Journal of Raman Spectroscopy Volume 47, Issue 3, 1 March 2016, Pages 321-328 A combined analytical approach applied to Medieval wall paintings from Puglia (Italy): The study of painting techniques and its conservation state (Article) Fico, D. , Pennetta, A., Rella, G., Savino, A., Terlizzi, V., De Benedetto, G.E. Laboratorio di Spettrometria di Massa Analitica Ed Isotopica, Dipartimento di Beni Culturali, Università Del Salento, Edificio M, campus Ecotekne, s.p. Lecce-Monteroni, Lecce, Italy View references (46) Abstract A combined analytical approach has been applied to the wall paintings, dated from 10th to 14th centuries, of the Santi Stefani crypt at Vaste (Lecce, Southern Italy). These paintings are a precious testimony of Medieval art in Southern Italy. However, the church shows problems of damp as well as clear evidences of flora, fungi and mold presence, and there is little knowledge of the pictorial methodologies used. Raman spectroscopy allowed to determine the palette and to reconstruct the worksite and the chronological sequence of the various paint layers. Kaolinite, calcite, carbon black, hematite, massicot, goethite, indigo and azurite were identified as pigments along with synthetic pigments, like phthalocyanine blue and chrome yellow. Attenuated total reflectance-Fourier transform infrared spectroscopy suggested the presence of egg as a binder in some pictorial layers. The conservation state of the crypt is poor, and detachments of pigmented layers are frequent because of the presence of subflorescence and efflorescence: nitrate, sulfate and chloride salts have been identified spectroscopically and quantified by ion chromatography. The extensive use of kaolinite in Santi Stefani, actually not uncommon in Medieval art, is observed for the first time in a crypt of Puglia: its use to stabilize some pigments and to improve their adhesion on substrate is proposed. Copyright © 2015 John Wiley & Sons, Ltd.

The Earth Sciences Museum of the University of Bari Aldo Moro (Italy) exhibits a wide collection of amber samples. These have been catalogued as Baltic amber (succinite), Sicilian amber (simetite), amber from New Jersey, Apennine amber and New Zealand copaline. However, some samples revealed to be erroneously classified as a consequence of incorrect information on the labels or in the museum catalogue. This may be due to historical forgeries, as is often the case of simetite, or to a possible exchange of samples that probably occurred during the displacement of the museum collection from the Central University Building to the Geo-environmental and Earth Sciences Department. In this study, all amber samples were systematically investigated with long wave UV rays, attenuated total reflectance (ATR), Fourier transform infrared (FTIR) spectroscopy and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) using on-line thermally assisted hydrolysis and methylation. The combined use of the latter two analytical techniques allowed for a complete characterisation of the ambers, whereas UV fluorescence showed to be of little value. The compositional data could be used for a better classification and valorisation of the amber samples of the museum collection. Two of the purported amber samples were shown to be copal, while four others are ambers but had been wrongly classified. Moreover, for some samples, it could be established that they had been subjected to treatment with a drying oil.

The investigation was aimed at defining the compositional and structural characteristics of a group of monochrome blue faiences recovered in Pompeii to assess provenance on the basis of their technological features. Different complementary analytical techniques were used: Scanning Electron Microscopy (SEM) to investigate the morphological aspects of the samples and in particular of the interfaces, micro-Raman Spectroscopy and XRPD to identify crystalline phases and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) to assess the elemental composition due to its sensitivity to a wide range of elements and the adequate lateral resolution. Statistical data treatment of the elemental concentrations of both the ceramic bodies and the glazes allowed us to classify the objects into compositional groups and to verify the previously established archaeological hypothesis suggesting an Egyptian provenance for faience of Pompeii.

