Peculiarities of Interactions in the CaCO3/CaO-SO2/SO3-Air System A review

The reactions occurring between CaCO3/CaO and SO2/SO3 in oxidizing atmospheres are discussed. Calcination and sulphation were carried out in a thermobalance under conditions relevant to atmospheric fluidized bed combustion. It is suggested that the quality of limestones as potential SO2 sorbents can be assessed on the basis of tests carried out in a TG apparatus adapted for use with corrosive gases. Limestone calcined under different conditions including the treatment with NaCl leads to changes in surface texture. Sulphated samples were examined in a SEM by energy dispersive X-ray and backscattered electron imaging. Two sulphur-bearing solids (CaSO4 and CaS) were identified. The sulphation rate and extent are determined by the product layer diffusion. The amount of CaS present at the end of the process depends on the particle size of the sorbent. This revised version was published online in July 2006 with corrections to the Cover Date.     

Application of thermoanalytical methods to the study of limestone sulphation

The role that can be played in the elucidation of the limestone sulphation mechanism by thermal analysis methods with some specific procedures is discussed. Contrasting examples of applications of thermoanalytical techniques using the variable conditions are provided. These examples deal with the programmed thermal analysis using different gas sequences, the influence the calcination and sulphation conditions on the capture of SO₂, the effect of catalysts on limestone sulphation and the thermal stability of CaSO₃. Two proposed mechanisms were supported by the phase identification of the solid products.     

Reactivity of oil shale ashes in the binding of SO<Subscript>2</Subscript>

The extensive use of fossil fuels in energy production causes serious pollution of atmosphere with SO₂, CO₂, NO_x, etc. In Estonia the electricity production is based mainly on the pulverized firing (PF) of low-grade local fuel – Estonian oil shale (EOS) which is characterized by a low calorific value (~9 MJ kg^–1) and a high content of mineral matter (65–70%) from which approximately 50% are carbonates. Since 2004, also two boilers based on circulating fluidized bed combustion (CFBC) of EOS are in exploitation. The present study is focused on the comparative investigation of the efficiency of different ashes collected from different technological points of CFB and PF boilers as sorbents for SO₂. The influence of experimental temperature on the SO₂-binding characteristics of ashes as well as the possibilities of activation of ashes (grinding, hydration) were investigated. It was shown that the SO₂-binding capacity of initial ashes at 700°C and p(SO₂)=190 mm Hg was for CFBC ashes 24–30 mg and for PF ashes 10–23 mg SO₂ per 100 mg sample, the best binding capacities belonging to economizer ash (ECOA) and electrostatic precipitator ash from the 1st field (PESPA1f), respectively. However, during initial stage of binding the best results were obtained with air pre-heater ash (PHAA) and ESPA1f (both CFBC ashes). Grinding improved the SO₂-binding ability, being the most effective in the case of bottom ash (BA) from CFBC and cyclone ash (PCA) from PF – increase in binding capacity 2 and 2.3 times, respectively. As compared to initial CFBC ashes, the binding characteristics of PF ashes remained lower even after grinding. Hydration and previous calcination improved the binding characteristics only of PF ashes. Hereby, the SO₂-binding ability of CFBC ashes is better than of PF ashes and they are more promising sorbents for acidic gases, for example, for sulphur dioxide.     

Effect of the Drawing Process on the Thermal Stability of Gelatine-polyacrylonitrile Graft Copolymer Fibres

The thermal stability of gelatine-polyacrylonitrile graft copolymers fibres obtained under various conditions of deformation has been studied. The thermal properties of examined fibres depend on the synthetic component of the fibre forming material – polyacrylonitrile which appears in the form of grafted PAN chains and PAN homopolymer. It was stated that the highest thermal stability have those fibres which formation process included two stages of drawing with the use of deformation close to the maximal values, with the value of the total draw ratio amounting to 691%. It should be supposed that with such a drawing process, already in its first stage, are created advantageous conditions for the formation of paracrystalline regions to a larger extent and their orientation along the fibre axis. This revised version was published online in August 2006 with corrections to the Cover Date.     

On the pyrolytic decomposition of cadmium carbonate

The pyrolytic decomposition of cadmium carbonate was studied by thermogravimetry (TG), derivative thermogravimetry (DTG), differential thermoanalysis (DTA) and exoemission of electrons (EEE).     

