Pb was r = 0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve obtained from reference solutions prepared in 0.2% (v/v) HNO₃ and analytical curves obtained from Pb additions in red and white wine vinegar samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analytical curves without. Analytical curves in the 2.5–15 μg L^− 1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analyte concentration, and typical linear correlations of r = 0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 μg L^− 1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 μg L^− 1 and the relative standard deviation was ≤ 3.8% and ≤ 8.3% (n = 12) for a sample containing 10 μg L^− 1 Pb with and without internal standard, respectively.     

Characteristics of excimer formation in langmuir-blodgett assemblies of 1-palmitoyl-2-pyrenedecanoylphosphatidylcholine and dipalmitoylphosphatidylcholine

Langmuir-Blodgett film alloys of PPDPC (1-palmitoyl-2-[10-(pyren-1-yl)]decanoyl-sn-glycero-3-phosphocholine) and DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine) were assembled in varying molar proportions on quartz glass slides. The transferred layers were then characterized according to their pyrene excimer to monomer fluorescence intensity ratio i_E/i_M and fluorescence quantum yields as a function of film composition. The observed deviation from non-ideal mixing is considered to be due to the formation of regular distribution patterns of PPDPC in a DPPC lattice. The observed critical mole fractions of PPDPC evident as steps in I_E/I_M versus X_PPDPC plots can be accounted for by a model involving a trigonal distribution of pyrenedecanoyl chains in the phospholipid acyl chain lattice. The implications of the distribution of PPDPC as superlattices to the excimer formation mechanism are discussed.     

An improved reagent for determination of aliphatic amines with fluorescence and online atmospheric chemical ionization-mass spectrometry identification

An improved reagent named 2-[2-(dibenzocarbazole)-ethoxy] ethyl chloroformate (DBCEC-Cl) for the determination of aliphatic amines by high-performance liquid chromatography (HPLC) with fluorescence detection and post-column online atmospheric chemical ionization-mass spectrometry (APCI-MS) identification has been developed. DBCEC-Cl could easily and quickly label aliphatic amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M+H]⁺ under APCI-MS in positive-ion mode. The ratios for fluorescence responses were I_DBCEC-amine/I_BCEC-amine = 1.02-1.60; I_DBCEC-amine/I_BCEOC-amine = 1.30-2.57; and I_DBCEC-amine/I_FMOC-amine = 2.20-4.12 (here, I was relative fluorescence intensity). The ratios for MS responses were IC_DBCEC-amine/IC_BCEC-amine = 4.16-29.31 and IC_DBCEC-amine/IC_BCEOC-amine = 1.23-2.47 (Here, IC: APCI-MS ion current intensity). Detection limits calculated from 0.0244 pmol injection, at a signal-to-noise ratio of 3, were 0.3-3.0 fmol. The relative standard deviations for within-day determination (n = 6) were 0.045-0.081% for retention time and 0.86-1.03% for peak area for the tested aliphatic amines. The mean intra- and inter-assay precision for all amine levels were <3.64% and 4.67%, respectively. The mean recoveries ranged from 96.9% to 104.7% with their standard deviations in the range of 1.80-2.70 (RSDs%). Excellent linear responses were observed with coefficients of >0.9991.     

A microfluidic chip based liquid-liquid extraction system with microporous membrane

A robust and simple approach for microfabricated chip based liquid-liquid extraction was developed for on-chip sample pretreatment. The chip based extraction system was composed of two microfabricated glass plates with a microporous membrane sandwiched in between. A simple bonding approach using epoxy was used to achieve bonding and sealing of the L-L extraction chip. Gravity was employed to drive the aqueous and organic flows through separate channels in the extraction system, separated by the membrane. During extraction, the analyte in an aqueous sample stream was transferred through the membrane into the organic stream. The fluorescence intensity of the analyte extracted into the organic stream was monitored in situ by a laser induced fluorescence detection system. The performance of the system was demonstrated using an aqueous solution of butyl rhodamine B (BRB) and isobutanol as sample and extractant, respectively. The system proved to be an efficient means for achieving chip based microporous membrane liquid-liquid extraction. The precision of fluorescence measurements was 1.5% R.S.D. (n = 4). A linear response range of 1 × 10⁻⁷ to 1 × 10⁻⁴ M BRB was obtained with a regression equation: I = 8.00 × 10⁶ C + 4.91. An enrichment factor of ca. 3 was obtained with an extraction efficiency of 69%.     

