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The Baroque monuments of several cities in eastern Sicily, built of local calcarenitic stone, are often subjected to conservation treatments, since they undergo many forms of alteration and degradation which can cause significant damage. However, a recent study of these building materials (Barone et al. in Environ. Geol. 54:1501, 2008) has demonstrated that some protective products, once applied, cause irreversible chromatic alterations.

An analytical procedure is described for the analysis of archaeological glass by inductively coupled plasma optical emission spectroscopy (ICP-OES). Glass samples were analysed in solution after fusion with lithium metaborate at 1100°C. The analyses were performed in the sequential multielemental mode of operation, with the determination of 15 elements in four analytical runs; only elements with not too large concentration difference were analysed in a single run. The following elements were accounted for: Si, Na, Ca, Al, Fe, Mg, Mn, Ti, Sr, Ba, Cr, Ni, Cu, Co, Pb.

The available mitochondrial DNA (mtDNA) data do not point to clear genetic relationships between current Tuscans and the Bronze-Age inhabitants of Tuscany, the Etruscans. To understand how and when such a genetic discontinuity may have arisen, we extracted and typed the mtDNAs of 27 medieval Tuscans from an initial sample of 61, spanning a period between the 10th and 15th century AD. We then tested by serial coalescent simulation various models describing the genealogical relationships among past and current inhabitants of Tuscany, the latter including three samples (from Murlo, Volterra, and Casentino) that were recently claimed to be of Etruscan descent. Etruscans and medieval Tuscans share three mitochondrial haplotypes but fall in distinct branches of the mitochondrial genealogy in the only model that proved compatible with the data. Under that model, contemporary people of Tuscany show clear genetic relationships with Medieval people, but not with the Etruscans, along the female lines. No evidence of excess mutation was found in the Etruscan DNAs by a Bayesian test, and so there is no reason to suspect that these results are biased by systematic contamination of the ancient sequences or laboratory artefacts. Extensive demographic changes before AD 1000 are thus the simplest explanation for the differences between the contemporary and the Bronze-Age mtDNAs of Tuscany. Accordingly, genealogical continuity between ancient and modern populations of the same area does not seem a safe general assumption, but rather a hypothesis that, when possible, should be tested using ancient DNA analysis.

Green colored samples on wall paintings and green powder from a pigment pot found in Pompeii area are investigated by micro-Raman, FT-IR and, for one sample, SEM-EDX. To obtain the green color, green earths and malachite were used, together with mixture of Egyptian blue and yellow ochre. The mineralogical identification of the green earths has been attempted through the comparison of the vibrational features, discriminating between celadonite and glauconite spectra. Traces of a modern synthetic pigment containing copper phthalocyanine were found in a fresco fragment.

BackgroundDNA sequences from ancient specimens may in fact result from undetected contamination of the ancient specimens by modern DNA, and the problem is particularly challenging in studies of human fossils. Doubts on the authenticity of the available sequences have so far hampered genetic comparisons between anatomically archaic (Neandertal) and early modern (Cro-Magnoid) Europeans.Methodology/principal findingsWe typed the mitochondrial DNA (mtDNA) hypervariable region I in a 28,000 years old Cro-Magnoid individual from the Paglicci cave, in Italy (Paglicci 23) and in all the people who had contact with the sample since its discovery in 2003. The Paglicci 23 sequence, determined through the analysis of 152 clones, is the Cambridge reference sequence, and cannot possibly reflect contamination because it differs from all potentially contaminating modern sequences.Conclusions/significanceThe Paglicci 23 individual carried a mtDNA sequence that is still common in Europe, and which radically differs from those of the almost contemporary Neandertals, demonstrating a genealogical continuity across 28,000 years, from Cro-Magnoid to modern Europeans. Because all potential sources of modern DNA contamination are known, the Paglicci 23 sample will offer a unique opportunity to get insight for the first time into the nuclear genes of early modern Europeans.

