Possible interference in the sequential voltammetric determination at trace and ultratrace concentration level of platinum group metals (PGMs) and lead : Application to environmental matrices

The present work describes a procedure for the sequential determination of Pd(II), Pt(II), Rh(III), by square wave adsorption stripping voltammetry (SWAdSV) and Pb(II) by square wave anodic stripping voltammetry (SWASV) in environmental matrices (sediments, soils and superficial water) in the presence of possible metal interferences, including high concentration ratios.The supporting electrolytes were 0.1 mol/L HCl, 0.1 mol/L HCl + 1.8 × 10⁻⁴ mol/L dimethylglyoxime (DMG) and 0.6 mmol/L formaldehyde + 1.2 mmol/L hydrazine (formazone complex) in 0.1 mol/L HCl.The voltammetric measurements were carried out using, as working electrode, a stationary hanging mercury drop electrode (HMDE), a platinum wire as auxiliary and an Ag|AgCl|KCl_sat as reference electrode.The analytical procedure was verified by the analysis of standard reference materials (CCRMP-CANMET-TDB-1 and CCRMP-CANMET-UMT-1 (rock soils), Sea Water BCR-CRM 403 and Fresh Water NIST-SRM 1643d). In the case of water standard reference materials, the solutions were spiked with known element concentrations, successively verifying the percentage recovery.In the presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique, even in the case of very high element concentration ratios.Once set up on the standard reference materials, the analytical procedure was transferred and applied to sediments, soils and superficial waters sampled in proximity of superhighway and in the Po River mouth area.A critical comparison with spectroscopic measurements is also discussed.     

粉煤灰水泥硬化浆体微结构的交流阻抗研究

采用交流阻抗方法对掺有粉煤灰的水泥硬化浆体的微结构及对不同龄期粉煤灰水泥硬化浆体的交流阻抗参数和硬化水泥浆体微结构的关系、抗压强度进行了研究,并与纯硅酸盐水泥体系进行了比较。结果表明,与纯硅酸盐水泥相比,粉煤灰水泥水化后期的水化程度较高,浆体总孔隙率较低。     

近红外光谱技术在食用油种类鉴别及脂肪酸含量检测中的应用

应用近红外光谱分析技术分别建立了快速鉴别食用植物油种类的定性分析模型以及测定食用植物油主要脂肪酸含量的定量分析模型.实验根据19份食用植物油样品的近红外光谱,结合系统聚类方法建立了纯橄榄-芝麻-花生油定性识别模型,识别率和预测率可达100%.根据59个食用植物油样品的近红外光谱,结合模型优化方法建立了食用植物油中棕榈酸、硬脂酸、油酸3种主要脂肪酸含量的近红外定量分析模型,且模型指标较好.实验表明近红外光谱分析技术在食用植物油品质快速检测领域有很好的应用前景.     

Spectroscopic determination of leaf water content using continuous wavelet analysis