Puglia (Italy) has always occupied a prominent place in the field of production and use of stone materials, because it is rich of limestone with good chemical, physical and mechanical characteristics and with satisfactory colors. As a result these stones have been widely used in recent and past construction in Salento (Puglia-Southern Italy); both carparo and pietra leccese (the names of the most important among these lithotypes) are known since ancient times and have been valued in the art achieving an international appraisal thanks to local handicraft. Over the centuries these stones have produced the complex and well known architecture of Lecce spanning from Romanique to Baroque. The skin of these buildings is an interesting topic because different conservation states can be acknowledged and art historians generally considered a different surface finish the main cause [Casciaro personal communication?]. Unfortunately only the geologist De Giorgi [3] in one of his book, reports that San Nicolò and Cataldo church (a Romanique church) was treated with encaustics, but PyGCMS analyses carried out on a few samples collected before restoration do not agree with this report [tesi? Poster nostro?]. Also workers protected both materials and techniques, making quite difficult today to identify the ancient product and procedures. A recent research reports that between the sixteenth century and the eighteenth century the facades were often left untreated whereas in other periods finishing techniques were applied for aesthetic, hygienic, protective or conservative purposes [1], however no material knowledge is reviewed. The study of literary, historical and oral sources has led to a list of organic products that could have been applied on the building surfaces as waterproof agent: among them, walnut oil, ovine or bovine milk, leaf of the prickly pear, wax, and bulb of the “Drimia maritima” plant [2]. Following this research, a collaborative project started in which all the organic products acknowledged in the different sources have been applied on laboratory samples. These “finished” samples have been aged naturally and artificially and studied by different analytical tools to identify potential biomarkers characteristic of the finishes. For this purpose, a multidisciplinary approach including optical, spectroscopic and chromatographic techniques was carried out and the relevant results will be presented and discussed in the present poster. [1] D. G. De Pascalis, L'arte di fabbricare e i fabbricatori, Nardò, Besa, 2001. [2] G. Siciliano, Tecniche di finitura dell’architettura in pietra a Lecce e provincia, tesi di laurea in “Storia delle tecniche artistiche”, Università degli Studi di Lecce, a.a. 2004-2005. [4] M. R. Derrick, D. Stulik, J. M. Landry, Infrared spectroscopy in conservation science. Scientific tools for conservation, Los Angeles, The Getty Conservation Institute, 1999.

The coupling of Laser Ablation (LA) with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is applied for the qualitative and quantitative determination of element in many areas of analytical chemistry (Di Franco et al., 2011; Giannossa et al., 2015). The aim of this work is the development of a method for the determination of heavy metals suspended by LA-ICP-MS in airborne inhalable particulate matter, sampled with an impactor high volume air sampler on quartz fiber filters. The easy, rapid, non-destructive method is proposed as a rapid screening procedure for this peculiar environmental specimen. The un-necessity of a preparative/extracting or diluting step and the absence of the stressing conditions generally included in that step (temperature, microwave power, strong acids) dramatically reduces the probability of interferences or underestimating errors (Rauch et al., 2001; Wang et al., 1999). On the other hand, a major statistical study is needed in planning instrumental conditions and data collecting, in order to ensure valuable and reproducible numerical data. We propose a cross-calibration procedure which uses the results obtained on some of the specimens of the sample batch, analysed after acidic digestion and interpolated on a aqueous standard solution calibration curve, as reference points for the direct quantification of the remaining samples, analysed under laser ablation. Real samples from a traffic city site and a rural site, taken as blank, were analysed and compared with acidic digestion analysis. The method was proved to be affordable, reliable and rapid to set. The method is also low environmental impact as it does not involve the use of harmful chemicals

Fibulae from the archaeological site of Egnatia (Fasano, Brindisi, ITALY) were examined by Laser Ablation Inductively Coupled Plasma Mass Spectrometry, micro-Raman Spectroscopy, Optical and Scanning Electron Microscopy with the aim of identifying kinds of alloys, process employed for their manufacturing and outlining the degrade. Obtained results, identifying the raw materials and the technological solutions used, allowed us to give convincing answers to the most part of archaeological questions: correct classification, dating and provenance of finds and confirmed the integration of Egnatia in a complex commercial network by sea because the significant port area along the Adriatic coasts and by land because the important Southern Adriatic arterial road. In addition, investigations refereed to the study of corrosion products in order to add a piece of knowledge in degradation mechanisms of ancient metallic items- nature of decay products, their depth distribution, correlation between patina nature and chemical composition of both, the underneath alloy and burial context – with a view to the planning more suitable restoration and preservation strategies.

Studies on the quality of marine environments in Italy have traditionally favoured heavily impacted areas, such as harbours and industrial areas, while there are few investigations aimed at the evaluation of the presence of organic pollutants in the areas of marine reserve. The aim of this study was to determine endocrine-disrupting compounds (EDCs) in the liver of white seabreams (Diplodus sargus sargus) from the Natural Reserve of Torre Guaceto, Italy. Among EDCs, alkyl-phenols 2,6-DTBP, 2,4-DTBP, OP, and BPA were identified and quantified. The mean concentration of 2,6-DTBP, 2,4-DTBP, OP, and BPA were 2.2, 2.0, 1.2 and 3.6ng/g of liver, respectively, confirming the occurrence and transfer of these organic pollutants in the food web of marine organisms in marine reserves.