Liquid–liquid microextraction in a multicommuted flow system for direct spectrophotometric determination of iodine value in biodiesel

A flow-based procedure was developed for the direct spectrophotometric determination of the iodine value (IV) in biodiesel. The procedure was based on the microextraction/reaction of unsaturated compounds with triiodide ions in an aqueous medium by inserting the reagent solution between the aliquots of biodiesel without any pretreatment. The interaction occurred through the biodiesel film formed on the inner walls of the hydrophobic tube used as the reactor and at the aqueous/biodiesel interfaces. The spectrophotometric detection was based on the discoloration of the I₃⁻ reagent in the aqueous phase by using a glass tube coupled to a fiber-optic spectrophotometer as the detection cell. Reference solutions were prepared by dilution of biodiesel samples with previously determined IV in hexane. The analytical response was linear for IV from 13 to 135 g I₂/100 g with a detection limit of 5 g I₂/100 g. A coefficient of variation of 1.7% (n = 10) and a sampling rate of 108 determinations per hour were achieved by consuming 224 μL of the sample and 200 μg of I₂ per determination. The slopes of analytical curves obtained with three different biodiesel samples were in agreement (variations in slopes lower than 3.1%), thus indicating an absence of any matrix effects. Results for biodiesel samples from different sources agreed with the volumetric official procedure at the 95% confidence level. The proposed procedure is therefore a simple, fast, and reliable alternative for estimating the iodine value of biodiesel.     

Fluorometric method for the determination of hydrogen peroxide and glucose with Fe3O4 as catalyst

In this paper, we utilized the instinct peroxidase-like property of Fe₃O₄ magnetic nanoparticles (MNPs) to establish a new fluorometric method for determination of hydrogen peroxide and glucose. In the presence of Fe₃O₄ MNPs as peroxidase mimetic catalyst, H₂O₂ was decomposed into radical that could quench the fluorescence of CdTe QDs more efficiently and rapidly. Then the oxidization of glucose by glucose oxidase was coupled with the fluorescence quenching of CdTe QDs by H₂O₂ producer with Fe₃O₄ MNPs catalyst, which can be used to detect glucose. Under the optimal reaction conditions, a linear correlation was established between fluorescence intensity ratio I₀/I and concentration of H₂O₂ from 1.8 × 10⁻⁷ to 9 × 10⁻⁴ mol/L with a detection limit of 1.8 × 10⁻⁸ mol/L. And a linear correlation was established between fluorescence intensity ratio I₀/I and concentration of glucose from 1.6 × 10⁻⁶ to 1.6 × 10⁻⁴ mol/L with a detection limit of 1.0 × 10⁻⁶ mol/L. The proposed method was applied to the determination of glucose in human serum samples with satisfactory results.     

Fluorescence optosensing implemented with sequential injection analysis: a novel strategy for the determination of labetalol

The coupling of sequential injection analysis and optosensing has been developed for the first time. It has been applied to the determination of labetalol in both pharmaceuticals and urine samples, with the analytical signal (native fluorescence) being monitored directly on sensing zone microbeads. The solid support used was the nonionic silica gel C₁₈, using 20% methanol–water (v:v) as a carrier. By using a 1.5-ml sample volume , we achieved a detection limit of 3.3 ng ml⁻¹. This sensitivity allowed the determination of the compound in urine samples. A recovery study was carried out at the labetalol levels usually found in urine after pharmaceuticals administration, and recovery percentages close to 100% were obtained. The relative standard deviation was 3.4% for 100 ng ml⁻¹ labetalol. No pretreatment was needed for urine samples, only an appropriate dilution, therefore minimizing the time required per sample analysis. In addition, the determination of the analyte was also carried out in one pharmaceutical, with a satisfactory result being obtained.     

Homogeneous Fluorescence Resonance Energy Transfer Immunoassay for the Determination of Zearalenone

This study demonstrates the use of antigen-antibody binding for the detection of zearalenone. Based on the principle of the fluorescence resonance energy transfer (FRET) phenomenon between antibody and antigen, an immunoassay, in which zearalenone coupled with the anti-zearalenone antibody, was developed, optimized, and applied. Owing to intrinsic fluorescence properties in basic pH conditions with the optimal cationic surfactant, anti-zearalenone and zearalenone played roles as the respective donor and acceptor in the FRET immunoassay. As the concentration of analyte increased, the antigen/antibody emission intensity ratio (I _430 nm/I _350 nm) was enhanced due to larger amounts of zearalenone/anti-zearalenone complexes. This assay, based on the ratio of intensities (I _430 nm/I _350 nm), displayed high specificity and sensitivity with a detection limit of 0.8 ng mL^?1 for zearalenone. The results obtained from analysis of spiked wheat grain samples were found to be in good agreement with those obtained by employing a direct competitive enzyme-linked immunosorbent assay. The label-free, noncompetitive, and homogeneous FRET immunoassay strategy served as a powerful tool for the simple, rapid, and sensitive quantitative determination of zearalenone in food and feed matrices.     

