EXAFS study on the reactions between iron and fulvic acid in acid aqueous solutions

Iron(III) competes with trace metals for binding sites on organic ligands. We used X-ray absorption fine structure (EXAFS) spectroscopy to determine the binding mode and oxidation state of iron in solutions initially containing only iron(III) and fulvic acid at pHs 2 and 4. EXAFS spectra were recorded at different times after sample preparation. Iron was octahedrally configured with inner-sphere Fe-O interactions at 1.98-2.10 A, depending on the oxidation state of iron. Iron(III) formed complexes with fulvic acid within 15 min. Iron(III) was reduced to iron(II) with time at pH 2, whereas no significant reduction occurred at pH 4. No signs of dimeric/trimeric hydrolysis products were found in any of the solution samples (<0.45 microm). However, the isolated precipitate of the pH 2 sample (>0.45 microm) showed Fe...Fe distances, indicating the presence of tightly packed iron(III) trimers and/or clusters of corner-sharing octahedra. It is suggested that the binding mode of iron(III) to fulvic acid at low pH may be phase-dependent: in solution mononuclear complexes predominate, whereas in the solid phase hydrolyzed polynuclear iron(III) complexes form, even at very low pH values. The observed pH dependence of iron(III) reduction was consistent with expected results based on thermodynamic calculations for model ligands.     

Analyzer system capable of determining energy and direction of charged particles in ultrahigh vacuum

We have constructed and tested a system capable of measuring the energy of charged particles emitted from a sample at any angle relative to the sample or the incident beam of exciting particles. The energy analysis is accomplished by a 180 degrees spherical deflecting-type analyzer, operated at constant pass energy with a series of electrostatic lenses. The analyzer system is properly apertured to accept incoming particles from a spot of 1.5 mm diameter at the sample and within a cone of 2.5 degrees half-angle. The lens system used has constant transmission independent of the incident energy. The energy analyzer is independently rotatable about two orthogonal axes, giving it complete freedom of access to any angle of collection relative to the sample orientation. The sample can rotate about two orthogonal axes so that any angle of incidence can be used. Specific examples are given of the performance of the system when used for the measurement of the angular distribution of photoelectrons excited by synchrotron radiation.     

Dissolution of softwood kraft pulps by direct derivatization in lithium chloride/N,N‐dimethylacetamide

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N‐dimethylacetamide (DMAc) by size exclusion chromatography is presented. The method is based on derivatization with ethyl isocyanate and the dissolution of samples in 8% LiCl/DMAc. In this study, the derivatization of hardwood kraft pulps did not influence the MMD. In the case of softwood pulps, however, the derivatization decreased the proportion of the high‐molecular‐mass material and increased the proportion of the low‐molecular‐mass material, which resulted in a distribution similar to the MMD of a hardwood kraft pulp. The results suggest that associations between hemicellulose and cellulose in the softwood kraft pulp were ruptured during derivatization. This led to a more correct estimation of the MMD of derivatized softwood kraft pulps than obtained by the dissolution of nonderivatized samples. This new method offers several advantages over derivatization with phenyl isocyanate: a precipitation step is not necessary, it is possible to follow the lignin distribution in the samples, and the method allows very high levels of dissolution of softwood kraft pulps up to a κ number of around 50. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 424–431, 2004     

Surface chemistry of intermetallic AlSb-anodes for Li-ion batteries

The solid electrolyte interphase (SEI) layer on AlSb electrodes has been studied in Li/AlSb cells containing a LiPF₆ EC/DEC electrolyte using X-ray photoelectron spectroscopy (XPS). Data were collected before SEI-formation, during formation, and after formation at 0.01 V versus Li⁰/Li⁺, and at full delithiation in cycled cells at 1.20 V. The thickness of the SEI layer increases during lithiation and decreases during delithiation. This dynamic behaviour occurs continuously on cycling the cells. The growth of the SEI layer can be attributed predominantly to the deposition of carbonaceous species below 0.50 V versus Li⁰/Li⁺; these species disappear almost completely during delithiation. The extra surface-layer formation is a consequence of the additional charge that is needed to lithiate the remaining Sb component of the micrometer-sized AlSb particles at low potentials as seen by synchrotron-based X-ray diffraction. Aluminium is not reactive to lithium alloying in this electrolyte. Relatively small amounts of LiF were detected in the AlSb SEI layers compared to that commonly found in the SEI layers on graphite electrodes.     

