Simultaneous determination of tantalum and hafnium in silicates by neutron activation analysis

A neutron activation procedure suitable for the routine determination of tantalum and hafnium in silicates is described. The irradiated sample is fused with sodium peroxide and leached, and the insoluble hydroxides are dissolved in dilute hydrofluoric acid-hydrochloric acid. After LaF₃ and AgCl scavenges, tantalum and hafnium are separated by anion exchange. Tantalum is obtained radiochemically pure; ²³³Pa and ⁹⁵Zr contaminants in the hafnium fraction are resolved by γ-ray spectrometry. The chemical yield of the procedure is detemined after counting by re-irradiation. Values for the 8 U.S. Geological Survey standard rocks are reported.     

Neutron activation analysis of scandium

A neutron activation method is proposed for the determination of trace quantities of scandium, down to submicrogram level, in rocks, ores and meteorites. The sample and standard are irradiated intermittently for a total of 30 h, at a neutron flux of 5·10¹¹ n/cm²/sec; the radiochemical separation consists essentially of a one-step anion exchange. The induced γ-activity of ⁴⁰Sc, 85 days, isolated from the sample is measured and compared with that of a standard. The chemical yield averages 85% and there is a considerable saving of time in the radiochemical work. Results are quoted for the scandium contents of 2 standard rocks, cassiterite and several stony meteorites. Details of conflicting nuclear reactions are also given.     

Near-infrared spectroscopic determination of human serum albumin, γ-globulin, and glucose in a control serum solution with searching combination moving window partial least squares

Near-infrared (NIR) spectra in the region of 5000-4000 cm⁻¹ with a chemometric method called searching combination moving window partial least squares (SCMWPLS) were employed to determine the concentrations of human serum albumin (HSA), γ-globulin, and glucose contained in the control serum IIB (CS IIB) solutions with various concentrations. SCMWPLS is proposed to search for the optimized combinations of informative regions, which are spectral intervals, considered containing useful information for building partial least squares (PLS) models. The informative regions can easily be found by moving window partial least squares regression (MWPLSR) method. PLS calibration models using the regions obtained by SCMWPLS were developed for HSA, γ-globulin, and glucose. These models showed good prediction with the smallest root mean square error of predictions (RMSEP), the relatively small number of PLS factors, and the highest correlation coefficients among the results achieved by using whole region and MWPLSR methods. The RMSEP values of HSA, γ-globulin, and glucose yielded by SCMWPLS were 0.0303, 0.0327, and 0.0195 g/dl, respectively. These results prove that SCMWPLS can be successfully applied to determine simultaneously the concentrations of HSA, γ-globulin, and glucose in complicated biological fluids such as CS IIB solutions by using NIR spectroscopy.     

Measurement of neutron-capture cross section and capture γ-ray spectrum of 105Pd(n,γ)106Pd reaction

We measured the neutron-capture cross section and the capture γ-ray spectrum of the ¹⁰⁵Pd(n,γ)¹⁰⁶Pd reaction with about 550 keV neutrons produced from the ⁷Li(p,n)⁷Be reaction at a 3-MV Pelletron accelerator. The capture yields of the palladium or gold sample were obtained by applying a pulse-height weighting technique to the corresponding net capture γ-ray pulse-height spectra. The neutron-capture cross section of the ¹⁰⁵Pd(n,γ)¹⁰⁶Pd reaction was determined with errors less than 5 % by using the standard capture cross sections of ¹⁹⁷Au. The neutron-capture γ-ray spectrum was obtained by unfolding the observed capture γ-ray pulse-height spectra. Theoretical calculations of cross sections and γ-ray spectra with the Empire code have been performed by utilizing the Hauser-Feshbach statistical model. The calculated results have a good agreement with present measurements.     