Determination of naproxen with solid substrate room temperature phosphorimetry based on an orthogonal array design

A solid substrate room temperature phosphorimetric method (SSRTP) for the determination of naproxen in pharmaceutical products was developed. The experimental conditions were optimized by a L₂₅ (5⁶) orthogonal array design (OAD) with five factors at five levels using statistical analysis. The five factors contained pH value of the sample solution, drying time (t_d) and drying temperature (T_d) of solid substrate paper in the oven, concentration (c_I⁻) of heavy atom (I⁻), and exposure time (t_e) of solid substrate paper after being dried. The pH value, t_d, c_I⁻ and t_e had significant influences on the measurement of phosphorescence intensity. The optimization for sample preparation improved greatly the analytical performance of SSRTP. Under the optimal conditions, naproxen can be determined in a linear range from 10 to 400 ng ml⁻¹ with a detection limit of 2.7 ng ml⁻¹ at 3σ. The method has been applied satisfactorily to the determination of naproxen in a commercial product.     

The novel Cs4Nb6F8.5I3.5I6 octahedral niobium cluster fluoro-iodide: a step towards the Nb6F12 cluster core excision

The solid state synthesis of Cs₄Nb₆Fⁱ_8.5Iⁱ_3.5I^a₆ starting from Nb₆F₁₅ binary fluoride, as well as its crystal structure determined by X-ray single crystal diffraction, are presented in this work. This novel cluster compound is based on a Nb₆Iⁱ₃Fⁱ₆Lⁱ₃I^a₆ (L=F, I) discrete unit and crystallizes in the monoclinic system (space group C2/m; Z=4 ; a=10.4363(4) Å, b=18.1227(7) Å, c=19.5102(9) Å β=101.223(1)°, V=3619.5(3) Å³, R₁=0.057; wR₂=0.159). This halide is the first octahedral niobium cluster compound containing unshared terminal I^a ligands together with ordered μ₂-Iⁱ and μ₂-Fⁱ ligands on nine inner positions whilst the three last ones (Lⁱ) are slightly affected by a I/F random occupancy. The structural findings are discussed and compared with those of Nb₆F₁₅, Nb₆I₁₁, CsNb₆I₁₁ and the fluorochlorides and fluorobromides recently reported.     

Increasing the sensitivity of the spectrophotometric determinations of the oxygen content in YBCO superconducting samples using the I3-starch compound

The conditions for formation of the I₃⁻-starch compound and measuring its absorbance have been found, and a spectrophotometric method has been developed for the determination of the oxygen content in YBa₂Cu₃O_y superconducting bulk samples. The method involves the following stages: a decomposition of the sample in an acid medium in the presence of iodide ions under inert atmosphere; formation of a complex between Cu(II) and glycine; binding the I₃⁻-complex with a starch and the absorbance measurement of the colored I₃⁻-starch compound. The coefficient of the active oxygen is calculated by the ratio of the absorbances of two solutions and the method does not require both calibration and precise measuring sample mass. The accuracy of the results is confirmed applying the comparative spectrophotometric method that uses the yellow I₃⁻-complex. The precision of the results evaluated by the relative standard deviation is 2%. The developed method is sensitive and allows a sample mass about 2 mg to be used. The analysis is rapid and requires a simple and inexpensive apparatus. Thus the new method would be useful for an express analytical control of the oxygen content of YBCO-superconducting materials produced for the electronics.     

Laser fluorescence excitation band profiles of jet-cooled tropolone

The fluorescence excitation spectrum of the A¹B₂−X¹A₁ transition of tropolone was investigated as a function of pulsed laser intensity, I. For 0.5 < I < 4.5 MW/cm² the weak fluorescence intensity was found to increase approximately as aI + bI². The band profiles, which showed no evidence of resolvable rotational fine structure, were modeled by computations assuming a Lorentzian lineshape for the individual rotational transitions.     