Two holy water fonts (dated at the beginning of the XVII century) in the Santa Maria della Steccata Church in Parma (Italy) have recently been restored. Before the intervention, a detailed investigation on their degradation products was carried out to understand the mechanisms of alteration of the materials and to suggest appropriate restoration procedures. The analyses were performed by means of powder X-ray diffraction (XRD), micro-Fourier transform infrared (FTIR) and micro-Raman spectroscopies. Calcite, iron oxides, silicates and sodium chloride (from salted holy water) were found in the red coloured calcarenite. On and under the lead coverings, different lead oxides (mainly massicot), other lead salts (lead basic carbonate, cerussite, plumbonacrite Pb 10 O(OH) 6 (CO 3 ) 6 and lead–chlorine compounds as laurionite PbOHCl and phosgenite Pb 2 CO 3 Cl 2 ) were identified by Raman spectroscopy and XRD. Haematite α-Fe 2 O 3 , goethite α-FeO(OH) and lepidocrocite γ-FeO(OH) were found on and around the iron hinges. Lead compounds and sodium chloride, through crystallization and solubilization cycles, were responsible for the stone's degradation, whereas the iron corrosion materials on the hinges produced mechanical stress and cracks in the stone. Various suggestions have been given on how to restore these fonts and to remove the causes of damage.

Times Cited: 1; International audience; It is difficult to obtain fossil data from the 10% of Earth's terrestrial surface that is covered by thick glaciers and ice sheets, and hence, knowledge of the paleoenvironments of these regions has remained limited. We show that DNA and amino acids from buried organisms can be recovered from the basal sections of deep ice cores, enabling reconstructions of past flora and fauna. We show that high-altitude southern Greenland, currently lying below more than 2 kilometers of ice, was inhabited by a diverse array of conifer trees and insects within the past million years. The results provide direct evidence in support of a forested southern Greenland and suggest that many deep ice cores may contain genetic records of paleoenvironments in their basal sections.

Neandertals are documented in Europe and Western Asia from about 230,000 to 29,000 years ago. Analyses of mitochondrial DNA (mtDNA) from Neandertal samples [1,2] and other analyses [3–5] appear incompatible with the hypothesis that Neandertals are direct ancestors of modern Europeans [6,7]. However, there are broad geographic gaps in the sampling of Neandertal DNA diversity. Here, we describe the sequence of the first mitochondrial hypervariable region (HVR1) in a new specimen from Monti Lessini (MLS) in Northern Italy.

Archaeological excavation in an Etruscan room tomb, from the Monterozzi necropolis in Tarquinia led to the recovery of four individuals. It was hypothesized that they could be members of a single family group. As both archaeological data and classical anthropological analysis provided little information in this direction, ancient DNA (aDNA) was extracted from bone and tooth fragments of the individuals. For each subject HVR-I of the mitochondrial DNA (mtDNA) was cloned and sequenced. To identify the sex of the individuals, amelogenine and SRY genes were analysed. Short tandem repeat (STR) characterization was also performed. DNA studies were preceded by the evaluation of amino acids racemization extent and thermogravimetric analysis (TGA), to evaluate, respectively, degradation and quantity of organic matter preserved in the samples. Results show that two subjects are males, whereas two are females. Furthermore, three of them share the same mtDNA sequence, and, as such, they could be related by maternal lineage. This evidence supports the hypothesis that the occupants of the tomb can be considered members of a family group composing two parents and their son and daughter. Molecular study supplies new data to better define the reconstruction previously proposed, based only on a morphological and archaeological approach. Multidisciplinary investigation also allows comparison of the different methods and integration of their contributions.