Painted Canosa ceramics were examined to identify the nature of the pigments employed and their manufacturing technology. A multi-technical approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to ICP-MS. The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period that ranges from the end of the mid-seventh century to the first half of the fourth century b.C., and they were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forthy-eight pottery fragments were available for this study. No handling of the samples is required by Raman and it is possible to excise the pigmented layer in such a way that the lacunae are not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA-ICP-MS is concerned. Their combination demonstrated to be quite useful tools for the investigation of these archaeological materials: the chemical nature of the white, red, brown, and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance as it enables the artisan to obtain in one oxidising firing cycle both brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms Canosa was an important centre connecting near East and central Italy and Europe since pre-Roman age.

This chapter illustrates the usefulness of capillary electrophoresis (CE) for the analysis of amino acids, and both normal and chiral separations are covered. In order to provide a general description of the main results and challenges in the biomedical field, some relevant applications and reviews on CE of amino acids are tabulated. Furthermore, some detailed experimental procedures are shown, regarding the CE analysis of amino acids in body fluids, in microdialysate, and released upon hydrolysis of proteins. In particular, the protocols will deal with the following compounds: (1) underivatized aminoacids in blood; (2) γ-Aminobutyric acid, glutamate, and L-Aspartate derivatized with Naphthalene-2,3-dicarboxaldehyde; (3) hydrolysate from bovine serum albumine derivatized with phenylisothiocyanate. By examining these applications on real matrices, the capillary electrophoresis efficiency as tool for Amino Acid analysis can be ascertained.

Bitumen was found to occur on archaeological potsherds collected from two Apulia Middle Bronze Age sites, Monopoli and Torre Santa Sabina (Italy). Bitumen from two different areas, Majella (Italy) and Selenice (Albania), were analyzed as potential reference samples to assess the geographic origin of the archaeological bitumen using geochemical analytical techniques. Analysis of the archaeological samples from different layers at both sites showed that the bitumen possesses the same gross composition and biomarker distribution patterns. Sterane and terpane profiles from the archaeological samples were very similar to some of the geological samples collected from Selenice. In both archeological and selected Selenice samples, sterane distributions were dominated by the C-29 homologues (46-54%), followed by the C-27 (26-33%) and C-28 homologues (ca. 21%). Other biomarkers, such as gammacerane and oleanane, as well as the stable carbon isotopic composition of the asphaltene fraction, also suggest that the bitumen from the two archaeological sites was imported from Albania during Middle Bronze Age. (C) 2016 Elsevier Ltd. All rights reserved.

Evidences of bitumen use were found in several Apulian Bronze Age coastal sites such as Otranto, Roca, Le Pazze (LE), Scoglio del Tonno (TA), Monopoli (BA) and Torre Santa Sabina (BR), but there are no archaeometric data about its source origin or use. Bitumen from archaeological potsherds collected from two Apulia excavations, Monopoli and Torre Santa Sabina, and geological samples from three different areas, Majella, Selenicë and Ragusa, were analysed by GC-MS/MS to assess the geographic origin of the archaeological bitumen. The distribution pattern of steranes and terpanes obtained from archaeological sample is very similar to those ofgeological samples collected from Selenicë.Archeological and Selenicë samples (SBI and SB2) are dominatedby C29 steranes (53–54%) followed by C27 steranes(26–33 %) and only minor proportions of C28 steranes(21%). This bitumen compositional family distinguished by having lower C27 regular steranes and higher C29 regular steranes is inferred to have a non-marine, possibly lacustrine source. Other biomarkers such as gammacerane and oleanane as well as carbon isotopic data on δ13C on asphaltene fractionalso suggested that the bitumen used for pottery came from the same source area in Selenicë. GC-MS was also employed to show the deliberate addition of fats to the archaeological bitumen, probably to lower the quite high softening point (about 120 °C) of Selenicë bitumen. Further, the presence of benzothiophene in selected samples suggests the use at temperatures below 220 °C (benzothiophene boiling point). The processing in such narrow temperature range, exclude direct contact of vessels with flame and points to indirect heating systems (e.g. water-bath heating). Since no direct evidences of use for bitumen were found, and taking into account its occurrence in Apulian coastal sites, its main utilization for caulking is supposed. Only in few cases, bitumen was used as adhesive to repair pottery.