Measurement of state-to-state rotational transfer rates in collision of I2*(B 0u+, υ = 15, j) with 3He, 4He,Ne, Ar,H2, D2 and I2

The selective laser excitation and induced fluorescence observation technique has been used to study rotationally inelastic collisions of I₂^*(B 0_u⁺, υ = 15,j) with I₂, ³He, ⁴He, Ne, Ar, H₂ and D₂. For each collision partner, several initial rotational levels ranging from j_i = 12 up to j_i = 146 have been excited. For purely rotational transfer within the υ = 15 level, our data are perfectly consistent with energy sudden (eventually corrected) scaling laws. Thus, any thermally averaged rate constant, k(j_i → j_f), can be expressed as a function of the basis rate constants k(l → 0). Furthermore, these k(l → 0) are found to follow simple empirical fitting laws. Consequently any k(j_i → j_f) can be predicted given a set of two or three fitting parameters. Collisions with relatively heavy particles (I₂, Ar and Ne) are well described by using the inverse power fitting law k(l → 0) = b[l(l+1)]^?γ, where b = 1.7, 1.2 and 1.2×10^?10 cm³ s^?1 and γ = 1.08, 1.02 and 1.17 for I₂^*-Ne, I₂^*-Ar and I₂^*-I₂ collisions respectively. For collisions with light particles (³He, ⁴He, H₂ and D₂), k(l → 0) shows a sharp decrease with l which can be accounted for by a hybrid power-exponential fitting law k(l → 0) = b[l(l+1)]^?γ exp[-l(l+1)/l^* (l^*+1)], where b = 0.84, 0.71, 2.77 and 2.78×10^?10 cm³ s^?1l⁺ = 20.6, 23.1, 18.8 and 31.4, and γ = 0.66, 0.66, 0.78 and 0.91 for I₂^*-³He, I₂^*-He, I₂^*-H₂ and I₂^*-D₂ collisions, respectively. We confirm that the rotational transfer dynamics in heavy molecules is mainly governed by angular momentum exchange.     

Error of sample preparation in pressing emitters for X-ray fluorescence analysis

When determining element concentrations in geological samples by X-ray fluorescence spectrometry using emitters obtained by pressing tablets from powder samples, we revealed the effect of a significant difference in line intensities of characteristic long-wavelength emission (ΔI _i) from opposite sides of the emitter. The effects of compacting pressure, mass of emitter, and its surface area on ΔI _i were investigated. It was shown that the account of this effect can reduce the error of sample preparation in using compacting pressures lower than 20 t.     

Specific features of matrix correction in the X-ray fluorescence analysis of samples of widely varied composition

The authors critically analyze the paper “Corrections for matrix effects in X-ray fluorescence analysis” [1], which was declared by R. Rousseau as a tutorial but contains some inaccuracies. Conclusions are confirmed by the results of experiments and theoretical calculations. It is shown that uniform linear calibration function I _i /I _i ^m = f(R _i ^th ) can hardly be obtained for test samples of any composition because of the difference in their microstructure and the variation of the background. At the same time, in the XRF analysis of multicomponent materials, such as steels, the Lucas-Tooth and Jongh equations provide a good alternative to the Rousseau algorithm.     

A convenient and label-free fluorescence “turn off–on” nanosensor with high sensitivity and selectivity for acid phosphatase

In this study, we reported a convenient label-free fluorescence nanosensor for rapid detection of acid phosphatase on the basis of aggregation-caused quenching (ACQ) and enzymolysis approach. The selectivity nanosensor was based on the fluorescence “turn off–on” mode, which possessed high sensitivity features. The original strong fluorescence intensity of CuInS₂ QDs was quenched by sodium hexametaphosphate (NaPO₃)₆. The high efficiency of the quenching was caused by the non-covalent binding of positively charged CuInS₂ QDs to the negatively charged (NaPO₃)₆ through electrostatic interactions, aggregating to form a CuInS₂ QDs/(NaPO₃)₆ complex. Adding acid phosphatase caused intense fluorescence of CuInS₂ QDs/(NaPO₃)₆ to be recovered, and this was because of enzymolysis. (NaPO₃)₆ was hydrolyzed into small fragments and the high negative charge density decreased, which would weaken the strong electrostatic interactions. As a result, the quenched fluorescence “turned on”. Under the optimum conditions, there was a good linear relationship between I/I₀ (I and I₀ were the fluorescence intensity of CuInS₂ QDs/(NaPO₃)₆ system in the presence and absence of acid phosphatase, respectively) and acid phosphatase concentration in the range of 75–1500 nU mL⁻¹ with the detection limit of 9.02 nU mL⁻¹. The proposed nanosensor had been utilized to detect and accurately quantify acid phosphatase in human serum samples with satisfactory results.