Molecularly imprinted polymer on a SiO2‐coated graphene oxide surface for the fast and selective dispersive solid‐phase extraction of Carbamazepine from biological samples

A surface carbamazepine‐imprinted polymer was grafted and synthesized on the SiO₂/graphene oxide surface. Firstly SiO₂ was coated on synthesized graphene oxide sheet using the sol–gel technique. Prior to polymerization, the vinyl group was incorporated on to the surface of SiO₂/graphene oxide to direct selective polymerization on the surface. Methacrylic acid, ethylene glycol dimethacrylate and ethanol were used as monomer, cross‐linker and porogen, respectively. Nonimprinted polymer was also prepared for comparison. The properties of the molecularly imprinted polymer were characterized using field‐emission scanning electron microscopy and Fourier‐transform infrared spectroscopy. The surface molecularly imprinted polymer was utilized as an adsorbent of dispersive solid‐phase extraction for separation and preconcentration of carbamazepine. The effects of the different parameters influencing the extraction efficiency, such as sample pH were investigated and optimized. The specificity of the molecular imprinted polymer over the nonimprinted polymer was examined in absence and presence of competitive drugs. The carbamazepine calibration curve showed linearity in the ranges 0.5–500 μg/L. The limits of detection and quantification under the optimized conditions were 0.1 and 0.3 μg/L, respectively. The within‐day and between‐day relative standard deviations (n = 3) were 3.6 and 4.3%, respectively. Furthermore, the relative recoveries for spiked biological samples were above 85%.     

The influence of aluminium and aluminium oxide on the effects of mechanical activation of nickel hydroxocarbonate

The chemical and physical processes occurring during the grinding of nickel hydroxocarbonate and mixtures of nickel hydroxocarbonate with aluminium and aluminium oxide were discussed. For mechanical treatment a planetary ball mill was used. The phase analyses of ground products were carried out using thermogravimetry and X-ray diffraction methods. The amount of Ni₂(OH)₂CO₃ undecomposed and Al₂O₃xH₂O, xNiO, Ni⁰, Ni_xAl_y alloys and remained Al⁰ in the systems strongly depends on the proportion of components and on the duration of grinding in a mill which was used in the study. The comparative results are presented.This revised version was published online in November 2005 with corrections to the Cover Date.     

Influence of Cr2O3 on the Structure and Property of Mg-Al Spinel Synthesized by Waste Slag in Aluminum Factory

Via the solid phase reaction, Mg-Al spinel has been synthesized by using industrial waste slag from aluminum factory, basic magnesium carbonate and a little amount of clay as the main raw materials. The influences of Cr2O3 mineralizer on crystalline structure, micro-morphology and properties of synthesized Mg-Al spinel are discussed. The synthesized product was characterized by using XRD and SEM, and the relative contents of each crystalline phase are calculated by relevant analytical software such as Philips plus, Rietveld quantification and so on. The experimental results show that a certain amount of Cr2O3 is helpful to the formation of Mg-Al spinel, and when the addition of Cr2O3 is 2.0%, Mg-Al spinel in the system exists in the form of solid solution (Mg0.68Al0.32)(Al0.84Mg0.16)2O4 whose content is the highest reaching 91%. Then the corresponding indexes of each property are as follows: water absorption 3.0%, apparent porosity 9.8%, bulk density 3.36 g·cm-3, and flexural strength 83.32 MPa. Therefore, we can confirm that the optimum addition of Cr2O3 mineralizer is 2.0%.     

NMR metabolic profiling of organic and aqueous sea bass extracts: implications in the discrimination of wild and cultured sea bass

The nuclear magnetic resonance (NMR) technique was used as analytical tool to determine the complete metabolic profiling of sea bass extracts: water-soluble metabolites belonging to different classes such as sugars, amino acids, dipeptides and organic acids as well as metabolites soluble in organic solvent such as lipids, sterols and fatty acids were identified. The metabolite profiling together with a suitable statistical analysis were used to discriminate between wild and cultured sea bass samples. Preliminary results show that discrimination between wild and cultured sea bass was obtained not only using fatty acid composition but also cholesterol and phosphatidylethanolamine and some water-soluble metabolites such as choline, trimethylamine oxide, glutamine, fumaric and malic acids.     

Speciation and detection of arsenic in aqueous samples: A review of recent progress in non-atomic spectrometric methods

Inorganic arsenic (As) displays extreme toxicity and is a class A human carcinogen. It is of interest to both analytical chemists and environmental scientists. Facile and sensitive determination of As and knowledge of the speciation of forms of As in aqueous samples are vitally important. Nearly every nation has relevant official regulations on permissible limits of drinking water As content. The size of the literature on As is therefore formidable. The heart of this review consists of two tables: one is a compilation of principal official documents and major review articles, including the toxicology and chemistry of As. This includes comprehensive official compendia on As speciation, sample treatment, recommended procedures for the determination of As in specific sample matrices with specific analytical instrument(s), procedures for multi-element (including As) speciation and analysis, and prior comprehensive reviews on arsenic analysis. The second table focuses on the recent literature (2005–2013, the coverage for 2013 is incomplete) on As measurement in aqueous matrices. Recent As speciation and analysis methods based on spectrometric and electrochemical methods, inductively coupled plasma-mass spectrometry, neutron activation analysis and biosensors are summarized. We have deliberately excluded atomic optical spectrometric techniques (atomic absorption, atomic fluorescence, inductively coupled plasma-optical emission spectrometry) not because they are not important (in fact the majority of arsenic determinations are possibly carried out by one of these techniques) but because these methods are sufficiently mature and little meaningful innovation has been made beyond what is in the officially prescribed compendia (which are included) and recent reviews are available.