The Earth Sciences Museum of the University of Bari Aldo Moro (Italy) disposes of an ample collection of amber samples. These are of unknown origin or have been classified as Baltic amber (succinite), Sicilian amber (simetite), amber from New Jersey and New Zealand. However, many samples revealed to be erroneously classified due to incorrect information on the labels or in the museum catalogue - also due to historical forgeries as is often the case of simetite - or to the exchange of samples that probably occurred during the displacement of the museum collection from the Central University Building to the Geo-environmental and Earth Sciences Department. In this study all amber samples were systematically investigated with long and short wave UV rays, Fourier transform infrared (FTIR) spectroscopy and pyrolysis/gas chromatography-mass spectrometry (Py/GC-MS) using on-line thermally assisted hydrolysis methylation and silylation. The combined use of these analytical techniques allowed for a complete characterisation of the ambers. The compositional data could then be used for a correct classification and better valorisation of the amber samples of the museum collection.

Heme is an essential molecule in many biological processes, such as transport and storage of oxygen and electron transfer, as well as a structural component of hemoproteins. Defects of heme biosynthesis in developing erythroblasts have profound medical implications, as represented by sideroblastic anemia. The synthesis of heme requires the uptake of glycine into the mitochondrial matrix where glycine is condensed with succinyl coenzyme A to yield δ-aminolevulinic acid. Herein we describe the biochemical and molecular characterization of yeast Hem25p and human SLC25A38, providing evidence that they are mitochondrial carriers for glycine. In particular, the hem25Δ mutant manifests a defect in the biosynthesis of δ-aminolevulinic acid and displays reduced levels of downstream heme and mitochondrial cytochromes. The observed defects are rescued by complementation with yeast HEM25 or human SLC25A38 genes. Our results identify new proteins in the heme biosynthetic pathway and demonstrate that Hem25p and its human orthologue SLC25A38 are the main mitochondrial glycine transporters required for heme synthesis, providing definitive evidence of their previously proposed glycine transport function. Furthermore, our work may suggest new therapeutic approaches for the treatment of congenital sideroblastic anemia.

The geology of Serbia is dominated by the Dinaride-Hellenide orogen that consists of lithological units with heterogeneous cherty material. This material occurs mainly within the Triassic porphyry-chert formation and the Jurassic diabase-chert formation. The latter is associated with a complex ophiolitic melange. These units contain blocks and olistoliths of layered and massive cherts and radiolarites, sometimes up to 15 m thick. In addition, post-ophiolitic Cretaceous limestones of western and eastern Serbia contain cherts and radiolarites as nodules and lenses, and they usually show gradual transitions to limestones or silicified limestones. This widespread cherty material, which could be used to knap the stone artefacts fount at prehistoric sites in Serbia, is very poorly characterized in terms of petrological and geochemical features.

Rifamycins are mainstay agents in treatment of many widespread diseases, but how an improved rifamycin producer can be created is still incompletely understood. Here, we describe a comparative genomic approach to investigate the mutational patterns introduced by the classical mutate-and-screen method in the genome of an improved rifamycin producer. Comparing the genome of the rifamycin B overproducer Amycolatopsis mediterranei HP-130 with those of the reference strains A. mediterranei S699 and U32, we identified 250 variations, affecting 227 coding sequences (CDS), 109 of which were HP-130-specific since they were absent in both S699 and U32. Mutational and transcriptional patterns indicated a series of genomic manipulations that not only proved the causative effect of mutB2 (coding for methylmalonyl-CoA mutase large subunit) and argS2 (coding for arginyl tRNA synthetase) mutations on the overproduction of rifamycin, but also constituted a rational strategy to genetically engineer a reference strain into an overproducer.

Information about dispersal scales of fish at various life history stages is critical for successful design of networks of marine protected areas, but is lacking for most species and regions. Otolith chemistry provides an opportunity to investigate dispersal patterns at a number of life history stages. Our aim was to assess patterns of larval and post-settlement (i.e. between settlement and recruitment) dispersal at two different spatial scales in a Mediterranean coastal fish (i.e. white sea bream, Diplodus sargus sargus) using otolith chemistry. At a large spatial scale (similar to 200 km) we investigated natal origin of fish and at a smaller scale (similar to 30 km) we assessed "site fidelity" (i.e. post-settlement dispersal until recruitment). Larvae dispersed from three spawning areas, and a single spawning area supplied post-settlers (proxy of larval supply) to sites spread from 100 to 200 km of coastline. Post-settlement dispersal occurred within the scale examined of similar to 30 km, although about a third of post-settlers were recruits in the same sites where they settled. Connectivity was recorded both from a MPA to unprotected areas and vice versa. The approach adopted in the present study provides some of the first quantitative evidence of dispersal at both larval and post-settlement stages of a key species in Mediterranean rocky reefs. Similar data taken from a number of species are needed to effectively design both single marine protected areas and networks of marine protected areas.

