Annali di chimica最新文献

Based on literature data of sunlight spectrum, photolysis quantum yields, and absorption spectra, the relative role of nitrite and nitrate as *OH sources in surface waters was assessed, and its dependence on the season and the depth of the water column studied. In the majority of surface water samples (river, lake and seawater) nitrite is expected to play a more important role as *OH source compared to nitrate, in spite of the usually lower [NO₂^-] values. Interestingly, under the hypothesis of a constant ratio of the concentrations of nitrate and nitrite (to be corrected later on for the actual concentration ratio in a given sample), the relative role of nitrite compared to nitrate would be minimum in summer, at noon, in the surface layer of natural waters. Any decrease in the sunlight intensity that can be experienced in the natural environment (different season than summer, water column absorption, time of the day other than the solar noon), with its associated influence on the sunlight spectrum, would increase the relative role of nitrite compared to nitrate.

The complexing properties of nitrilo-tris(methylphosphonic acid) (NTP) with cadmium(II) were investigated pH-metrically at 25 °C and at ionic strength of 0.1 mol dm^-3 (NaNO₃). Stoichiometry and stability constants for the complexes formed are reported. Cadmium (II) forms Cd(NTP)^4- and the corresponding hydroxy complexes. The ternary complexes are formed in a stepwise mechanism whereby NTP binds to cadmium(II), followed by coordination of amino acids, peptides or DNA. The concentration distribution of the various complex species has been evaluated.

The information content of visible spectra has been evaluated, by means of some selected chemometrical techniques, for its ability to trace the geographical origin of extra virgin olive oils coming from several Mediterranean regions. Special attention was paid to extra virgin olive oil produced in West Liguria, a North Italy region which leans over the Mediterranean Sea and borders France. The peculiar organoleptic features of this “niche product” deserved the protected designation of origin “Riviera Ligure-Riviera dei fiori”. Unfortunately, this expensive oil is often submitted to profitable adulterations, commonly involving addition of other cheaper Mediterranean oils. Using suitable transforms, such as profiles and derivatives, the visible spectra of extra virgin olive oils showed a very important discriminant power in that regards the geographical characterization of the studied samples. In particular, the developed class models for West Liguria oils have 100% sensitivity and specificity. Moreover, even if this paper is focused on West Liguria oil, it is important to emphasize that a similar study, involving a so widespread and timesaving technique, could be analogously developed for all the other Mediterranean regions taken into account and it could be used in other olive oil characterization problems.

In the present article an attempt is being made to elucidate the inorganic colorants encountered in the Russian avant-garde painting palette by a combined art historical, documentary and physicochemical investigation; and to examine the influence of environmental factors on the chromatic profile originally sought by the artist. The overall approach based on written sources is confirmed by measurements on representative paintings from the Costakis Collection in the State Museum for Contemporary Art, Thessaloniki. The documentary research deals with the influences of Orthodox iconography, folkloric art, and occidental modernist tendencies on the Russian avant-garde palette; and is studying the effects of contradictory historical processes in the chromatic profile of individual paintings. In the experimental section a series of colorants are investigated concerning the effects of accelerated ageing on experimental painting tables, prepared as watercolour and gouache layers on paper ground. The resulting samples are subject to colorimetric, and spectroscopic measurements; and analogous analytical procedures are applied on samples taken from selected paintings belonging to the Costakis Collection. A systematic comparative study of all data permits evaluating the materials used as to their stability towards exstrincic factors, and proposing degradation routes, in order to assist museum curators and conservators in every concrete case related to the broad spectrum of pigments examined.

In the Vinica Fortress, Republic of Macedonia, 50 undamaged terra cotta icons and 100 fragments, all dated 6th–7th century, were found. In order to determine the provenance of these unique terra cotta icons, the mass fractions of 19 different chemical elements were previously determined in ten fragments of the terra cotta icons and thirty three samples of clays from eight different sites from the region. Due to the dimensionality and complexity of the experimental data, the archaeometric results were treated with self-organising maps (SOM). The results obtained using SOM were compared with the ones obtained using principal component analysis. Both chemometric methods revealed that Vinica terra cotta icons were made from clay from Grnčarka, 2.5 km South-East from the Vinica Fortress.

Large sample neutron activation analysis compliments and significantly extends the analytical tools available for cultural heritage and authentication studies providing unique applications of non-destructive, multi-element analysis of materials that are too precious to damage for sampling purposes, representative sampling of heterogeneous materials or even analysis of whole objects. In this work, correction factors for neutron self-shielding, gamma-ray attenuation and volume distribution of the activity in large volume samples composed of iron and ceramic material were derived. Moreover, the effect of inhomogeneity on the accuracy of the technique was examined.

Metallic objects are considered among the most significant findings in Cultural Heritage and represent the ‘culture of Materials’ and the habits of an historical period and of a population. They also preserve traces of time: from the transformation of the ores in metal (by smelting) to the degradation from metal to oxidised compounds (by corrosion processes). Metallography, historically devoted to connect the microstructural features to production processes and to chemical-physical-mechanical properties is a powerful and relatively easy approach to characterise metallic findings. All analytical tools and methods in the hands of a metallographer are improved through experience and practice and provide a large number of information (elemental composition, primary and secondary microstructures, surface treatments, corrosion rate, original ores traces) by the preparation of a fairly small microdestructive sample. A wise and careful use of the metallography allows the balance “object sacrifice / knowledge improvement” to lean on the right side contributing to the hard work of rebuilding humankind history. Beside a description of a research protocol some practical examples concerning archaeological findings are presented in this paper.

Tars and pitches were prepared from wood and bark of various deciduous trees and conifers and analysed with the intention to distinguish between various starting materials. All this was done before the background of an archaeometrical problem: to provide a basis for the chemical identification of those pitches which are frequently found in archaeological excavations.

Intending to extend the already existing possibilities for such analyses the present paper is dealing with the application of pyrolysis coupled with capillary gas chromatography and by subsequent chemometric studies. It could be shown that by this technique indeed not only tars and pitches prepared from deciduous trees and from conifers could clearly be differentiated, but that even respective species could be identified. Thus a fundament is provided for future studies aiming to identify the starting material of real archaeological finds by a novel method which requires by far less quantities of sample material as compared to the methods hitherto used by us.