Neutron activation analysis of copper in bismuth by γ, γ-coincidence measurement

Copper was determined non-destructively by neutron activation analysis in high-purity bismuth down to concentrations of 30 p.p.b. By using γ, γ-coincidence counting of the annihilation photons of ⁶⁴Cu, interferences from the bremsstrahlung of the matrix could be completely suppressed, together with the interferences due to the induced γ-activities of other impurities as Zn, Cd, Au, Ag, Sb and As.The accuracy of the method was tested by spectrophotometry and by destructive activation analysis. The technique was applied to the analysis of a high-purity bismuth rod.     

Measurement of uranium in small quantities in phosphates by use of γ-ray spectrometry and the 1001 keV peak of <Superscript>234m</Superscript>Pa

Phosphates, naturally containing trace amounts of uranium, were examined using direct γ-ray spectrometry. Both normal and Compton-suppressed counting modes were utilized. The 1001 keV photo peak of the second daughter of ²³⁸U was chosen because of its isolation from other, potentially interfering peaks. The findings suggest that with the aid of Compton suppression, it is possible to quantify low uranium levels in phosphates using samples sizes of order 10 grams within an accuracy of 5%. The uranium content was determined in several sample types and was found to range from 60±4 to 70±8 μg/g, depending on the sample composition. This investigation also considered the effects of sample size, counting time, and counting technique as sources of precision maximization. This work has shown that only a small amount of phosphate is needed to determine the constituent concentration, instead of the standard several hundred grams of material.     

Rapid Analysis of Trace Quantities (1 PPM) of Bromide in Natural Water

Abstract

An analytical procedure for the rapid assay of trace quantities of bromide ion is described. An exchange resin contained in a filter disk is used to separate the ion and the bromide concentration is then measured as an emission intensity on the x-ray spectrograph. Analytical error is estimated at 5% and 0.05 ppm Br is the statistical detectability limit when compared with a standard disk containing 100 ppm Br^?.     

Solid sampling Fourier transform infrared determination of Mancozeb in pesticide formulations

A series of approaches have been assayed for FTIR determination of Mancozeb in several solid commercial fungicides using different calibration strategies. The simplest procedure was based on the use of the ratio between the absorbance of a characteristic band of Mancozeb and that of a KSCN internal standard measured in the FTIR spectra obtained from KBr pellets. It was employed the quotient between peak height absorbance values at 1525 cm⁻¹ for Mancozeb and 2070 cm⁻¹ for KSCN. In these conditions a precision as relative standard deviation (RSD) of 0.6% and a relative accuracy error of 0.8% (w/w) were found. For complex formulations, containing other compounds with characteristic absorption bands at different wavenumbers than Mancozeb, one of them was used as internal reference being employed the standard addition approach. In this case, the Mancozeb bands at 1525 cm⁻¹ or at 1289 cm⁻¹ were employed, being used the ferrocyanide band at 2075 cm⁻¹ as internal reference. RSD values between 0.7-1.4% and a relative accuracy error of 3% (w/w) were found. A third strategy was based on the use of partial least squares (PLS) calibration. A reference set was prepared mixing Mancozeb, Kaolin, Cymoxanil and KBr, being predicted the Mancozeb concentration in pesticide formulations by using the quotient between absorbance bands of Mancozeb and those of Cymoxanil. In these conditions a relative accuracy error of 0.6% (w/w) and a relative standard deviation of 1.3% were found.     

主成分-人工神经网络在近红外光谱定量分析中的应用

近红外光谱的主成分由非线性迭代偏最小二乘法（ＮＩＰＡＬＳ）求出。主成分作标准化处理后,作为Ｂ－Ｐ神经网络的输入结点进行非线性迭代。该法的优点是,充分利用了全光谱的数据,得到消除噪声后的最佳主成分,能建立非线性模型,Ｂ－Ｐ神经网络迭代时间显著缩短。用该法对大麦中的淀粉含量进行了定量分析研究。结果为：校准和预测的相关系数分别为０．９８１和０．９５３,校准和预测的相对标准偏差分别为１．７０％和２．４８％。     

Isotope ratios and abundance sensitivity obtained with an inductively coupled plasma-time-of-flight mass spectrometer