In the marine context, information about dispersal is essential for the design of networks of marine protected areas (MPAs). Generally, most of the dispersal of demersal fishes is thought to be driven by the transport of eggs and larvae in currents, with the potential contribution of dispersal in later life stages relatively minimal. Using otolith chemistry analyses, we estimate dispersal patterns across a spatial scale of approximately 180 km at both propagule (i.e. eggs and larvae) and juvenile (i.e. between settlement and recruitment) stages of a Mediterranean coastal fishery species, the two-banded seabream Diplodus vulgaris. We detected three major natal sources of propagules replenishing local populations in the entire study area, suggesting that propagule dispersal distance extends to at least 90 km. For the juvenile stage, we detected dispersal of up to 165 km. Our work highlights the surprising and significant role of dispersal during the juvenile life stages as an important mechanism connecting populations. Such new insights are crucial for creating effective management strategies (e.g. MPAs and MPA networks) and to gain support from policymakers and stakeholders, highlighting that MPA benefits can extend well beyond MPA borders, and not only via dispersal of eggs and larvae, but also through movement by juveniles.

The application of analytical chemistry to archaeological research has increased substantially over the last half-century and today represents a major methodological subfield within archaeological science. The paper reports the results obtained onto a selection of Final Bronze Age ceramic materials from Bronze Age site of Roca. Two pithoi in fine fabric -figulina- and five vessels in coarse fabric -impasto- (one olla, one dipper, three small cups) have been selected and analyzed. Regarding the archaeological contexts of provenience, one pithos comes from the so called Capanna-Magazzino located in SAS VI and all the other materials come from the South-East sector of the so called Capanna-Tempio located in SAS IX. Using high temperature gas chromatography and compound specific isotopic ratio, it has been possible to identify different types of lipids absorbed by the ceramic core. The pithos from the Capanna-Tempio shows residues of lipids clearly identified as olive oil. The olla and the dipper show residues of lipids referable to non-ruminant animals. One of the three small cups does not contain any traces of lipids but quantities of beeswax and some evidence of conifer's resins. Two cups contain residues of animal lipids that can be attributed to ruminant animals, particularly to sheep. The pithos from the Capanna-Tempio demonstrates processes of accumulation of huge quantities of olive oil in a ritual context characterized by precise comparisons with the Bronze Age Aegean. The traces of resin in the pithos from the Capanna-Magazzino could be interpreted both as results of surface treatment or as residues of various contents different from olive oil, such as flavored wine. The animal lipids found in the olla seem to confirm the use of this shape in food-preparing activities.

In recent decades, archaeometric research about obsidian sources and circulation in Central Mediterranean area has achieved good results, despite what has happened with other knappable materials. Detailed archaeometric literature on cherty materials is poor and discontinuous in time and space. Difficulties in unambiguous characterisation to identify distinguishing features of chert for sourcing, makes it relatively hard to compare materials from different regions and retrace ancient trade routes. Current archaeological knowledge about the circulation of chert in the central Mediterranean Sea identifies Gargano Promontory as one of the main sources. In addition, the Gargano Promontory is located along one of the supposed routes of the spread of the Neolithic in southern Italy, which is the “bridge” of Adriatic islands connecting southern Croatia to the north of Apulia. In the current state of research, the geography of the Early Neolithic landscape of the promontory shows that only the area exploited for chert sources was inhabited. Early Neolithic sites and mines lie along the coast in a well-defined area, and no other site is present within a radius of about 25 km. This fact suggests an interpretation of the Neolithic mining area as an “island” area and thus the establishment of maritime expedition for the supply of Gargano chert, just as the Mediterranean islands were rich in obsidian. This suggests the possibility of a special status in the Neolithic of these territories rich in lithic raw material. In general terms, our analytical approach focuses on the correlation among quantitative data of texture or structure, colorimetry, reflectance or gloss and chemistry (through LA-ICP-MS) obtained from geological chert samples and mine debris from Gargano Promontory. Three out of the four geological formations investigated (i.e. Calcare di Peschici Formation, Maiolica Formation, and Scaglia Formation) were mined in the past, whereas traces of mining in the Marne a Fucoidi Formation are unknown to-date. In this work we present our results based on macroscopic and chemical analysis of a selection of 151 samples of chert to understand the variability of the intrinsic features and use them as potential discriminant factors for provenance. In each formation, cherts with different features and quality coexist. Among multiple sampling in outcrops with several chert layers, macroscopic and chemical results show lateral homogeneity and vertical heterogeneity. The chemical variability of chert samples is influenced by the distance from the cortex, when present. Geochemistry and colorimetry are not able to distinguish cherts of the four formations investigated. However, we observed some chromatic and chemical homogeneity on the level of sites (e.g., Defensola, Arciprete, Tagliacantoni for Peschici Formation, and Martinetti, Guariglia or Valle Sbernia, Bosco della Risega for Maiolica Formation).