The gravimetric water content (GWC, %), a commonly used measure of leaf water content, describes the ratio of water to dry matter for each individual leaf. To date, the relationship between spectral reflectance and GWC in leaves is poorly understood due to the confounding effects of unpredictably varying water and dry matter ratios on spectral response. Few studies have attempted to estimate GWC from leaf reflectance spectra, particularly for a variety of species. This paper investigates the spectroscopic estimation of leaf GWC using continuous wavelet analysis applied to the reflectance spectra (350-2500 nm) of 265 leaf samples from 47 species observed in tropical forests of Panama. A continuous wavelet transform was performed on each of the reflectance spectra to generate a wavelet power scalogram compiled as a function of wavelength and scale. Linear relationships were built between wavelet power and GWC expressed as a function of dry mass (LWC_D) and fresh mass (LWC_F) in order to identify wavelet features (coefficients) that are most sensitive to changes in GWC. The derived wavelet features were then compared to three established spectral indices used to estimate GWC across a wide range of species.Eight wavelet features observed between 1300 and 2500 nm provided strong correlations with LWC_D, though correlations between spectral indices and leaf GWC were poor. In particular, two features captured amplitude variations in the broad shape of the reflectance spectra and three features captured variations in the shape and depth of dry matter (e.g., protein, lignin, cellulose) absorptions centered near 1730 and 2100 nm. The eight wavelet features used to predict LWC_D and LWC_F were not significantly different; however, predictive models used to determine LWC_D and LWC_F differed. The most accurate estimates of LWC_D and LWC_F obtained from a single wavelet feature showed root mean square errors (RMSEs) of 28.34% (R² = 0.62) and 4.86% (R² = 0.69), respectively. Models using a combination of features resulted in a noticeable improvement predicting LWC_D and LWC_F with RMSEs of 26.04% (R² = 0.71) and 4.34% (R² = 0.75), respectively. These results provide new insights into the role of dry matter absorption features in the shortwave infrared (SWIR) spectral region for the accurate spectral estimation of LWC_D and LWC_F. This emerging spectral analytical approach can be applied to other complex datasets including a broad range of species, and may be adapted to estimate basic leaf biochemical elements such as nitrogen, chlorophyll, cellulose, and lignin.     

Spectroscopy of sediments in the Ganges-Brahmaputra delta: Spectral effects of moisture, grain size and lithology

The lithologic composition and grain size distribution of sediments are primary determinants of their inherent reflectance properties. However, moisture content is also known to have a strong influence on reflectances of soils and sediments. If the effects of sediment composition, grain size and moisture content could be distinguished spectrally, it might be possible to map these properties at synoptic scales using hyperspectral, or perhaps even broadband, remote sensing. Mapping the spatiotemporal distribution of sediment composition and moisture content could provide unique constraints on both the processes by which the sediments are deposited as well as the constraints they may impose on subsequent water flow and sediment transport. The Ganges-Brahmaputra delta (GBD) is formed by the convergence of these two great rivers and is superlative in both size and geologic activity. Sediment redistribution and channel migration associated with the annual floods disrupt the lives of hundreds of thousands of people living on the GBD but is also critical for maintaining the delta area fertile and above sea level. The 30+ year archive of Landsat imagery could provide a basis for spatiotemporal analysis of these fluvial dynamics if sediment properties could be inferred or measured from reflectance spectra. However, before confronting the challenge of broadband detection we must understand the spectral properties of the sediments under more controlled laboratory conditions. Bidirectional reflectance spectroscopy of 109 sediment samples from the GBD yields a spectral mixing space that appears to be structured by variations in moisture content, grain size and possibly lithology. Although the individual Empirical Orthogonal Functions of the Principal Components do not correspond to unique absorption features, clustering within the mixing space is clearly influenced by moisture content and grain size. Laboratory spectra of sediment reflectance measured under varying moisture content yield distinct trajectories through the spectral mixing space for different grain size distributions of sieved sediments. These variations in moisture content account for > 98% of spectral variance observed in these samples. Drying trajectories of coarse, fine and mixed sediments are distinct and suggest that moisture and grain size might be spectrally distinguishable. These results are consistent with Angstrom's hypothesis of moisture-driven spectral absorption but more controlled experiments are necessary to test the hypothesis rigorously.     

Multilayer design of hybrid phosphor film for application in LEDs

Crosslinked polydimethylsiloxane (PDMS) composite coatings containing luminescent micrometer-sized yellow Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) particles were prepared by spraying for potential applications in solid-state lighting. Blue light was down converted by phosphor particles to produce white light, yet poor color properties of YAG:Ce³⁺ stemmed from a deficiency of red. When nitride-based red phosphor was simply blended into the system, the electrostatic interaction of negatively charged YAG:Ce³⁺ and positively charged red phosphor particles caused remarkable clustering and heterogeneity in particle dispersion. Consequently, the light is dominantly blue and shifted to cold white. In other case, phosphor particles were sprayed onto the diffused polycarbonate substrate in stacked layers. Coatings with >80% inorganic content by mass with a thickness of 60 μm were subjected to thermal crosslinking, which the presence of the phosphor particles obstructed, presumably due to the hindrance of large phosphor particles in the diffusion of PDMS precursors. The coating of YAG:Ce³⁺ first followed by red phosphor in stacked layers produced better light output and color properties than the coating obtained by spraying the mixture at once. Monte Carlo simulation validated the hypothesis.     