The origins of the Etruscans, a non-Indo-European population of preclassical Italy, are unclear. There is broad agreement that their culture developed locally, but the Etruscans’ evolutionary and migrational relationships are largely unknown. In this study, we determined mitochondrial DNA sequences in multiple clones derived from bone samples of 80 Etruscans who lived between the 7th and the 3rd centuries b.c. In the first phase of the study, we eliminated all specimens for which any of nine tests for validation of ancient DNA data raised the suspicion that either degradation or contamination by modern DNA might have occurred. On the basis of data from the remaining 30 individuals, the Etruscans appeared as genetically variable as modern populations. No significant heterogeneity emerged among archaeological sites or time periods, suggesting that different Etruscan communities shared not only a culture but also a mitochondrial gene pool. Genetic distances and sequence comparisons show closer evolutionary relationships with the eastern Mediterranean shores for the Etruscans than for modern Italian populations. All mitochondrial lineages observed among the Etruscans appear typically European or West Asian, but only a few haplotypes were found to have an exact match in a modern mitochondrial database, raising new questions about the Etruscans’ fate after their assimilation into the Roman state.

Micro-Raman spectroscopy, combined with gas chromatography and ultra-violet fluorescence photography, was used to study some wall paintings in the S. Giovanni Evangelista Abbey in Parma, Italy. The restoration of some painted chapels enabled a comparison between two painters of the 16th century: Parmigianino (Girolamo Francesco Maria Mazzola, 1503–1540) and Michelangelo Anselmi (1492?–1556?). Micro-Raman spectroscopy determined the palette used by the artists, leading to the identification of different white, yellow, red, brown, green, blue and black pigments. Some pigments are evidence of later restorations. Gas chromatography combined with mass spectroscopy revealed the presence of organic binding media and enabled to distinguish between fresco and secco paintings.

The organic material present in oxalate patinas, collected from the stone external surfaces of the Baptistery in Parma (Italy), was analysed by GC-MS. The high racemisation levels determined for several specific amino acids indicate that microbial activity could contribute to the formation and modification of the organic material leading to the calcium oxalate patinas.

Publisher Summary Calcium oxalate patinas have been found over a variety of substrates (including calcareous and noncalcareous stone) from different locations throughout the world. The application of organic materials on the surfaces of artifacts or buildings for protective and/or aesthetic purposes is considered as the cause of formation of calcium oxalate. This chapter describes the gas chromatography-mass spectrometry (GC/MS) analysis of proteinaceous material in calcium oxalate patinas to look at the racemization level of the amino acids present in the organic material. The oxalate patina samples were collected from the stone surfaces of the Baptistery in Parma (Italy). Four oxalate patina samples were taken for experimentation and were treated with acid. All the four oxalate patina samples collected from the stone surfaces of the Baptistery showed the presence of D,L amino acids. The level of racemization of amino acids of these samples presented a wide variabilty. Alanine presented the highest D/L value. This can be attributed to aging and microbial growth. The high racemization levels detected indicates that microbial flora contributes to the accumulation and modification of the organic material that leads to the formation of oxalate patinas on the monument stones.

We report the mitochondrial DNA (mtDNA) analysis of the supposed remains of Francesco Petrarca. The optimal preservation of the remains permitted the retrieval of sufficient mtDNA for genetic analysis. DNA was extracted from a rib and a tooth. MtDNA sequences from the tooth and rib were not identical, suggesting they belonged to different individuals. Indeed, molecular gender determination showed that the postcranial remains belonged to a male while the skull belonged to a female. These results are consistent with morphological investigations. © 2008 Elsevier Ireland Ltd. All rights reserved.