Both academic and industrial laboratories currently use constraint - based reconstruction methods to predict optimal genetic modifications aiming at improving the yield of chemical production. Streptomyces ambofaciens, a prolific producer of bioactive compounds has been studied with different modeling tools . The interest is linked to its ability to produce a wide range of secondary metabolites such as spiramycin, kinamycin, antimycin and stambomycins, and novel polyketides with antibacterial and antiproliferative activities. In this study, the metabolic pattern of Streptomyces ambofaciens has been globally explored: a set of candidate overexpression gene targets supposed to lead to spiramycin overproduction have been evidenced through metabolic modeling. Model predictions were experimentally validated by genetic manipulation of the ethylmalonyl-CoA metabolic node, providing evidence that spiramycin productivity may be increased by enhancing the carbon flow through this pathway. The goal was achieved by over - expressing the ccr paralog srm4 in an ad hoc engineered plasmid. The first metabolic reconstruction of S. ambofaciens and the successful experimental validation of model predictions have been described and the validity and the importance of in silico modeling tools for the overproduction of molecules with a biotechnological interest demonstrated. As a result, the proposed metabolic reconstruction represents a solid platform for the future exploitation of S. ambofaciens biotechnological potential.

A multi-analytical approach was used to investigate Roman lead-glazed ceramic artefacts from archaeological excavations at Pompeii and Herculaneum (Italy) aiming at defining the production technology of both glaze and ceramic body, by way of integrated investigations. The chemical, structural, and micro-morphological characterisations were performed using a combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), optical microscopy (OM), scanning electron microscopy (SEM), and micro-Raman spectroscopy. Fragments of artefacts (skyphoi, oil lamps, bowls, askoi, amphorae, krateres) of great historical and archaeological interest were sampled. LA-ICP-MS was used to determine the elemental composition by virtue of its effective lateral resolution, its ability to detect most elements and also to analyse comparably small samples. All the archaeological objects were coated with a lead-based glaze produced using a lead oxide-plus-quartz mixture, with sodium/potassium feldspars added as a flux and two different metals used: copper and iron. Two types of ceramic pastes have been identified, but chemometric techniques support the hypothesis of a Campanian provenance for the raw materials. Degradation phenomena such as the partial devitrification of the glaze, i.e. the slow structural reorganisation towards stable crystalline phases, and the leaching by mineral dissolution in the soil, were determined.

The present paper submits the study of a potsherds sample collected during the Grotte di Pertosa-Auletta (SA) 2013 research campaign. The survey was carried out in the temporarily drained riverbed area of the “antegrotta”: the nearest sector to the entrance of the cave, where traces of a Bronze age pile-dwelling have been found. The high grade of fragmentation of the pottery assemblage and the lack of stratigraphic data makes the interpretation of the ndings more complex. Therefore a comparison between our sample and the ceramics from the Carucci Collection, kept in the Museo Preistorico ed Etnogra co Luigi Pigorini in Rome, has been made. On the one hand this allowed us to make a comparison with a very well- preserved sample although belonging to a late XIX selection, as it often happens for historical collections. On the other hand the 2013 sample represents an excellent specimen to carry out GC-MS analyses, performed by the Laboratorio di Spettrometria di Massa Analitica e Isotopica of the Università del Salento. These analyses provided early data concerning the function of the pottery items and shed new light on the use of the cave during the Bronze Age.

Pelagic larval duration (PLD) and trace elements in otoliths provide basic information to investigate the dispersal history of marine fishes. Due to the paucity of such information in the Mediterranean region, we assessed PLD, hatching and settlement duration and timing, and otolith microelemental composition of the White Sea bream (Diplodus sargus sargus) from multiple locations (hundreds of kilometers from each other) along the Italian coast (Mediterranean Sea). Otoliths were read to assess PLD and analyzed by a laser ablation inductively coupled plasma mass spectrometer in the core, larval and juvenile regions. PLD ranged from 14 to 17 days and significantly changed among locations, similarly to hatching (temporal windows of 10-24 days) and settlement (8-22 days) duration and timing, and microelemental fingerprints. These results show (1) a non-negligible large-scale variability in juvenile fish traits and otolith chemistry ever tested before for any Mediterranean fish; (2) the usefulness to properly estimate those traits and chemical features that may help shed light on spatial patterns of population connectivity and dispersal of marine fishes.