Source apportionment of atmospheric PAHs in the western Balkans by natural abundance radiocarbon analysis

Progress in source apportionment of priority combustion-derived atmospheric pollutants can be made by an inverse approach to inventory emissions, namely, receptor-based compound class-specific radiocarbon analysis (CCSRA) of target pollutants. In the present study, CCSRA of the combustion-derived polycyclic aromatic hydrocarbons (PAHs) present in the atmosphere of the countries of the former republic of Yugoslavia was performed. The carbon stable isotope composition (delta13C) of PAHs varied between -27.68 and -27.19 per thousand, whereas delta14C values ranged from -568 per thousand for PAHs sampled in Kosovo to -288 per thousand for PAHs sampled in the Sarajevo area. The application of an isotopic mass balance model to these delta14C data revealed a significant contribution (35-65%) from the combustion of non-fossil material to the atmospheric PAH pollution, even in urban and industrialized areas. Furthermore, consistency was observed between the isotopic composition of PAHs obtained by high-volume sampling and those collected by passive sampling. This encourages the use of passive samplers for CCSRA applications. This marks the first time that a CCSRA investigation could be executed on a geographically wide scale, providing a quantitative field-based source apportionment, which points out that also non-fossil combustion processes should be targeted for remedial action.     

The fundamental role of general orthonormal bases in systemidentification

The purpose of this paper is threefold. Firstly, it is to establish that contrary to what might be expected, the accuracy of well-known and frequently used asymptotic variance results can depend on choices of fixed poles or zeros in the model structure. Secondly, it is to derive new variance expressions that can provide greatly improved accuracy while also making explicit the influence of any fixed poles or zeros. This is achieved by employing certain new results on generalized Fourier series and the asymptotic properties of Toeplitz-like matrices in such a way that the new variance expressions presented here encompass pre-existing ones as special cases. Via this latter analysis a new perspective emerges on recent work pertaining to the use of orthonormal basis structures in system identification. Namely, that orthonormal bases are much more than an implementational option offering improved numerical properties. In fact, they are an intrinsic part of estimation since, as shown here, orthonormal bases quantify the asymptotic variability of the estimates whether or not they are actually employed in calculating them     

Use of Tablet Tensile Strength Adjusted for Surface Area and Mean Interparticulate Distance to Evaluate Dominating Bonding Mechanisms

In this study, tablet tensile strength has been adjusted for tablet surface area and the average distance between particles in compacts of different materials. The aim of the study was to evaluate the feasibility of using this concept to assess the dominating interparticulate bonding mechanisms. Adjustment of the tensile strength for both tablet surface area and mean pore radius gave similar bonding strength values for materials bonding mainly by weak distance forces (crystalline lactose, sucrose, and microcrystalline cellulose) almost independently of compaction pressure. However, particle size and other factors may still affect the compensated strength values. The bond strength was much higher and more varied for materials bonding also with solid bridges (potassium chloride, sodium chloride, and possibly also sodium bicarbonate and amorphous lactose). For these materials, particle size and compaction pressure had a substantial effect on the bond strength. It is probably the formation of continuous bridges between adjacent particles that is important in these materials rather than the surface properties and the average distance between particles positioned at some distance from each other. Hence, adjusting the tensile strength of compacts does not necessarily reflect all the dominating factors responsible for interparticulate bonding. Nonetheless, adjustment for tablet surface area and mean pore radius allowed discrimination between different dominating interparticulate bonding mechanisms in these compacted materials.     

I5M: 3D widefield light microscopy with better than 100 nm axial resolution

Sevenfold improved axial resolution has been achieved in three-dimensional widefield fluorescence microscopy, using a novel interferometric technique in which the sample is observed and/or illuminated from both sides simultaneously using two opposing objective lenses. Separate interference effects in the excitation light and the emitted light give access to higher resolution axial information about the sample than can be reached by conventional widefield or confocal microscopes. Here we report the experimental verification of this resolution performance on complex biological samples.     

Tetradecane and hexadecane binary mixtures as phase change materials (PCMs) for cool storage in district cooling systems

As the demand for refrigeration and air-conditioning has increased during the last decade, district cooling systems have been introduced in some major European cities. In a district cooling system, the combination of central cooling facilities and cool storage systems provides economic advantages over older conventional cooling plants. A cool storage system can meet the same total cooling load as a non-storage system over a given period of time with a smaller chiller. Cool storage systems using Phase Change Materials (PCMs) have a low temperature range and high energy density in the melting solidification of PCMs compared to sensible heat storage. Thus they are advantageous in reducing the storage volume, heat loss, and size of the chilling equipment. In this paper we describe some paraffin waxes and their binary mixtures. We discuss the thermal properties of laboratory-grade tetradecane, hexadecane and their binary mixtures, and we demonstrate their potential for use as PCMs for cool storage. The thermal properties include freezing point, the heat of fusion, thermal stability and volume expansion during the phase change process. In the study, a Differential Scanning Calorimeter (DSC) was used to determine the heat of fusion of these materials and to generate thermal data for study and analysis. The results show that these materials are attractive candidates as potential PCMs for cool storage in district cooling systems. However, because of the high cost of laboratory-grade materials, technical-grade materials must be used for cool storage.