Isotope ratios and abundance sensitivities have been determined with an inductively coupled plasma-time-of-flight mass spectrometer (ICP-TOFMS). Abundance sensitivities are at least in the 10⁶ range for low abundance ions that precede high abundance ions. Three methods of detection for isotope-ratio measurement have been compared. The three systems involve gated detection followed by analog integration, analog averaging, or ion counting. Gated ion counting offers excellent precision—between 0. 64 and 1. 00% relative standard deviation (RSD). These values approach those predicted from counting statistics and are comparable to those reported for other inductively coupled plasma-mass spectrometry (ICP-MS) instruments. In addition, a greater number of accumulated counts or longer analysis times would afford precisions of 0. 1% with stable gating electronics. The accuracy of the counting method is in the 1–10% range if no correction for mass bias is performed. However, this ion counting method suffers from a limited dynamic range due to pulse pileup. Constant-fraction discrimination gated integration and commercial boxcar averager techniques offer a broader dynamic range because of their analog nature, but the attainable RSD values are limited by drift in the detection systems and by the methods employed to calculate an accurate ratio. Overall, mass bias in the ICP-TOFMS is more severe than previous work in ICP-MS due primarily to detection system bias.     

Comparison between ordinary least squares regression and weighted least squares regression in the calibration of metals present in human milk determined by ICP-OES

In this study we compared the use of ordinary least squares and weighted least squares in the calibration of the method for analyzing essential and toxic metals present in human milk by ICP-OES, in order to avoid systematic errors in the measurements used. Human milk samples were provided by maternity clinic Odete Valadares and digested by means of a high-performance microwave (MW) oven. Evaluation of plasma short and long-term stability was made using a solution of digested milk (1:50) with 2.0 mg L⁻¹ Mg in HNO₃ 2% (v/v). The detection power resulted to be at or below the μg L⁻¹ level, whilst the precision expressed as relative standard deviation R.S.D. was almost always equal to or better than 3.3%. Certified reference material Infant Formula (NIST SRM 1846) was used to assess the accuracy of the proposed method, which proved to be accurate and precise. Recovery rates were in the range of 83-117%. Aqueous calibration was carried out for each element under study.     

Liquid scintillation counting of radionuclides emitting high-energy beta radiation

Liquid scintillation counting of radionuclides emitting beta radiation with E_max>2 MeV has been investigated. Fluor volume effects were similar to those for low energy beta radiation, and pulse height spectra broadened in a predictable manner with no pulse clipping up to 4.913 MeV. Large changes in sample channels ratio due to color quenching resulted in progressively smaller losses of counting efficiency as beta energy increased. Counting efficiences were estimated to be near 100 percent for³⁴Cl^m,³⁶Cl,³²P and³⁸Cl. Cerenkov counting of³⁸Cl by liquid scintillation counter was volume dependent for both counting efficiency and pulse height spectrum. Counting efficiencies for³⁴Cl^m,³⁶Cl,³²P and³⁸Cl were estimated to be 57.0, 7.5, 42.7 and 66.3%, respectively. Pulse height spectra were shifted to greater pulse heights as a function of beta E_max, supporting the possibility of energy discrimination for beta emitters by Cerenkov pulse height spectrum analysis. The advantage of singles Cerenkov counting over coincidence Cerenkov counting was greatest for³⁶Cl and least for³⁸Cl; this advantage was amplified more for samples of³⁶Cl which had been color quenched than for similarly quenched samples of³⁸Cl or³²P.     

Quantitative determination of sodium perborate and sodium percarbonate in detergent powders by infrared spectrometry

Sodium perborate (SPB) and sodium percarbonate (SPC) are solid compounds which act as sources of H₂O₂ in solution for stain bleaching, being considered as oxidizing agents in washing powder. This research deals with the quantitative determination of SPB and SPC by an analytical procedure based on attenuated total reflectance Fourier transform infrared spectrometry, utilizing partial least squares for data processing in the 1600-800 cm⁻¹ spectral region. The statistical parameters such as R ², standard error of prediction and relative standard deviation have been evaluated, while number of factors, number of scans and resolution were optimized. The standard deviation of method was 0.006 and 0.010 for SPC and SPB, respectively.     