This work presents an analytical procedure based on gas chromatography-mass spectrometry which allows the determination of aldoses (glucose, mannose, galactose, arabinose, xylose, fucose, rhamnose) and chetoses (fructose) in plant material. One peak for each target carbohydrate was obtained by using an efficient derivatization employing methylboronic acid and acetic anhydride sequentially, whereas the baseline separation of the analytes was accomplished using an ionic liquid capillary column. First, the proposed method was optimized and validated. Successively, it was applied to identify the carbohydrates present in plant material. Finally, the procedure was successfully applied to samples from a XVII century painting, thus highlighting the occurrence of starch glue and fruit tree gum as polysaccharide materials.

Protein analysis in biological fluids, such as urine, by means of mass spectrometry (MS) still suffers for insufficient standardization in protocols for sample collection, storage and preparation. In this work, the influence of these variables on healthy donors human urine protein profiling performed by matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was studied. A screening of various urine sample pre-treatment procedures and different sample deposition approaches on the MALDI target was performed. The influence of urine samples storage time and temperature on spectral profiles was evaluated by means of principal component analysis (PCA). The whole optimized procedure was eventually applied to the MALDI-TOF-MS analysis of human urine samples taken from prostate cancer patients. The best results in terms of detected ions number and abundance in the MS spectra were obtained by using home-made microcolumns packed with hydrophilic-lipophilic balance (HLB) resin as sample pre-treatment method; this procedure was also less expensive and suitable for high throughput analyses. Afterwards, the spin coating approach for sample deposition on the MALDI target plate was optimized, obtaining homogenous and reproducible spots. Then, PCA indicated that low storage temperatures of acidified and centrifuged samples, together with short handling time, allowed to obtain reproducible profiles without artifacts contribution due to experimental conditions. Finally, interesting differences were found by comparing the MALDI-TOF-MS protein profiles of pooled urine samples of healthy donors and prostate cancer patients. The results showed that analytical and pre-analytical variables are crucial for the success of urine analysis, to obtain meaningful and reproducible data, even if the intra-patient variability is very difficult to avoid. It has been proven how pooled urine samples can be an interesting way to make easier the comparison between healthy and pathological samples and to individuate possible differences in the protein expression between the two sets of samples.

PON 254/Ric. Potenziamento del “Centro Ricerche per la Salute dell’Uomo e dell’Ambiente” Cod. PONa3_00334;Consorzio Interuniversitario di Ricerca in Chimica dei Metalli nei Sistemi Biologici (CIRCMSB), Bari (Italy).

Celiac disease (CD) is one of the most common digestive disorders caused by an abnormal immune reaction to gluten. So far there are no available therapies, the only solution is a strict gluten-free diet, which however could be very challenging as gluten can be hidden in many food products. Furthermore an additional problem is related to cross-contamination of nominal gluten-free foods with gluten-based ones during manufacturing. Here we propose a lab on chip platform as a powerful tool to help food manufacturers to evaluate the real amount of gluten in their products by an accurate in-situ control of the production chain and maybe to specify the real gluten content in packages labeling. Our portable gliadin-immunochips, based on an electrochemical impedance spectroscopy transduction method, were first calibrated and then validated for both liquid and solid food matrixes by analyzing different beers and flours. The high specificity of our assay was also demonstrated by performing control experiments on rice and potatoes flours containing prolamin-like proteins. We achieved limit of quantification of 0.5 ppm for gliadin that is 20 times lower than the worldwide limit established for gluten-free food while the method of analysis is faster and cheaper than currently employed ELISA-based methods. Moreover our results on food samples were validated through a mass spectrometry standard analysis.

The assessment of fish dispersal is fundamental for both conservation and management of fishery resources as it provides crucial information for the establishment of more effective marine protected areas (MPAs) and networks of MPAs. In this study, we investigated the elemental composition of otoliths in early life stages of the saddled sea bream Oblada melanura (Linnaeus, 1758) (Perciformes: Sparidae) in order to obtain information on its propagule (egg and larva) dispersal in the south-western Mediterranean Sea. Specifically, using pre-settlement individuals we investigated (1) larval patch cohesiveness during the last phase of larval life; and with early post-settlement individuals we investigated (2) the number of potential natal sources, and (3) propagule dispersal distances. Results indicated that different larval patches can merge in the pelagic environment after having travelled separately for some days. In total, 7 natal sources were found to replenish, with different proportions, almost all sampling sites along a stretch of coastline of similar to 180 km, suggesting that propagule dispersal can extend at least up to similar to 90 km. This information provides important insights for understanding fish dispersal processes and supports the appropriate establishment of spatially explicit conservation strategies such as MPAs and MPA networks in the south-western Mediterranean Sea.