International audience; Abstract Background The aurochs ( Bos primigenius ) was a large bovine that ranged over almost the entirety of the Eurasian continent and North Africa. It is the wild ancestor of the modern cattle ( Bos taurus ), and went extinct in 1627 probably as a consequence of human hunting and the progressive reduction of its habitat. To investigate in detail the genetic history of this species and to compare the population dynamics in different European areas, we analysed Bos primigenius remains from various sites across Italy. Results Fourteen samples provided ancient DNA fragments from the mitochondrial hypervariable region. Our data, jointly analysed with previously published sequences, support the view that Italian aurochsen were genetically similar to modern bovine breeds, but very different from northern/central European aurochsen. Bayesian analyses and coalescent simulations indicate that the genetic variation pattern in both Italian and northern/central European aurochsen is compatible with demographic stability after the last glaciation. We provide evidence that signatures of population expansion can erroneously arise in stable aurochsen populations when the different ages of the samples are not taken into account. Conclusions Distinct groups of aurochsen probably inhabited Italy and northern/central Europe after the last glaciation, respectively. On the contrary, Italian and Fertile Crescent aurochsen likely shared several mtDNA sequences, now common in modern breeds. We argue that a certain level of genetic homogeneity characterized aurochs populations in Southern Europe and the Middle East, and also that post-glacial recolonization of northern and central Europe advanced, without major demographic expansions, from eastern, and not southern, refugia.Background The aurochs ( Bos primigenius ) was a large bovine that ranged over almost the entirety of the Eurasian continent and North Africa. It is the wild ancestor of the modern cattle ( Bos taurus ), and went extinct in 1627 probably as a consequence of human hunting and the progressive reduction of its habitat. To investigate in detail the genetic history of this species and to compare the population dynamics in different European areas, we analysed Bos primigenius remains from various sites across Italy. Results Fourteen samples provided ancient DNA fragments from the mitochondrial hypervariable region. Our data, jointly analysed with previously published sequences, support the view that Italian aurochsen were genetically similar to modern bovine breeds, but very different from northern/central European aurochsen. Bayesian analyses and coalescent simulations indicate that the genetic variation pattern in both Italian and northern/central European aurochsen is compatible with demographic stability after the last glaciation. We provide evidence that signatures of population expansion can erroneously arise in stable aurochsen populations when the different ages of the samples are not taken into account. Conclusions Distinct groups of aurochsen probably inhabited Italy and northern/central Europe after the last glaciation, respectively. On the contrary, Italian and Fertile Crescent aurochsen likely shared several mtDNA sequences, now common in modern breeds. We argue that a certain level of genetic homogeneity characterized aurochs populations in Southern Europe and the Middle East, and also that post-glacial recolonization of northern and central Europe advanced, without major demographic expansions, from eastern, and not southern, refugia.

Etude du comportement de composes, produits des reactions de (cp) 2 Ni 2 (PPh 2 C≡CR) ou (cp) 2 Ni 2 (RC≡CR') avec Fe 3 (CO) 12 ou Fe 2 (CO) 9

2,6-Diacetylpyridine bis(benzoylhydrazone) (H2DPBH) is proposed as a ligand for the extraction of uranium(VI). Complete extraction from aqueous solutions into dichloromethane is achieved with a ligand/metal mole ratio of < for 10−5−10−4 M uranyl ion. Potentiometric measurements indicate that the extracted species is UO2 (DPBH). Uranium can be determined in the extract by spectrophotometric measurements at 420 nm and by differentail pulse polarography (Ep = −0.67 V) with tetraethylammonium bromide as supporting electrolyte. For both methods, the detection limit is about 2 × 10−6 M in the extract.

In spite of the large number of methods already reported, the determination of the uranyl ion is still a relevant analytical problem because the usual techniques of atomic absorption and emission spectroscopy are not suitable for the trace analysis of UO/sub 2//sup 2 +/, owing to their high detection limits. In this paper a new chromatographic procedure is proposed; this procedure is based on the separation and determination of UO/sub 2//sup 2 +/ as a neutral complex, using reversed-phase chromatography and spectrophotometric detection. In this work the ligand 2,6-diacetylpyridine bis(benzoyl-hydrazone) was used for the solvent extraction and chromatographic determination of uranium. The compounds of this class of bis(aroylhydrazone) derivatives are potential pentadentate chelating agents which can behave as neutral or bisdeprotonated ligands. Because of its steric and electronic features, H/sub 2/DIB is particularly suitable for complexing the uranyl ion. High extraction yields of UO/sub 2//sup 2 +/ from aqueous to dichloromethane solutions have been obtained, copper being the only metal with comparable extraction yield. The behavior of this ligand in the extraction of the uranyl ion, in addition to the high molar absorption of the complex in the UV region, suggested its use for the chromatographic determination of uranium, usingmore » a commercial apparatus with spectrophotometric detection.« less