Simultaneous determination of tin, germanium and molybdenum by diode array detection-flow injection analysis with partial least squares calibration model

Simultaneous determination of tin, germanium and molybdenum in food samples has been established by flow injection-charge coupled detector (CCD) diode array detection spectrophotometry with partial least squares (PLS) algorithm. The method was based on the chromogenic reaction of metal ions and salicylflurone in the presence of cetyltrimethyl ammonium bromide. The overlapping spectra of these complexes are collected by CCD diode array detector and the multi-wavelength absorbance data are processed using partial least squares algorithm. The reaction conditions and analytical parameters of flow injection analysis have been investigated. The method was applied to directly determine Ge, Mo and Sn in several food samples after digestion with satisfactory results. The recoveries of spiked samples were 80.0-102.0% for tin, 86.3-92.0% for germanium and 83.2-95.2% for molybdenum, and the relative standard deviations for samples were 4.4-7.8%. Molybdenum in certified reference material of cattle liver was determined by the proposed method (n=8). The differential values between determined and guarantee values were within the given uncertain value ranges (t=1.687, P>0.05 for t-test). The samples of mung bean, kelp and pork liver were analyzed by the proposed method and inductively couple plasma-atomic emission spectroscopy (ICP-AES) method. The determination results of the two methods are in good agreement. The sampling rate is 30 samples h⁻¹.     

Direct rapid analysis of trace bioavailable soil macronutrients by chemometrics-assisted energy dispersive X-ray fluorescence and scattering spectrometry

Precision agriculture depends on the knowledge and management of soil quality (SQ), which calls for affordable, simple and rapid but accurate analysis of bioavailable soil nutrients. Conventional SQ analysis methods are tedious and expensive. We demonstrate the utility of a new chemometrics-assisted energy dispersive X-ray fluorescence and scattering (EDXRFS) spectroscopy method we have developed for direct rapid analysis of trace ‘bioavailable’ macronutrients (i.e. C, N, Na, Mg, P) in soils. The method exploits, in addition to X-ray fluorescence, the scatter peaks detected from soil pellets to develop a model for SQ analysis. Spectra were acquired from soil samples held in a Teflon holder analyzed using ¹⁰⁹Cd isotope source EDXRF spectrometer for 200 s. Chemometric techniques namely principal component analysis (PCA), partial least squares (PLS) and artificial neural networks (ANNs) were utilized for pattern recognition based on fluorescence and Compton scatter peaks regions, and to develop multivariate quantitative calibration models based on Compton scatter peak respectively. SQ analyses were realized with high CMD (R² > 0.9) and low SEP (0.01% for N and Na, 0.05% for C, 0.08% for Mg and 1.98 μg g⁻¹ for P). Comparison of predicted macronutrients with reference standards using a one-way ANOVA test showed no statistical difference at 95% confidence level. To the best of the authors’ knowledge, this is the first time that an XRF method has demonstrated utility in trace analysis of macronutrients in soil or related matrices.     

Vibrational and high pressure conformational studies of 1,1,2-trichloroethane

The infrared spectra of 1,1,2-trichloroethane were recorded from 4000 to 50 cm^?1 in the vapour and liquid states. Additional spectra above 200 cm^?1 of the low temperature crystal and of two crystalline solids, prepared by compressing the sample in a diamond anvil cell, were obtained. Also, infrared spectra of the liquid and of the compound dissolved in CS₂ were recorded at increased pressures. Raman spectral data of the liquid (including polarization measurements) and of the low temperature crystal were obtained.The fundamental frequencies for each of the two conformers, C₁ and C_s, were assigned and the results checked by normal coordinate analysis. The same diagonal and off-diagonal force constants were employed for the two conformers and the force fields were derived by means of a least squares refinement, including data for chloroethane, 1,1-dichloroethane and various deuterated species. A standard deviation of 3 % was obtained in the final fit.From the changes in relative intensities for infrared bands belonging to the C₁ and C_s conformers with increasing pressure, the volume differences (ΔV¯between the conformers were determined in CS₂ solution and in the pure liquid.     