Effect of different acid oxidation on morphology,dispersion and optical band-gap of multi-walled carbon nanotubes

In this paper the effect of different acid oxidation on morphology, dispersion and optical band gap of multi-walled carbon nanotubes (CNTs) is reported. Oxidation of CVD synthesized MWCNTs were carried out in 8M HNO₃, 8M H₂SO₄, 8M HNO₃/H₂O₂ and 8M H₂SO₄/HNO₃. Oxidized nanotubes sample were characterized by XRD, SEM, FT-IR, TGA, UV-Vis spectroscopy and Raman analysis. Oxidized-nanotubes show a lower shift in XRD peak and an increase in d-spacing, which implies deterioration of MWNTs. New peaks in FT-IR spectra of oxidized-nanotube samples at around 1742 cm^?1 confirms the presence of carbonyl groups. Optical bandgap, molar absorptivity coefficient is estimated for pristine and oxidized nanotubes sample using UV-Vis spectroscopy data and Tauc plot. It is observed that optical bandgap decreases on oxidation and lowest bandgap 2.92 eV is observed for H₂SO₄ treated MWNTs. The information on the optical bandgap of the MWNTs is of great importance for the development of optoelectronic devices.     

Experimental measurement of diffusion coefficients and assessment of diffusion mobilities in HCP Mg–Li–Al alloys

An atomic mobility database was established for the ternary HCP Mg–Li–Al system as a part of an ongoing effort to enable rapid development of novel lightweight Mg alloys. Three sets of three diffusion couples were assembled and annealed at temperatures ranging from 400 to 500 °C. Li concentration profiles were measured using a combination of Auger electron spectroscopy (AES) and inductively coupled plasma optical emission spectrometry (ICP-OES), while Al composition profiles were acquired using electron probe microanalysis (EPMA). The forward-simulation analysis (FSA) was employed to extract both interdiffusion and impurity diffusion coefficients from the collected experimental composition profiles. These measured diffusivity data were used to assess and iteratively optimize mobility parameters for the Mg–Li–Al system using the diffusion module within the Thermo-Calc Software package (DICTRA). The reliability of the assessed mobility parameters was further confirmed by two validation diffusion couples that were annealed at 425 and 475 °C for 96 and 48 h, respectively. It was observed that additions of Li increased the diffusivity of Al in HCP Mg, whereas additions of Al decreased the diffusivity of Li in HCP Mg.     

光诱导反应机理研究 ⅩⅦ.ESR波谱法研究多氯甲烷对降冰片二烯的光敏化加成反应机理

在以前的研究工作中我们已经证明芳胺可以有效地光敏化多氯甲烷对双环[2,2,1]-2,5-庚二烯的加成反应。该反应具有百分之百的区域选择性,在我们所选择的实验体系中只得到了3.5-加成物,而没有2.3-加成物。这一结果不同于典型的热诱导自由基加成反应。Latowski等人曾对包含有N-取代芳胺-多氯甲烷体系的光物理和光化学行为进行过详细的研究。指出多氯甲烷有效地猝灭电子给体芳胺化合物的荧光,而这一过程是与二者之间经由基态复合物或激基复合物的电子转移过程相关。根据产物的结构及芳胺-多氯甲烷体系的光物理行为,我们给出了N,N,N′,N′-四甲基联苯二胺(I)(NTMB)光敏化多氯甲烷对双环[2.2.1]-2.5-庚二烯(NBD)的加成反应机理。在该反应机理中包含有离子自由基对[ArNR_2~+CH_(4-x)Cl_x~-]和两性离子自由基复合物(Ⅱ).