Etude de l'influence des coordinats bidentes sur le comportement en HPLC du complexe suivant: HRu 3 (C≡CBu)(CO) 9 (Ph 2 PXEPh 2 ) ou Bu=tertbutyl; Ph=phosphine; X=CH 2 , CH 2 CH 2 , CH=CH; E=PPh 2 , AsPh 2

Reference proteinaceous binding media of the kinds historically used in painting (specially prepared for this study) and samples collected from ancient polychrome works of art were analysed by gas chromatography – mass spectrometry. The data have been processed by several multivariate chemometric techniques, such as cluster analysis, principal component analysis, factor analysis and SIMCA technique in order to classify the binding media of the ancient works of art on the basis of the proteinaceous material used. The characterisation of ancient samples was possible by the joint use of SIMCA technique and factor analysis. The latter, in particular, has made it possible to point into evidence the presence of at least two latent factors. The first factor seems to be connected with the chemical composition of the painting media, while the second factor is likely to be connected with ageing processes.

The chromatographic behaviour of some monosubstituted derivatives of the tetranuclear cluster (Cp)NiOs 3 (μH) 3 (CO) 9 (Cp = cyclopentadienyl) with group V donor ligands (benzonitrile tertiary phosphines, triphenylamine and triphenylstibine) is reported. In reversed-phase and adsorption liquid chromatography, the kind of the substituents strongly influences the retention volumes, the dimension of the whole cluster having less effect. Correlations of retention volumes with the nature of the substituents were found only for small of compounds.

Binding media in samples taken from XIIth–XIIIth century polychrome sculptures in the Baptistery of Parma (Italy) were characterized by gas chromatography-mass spectrometry, after hydrolysis and derivatization procedures. The use of SE-52 capillary columns and the application of selected ion monitoring (SIM) allowed an increasing in the sensitivity and the ability to differentiate between animal glues, casein, egg and drying oils as components of the binders of paint and ground layers. Small amounts of material were enough for a satisfactory characterization.

Scanning electron microscopy (SEM) coupled with energy-dispersive x-ray detection was used to study fragments of fine pottery excavated on the archaeological site at Locri Epizephiri (Southern Italy). The fragments analysed were specimens of black coated ware and included pieces suspected to have been produced on the site in the course of the fourth and third centuries BC and suspected imports from foreign centres of production. Comparison between the composition of slip and body of the samples indicated that selection and refinement of clays led to silicon and calcium depletion and aluminium, iron and potassium enrichment in the coating. In addition, pronounced depletion of magnesium was observed in the slip of the imported wares and the earlier local products, but not of the later local wares; this might account for the low quality of some 3rd century products with respect to the earlier pieces. Examination of SEM images indicated that the thickness of the surface slip reaches up to about 20-25 μm on the imported sherds, but measures ca. 10-20 μm on most of the local products.

Reflectance and electron paramagnetic resonance (EPR) spectroscopies were used to study 25 fragments of Roman glass. Colour coordinates were used for an unbiased classification of the glasses in colour groups, which accounted for the presence of blue, blue-green, green, yellow-green, yellow and purple samples. Reflectance spectra were recorded in the 250–2500 nm wavelength range and showed absorption bands characteristic of FeII, FeIII and MnIII ions; furthermore, CoII and CuII bands were observed in the spectra of the blue glasses. A decrease of the absorbance ratio of FeII to FeIII ions was observed moving from blue-green to green and yellow-green glasses; however, yellow fragments still proved to be reduced glasses. EPR spectra displayed the characteristic patterns of FeIII and MnII ions, with g-values in the 2–5 interval and spectral features depending on the relative content of the two elements. The characteristic pattern of the VIV ion (g ≈ 2) and signals due to the formation of iron-sulphur complexes (g ≈ 6) appeared in the spectrum of a dark yellow glass, recorded at 77 K.