Determination of additives in an electrolytic zinc bath by q1H-NMR spectroscopy

The use of proton nuclear magnetic resonance (¹H-NMR) for the quantification of additives in an electrolytic Zn bath is reported. A simple and quick method is described that does not need any prior sample preparation. Contrary to other analytical methods, the three additives in the bath, benzylidene acetone (BDA), benzoic acid (BA) and poly(ethylene glycol) (PE400), can be quantified. Two calibration methods were tried: integration of NMR signals with the use of an internal standard and partial least squares (PLS) regression applied to the characteristic NMR peaks. Both methods are compared and the univariate method was preferred because of simplicity, accuracy and precision. The following limits of detection were found: 0.30 g L⁻¹ BA, 0.08 g L⁻¹ BDA and 0.7 g L⁻¹ PE400 with dynamic ranges of at least 1.0–6.0, 0.1–0.6 and 3.0–18.0 g L⁻¹ respectively. Those concentration ranges are suitable to follow the concentration of additives in the bath in real time. ¹H-NMR spectra provide evidence for the BDA degradation pattern.     

Effect of Surfactant Loading on the Extraction Properties of C-18 Bonded Silica used for Solid-Phase Extraction of Phenols

ABSTRACT

A solid phase extraction (SPE) system has been modified with cationic surfactants and evaluated for extraction and preconcentration of trace phenolic compounds contaminants in water at low ppb concentrations. Cationic surfactants such as cetyl trimethyl ammonium bromide (CTAB) has been steadily adsorbed on the surface of C-18 bonded silica, and the ionized functional group of the surfactant can then act as an ion–exchange site to attract the ionized phenolic compounds from water samples. The method includes enrichment of the phenolic compounds by the surfactant-loaded solid phase extraction system, followed by elution of the analyte with methylene chloride and derivatization of the phenolic compounds with acetic anhydride. Thirty-two phenolic analytes were identified and quantitatively determined by this method; identification and quantification of the compounds is performed with GC/FID using 2-bromophenol as internal standard. SPME analysis with this method was linear over 3-6 orders of magnitude, with linear correlation coefficient (R²) greater than 0.96. Experimentally determined FID detection limits ranged from ～30 ppt for methyl-substituted phenols to ～0.1ppb for phenol and chloro-substituted phenols. We tested the influence of sample pH, the loading amount of surfactant on the solid phase, and the volume and matrixes of the sample were studied. Absolute recoveries from pure water spiked with 0.2 ppb phenolic compounds were 96 – 103%. The method has been applied to analysis of various natural waters, including ground water, lake water, seawater, and wastewater. Recoveries from ground water, lake water, seawater, and wastewater were 92 – 106%, 75 – 93%, 87 – 103%, 86 – 99%, respectively. Therefore, the new technique proved to be an excellent tool for trace enrichments of phenolic compounds at low ppb concentration of these analytes, from different natural water samples.     

A new method for simultaneous determination of 226Ra and uranium in aqueous samples by liquid scintillation using chemometrics

In this work, simultaneous determination of low levels of ²²⁶Ra and uranium in aqueous samples were performed by alpha-liquid scintillation counting (LSC) in conjunction with artificial neural network (ANN) and partial least squares (PLS). The counting rates at 73 channels, which were selected by genetic algorithm, were used for training. A PLS model with four latent variables and a principle component ANN model (4-4-2) with linear transfer function after hidden and output layers were created. Total relative error of prediction for PLS and ANN in synthetic mixtures was 18.05% and 24.78%, respectively. The matrix effect was studied by spiking the real samples with radium and uranium. Laser induced fluorescence was used for assessment of uranium prediction results in real samples.