Bitumen has been used frequently in the Near East throughout history until modern times. Natural bitumen, found in solid or liquid form, was exploited and processed by ancient populations in Egypt, Mesopotamia and Syria for several uses such as to repair broken pottery, to waterproof containers or boats, to build the massive ziggurat temple mounds or to haft composite flint tools. Together with the more widely studied and archaeologically important bitumen deposits in the Near East and Middle East, there are several seepages in Central Mediterranean which deserve more attention with respect to their exploitation and circulation in Antiquity. Evidence of bitumen use was found at several Apulian Bronze Age coastal sites 6 , such as Otranto, Roca, Le Pazze (Lecce), Scoglio del Tonno (Taranto), Monopoli (Bari) and Torre Santa Sabina (Brindisi), but there are no archaeometric data about the relevant source(s). Different bitumens from the central mediterranean sea region were studied as a possible source and analysed together with the archa eological samples using a geochemical, biomarker - based approach. The compositions of geological and archaeological samples were determined and provenance established. In the present communication, the relevant results will be described.

Comparison of fine and coarse fractions in terms of sources and dynamics is scarce in southeast Mediterranean countries; differences are relevant because of the importance of natural sources like sea spray and Saharan dust advection, because most of the monitoring networks are limited to PM10. In this work, the main seasonal variabilities of sources and processes involving fine and coarse PM (particulate matter) were studied at the Environmental-Climate Observatory of Lecce (Southern Italy). Simultaneous PM2.5 and PM10 samples were collected between July 2013 and July 2014 and chemically analysed to determine concentrations of several species: OC (organic carbon) and EC (elemental carbon) via thermo-optical analysis, 9 major ions via IC, and 23 metals via ICP-MS. Data was processed through mass closure analysis and Positive Matrix Factorization (PMF) receptor model characterizing seasonal variabilities of nine sources contributions. Organic and inorganic secondary aerosol accounts for 43% of PM2.5 and 12% of PM2.5–10 with small seasonal changes. SIA (secondary inorganic aerosol) seasonal pattern is opposite to that of SOC (secondary organic carbon). SOC is larger during the cold period, sulphate (the major contributor to SIA) is larger during summer. Two forms of nitrate were identified: NaNO3, correlated with chloride depletion and aging of sea-spray, mainly present in PM2.5–10; NH4NO3 more abundant in PM2.5. Biomass burning is a relevant source with larger contribution during autumn and winter because of the influence of domestic heating, however, is not negligible in spring and summer, because of the contributions of fires and agricultural practices. Mass closure analysis and PMF results identify two soil sources: crustal associated to long range transport and carbonates associated to local resuspended dust. Both sources contributes to the coarse fraction and have different dynamics with crustal source contributing mainly in high winds from SE conditions and carbonates during high winds from North direction.

We show that anthocyanines extracted from 3 different local cultivar of grapes characteristic of the South Italian region named ''Salento'' can effectively act as nature-friendly and eco-sustainable sensitizers in Dye-sensitized Solar Cells (DSSC) type devices. The natural pigments have been extracted in a simple way by immersing both the whole fruits and the fruit epicarps in methanol and in an ultrasonic bath, without any further purification step. The measured open circuit voltage and the fill factors are among the best values reported in literature. We compare the effectiveness of the extraction process from fermented and from fresh grapes, showing that the devices realized starting from the fresh fruit epicarps perform slightly better than those realized starting from the fermented fruit. We correlate this behavior with an interaction of different dye molecules in the device.

Spiramycin is a macrolide antibiotic and antiparasitic that is used to treat toxoplasmosis and various other infections of soft tissues. In the current study, we evaluated the effects of α-cyclodextrin, β-cyclodextrin, or methyl-β-cyclodextrin supplementation to a synthetic culture medium on biomass and spiramycin production by Streptomyces ambofaciens ATCC 23877. We found a high stimulatory effect on spiramycin production when the culture medium was supplemented with 0.5% (w/v) methyl-βcyclodextrin, whereas α-cyclodextrin or β-cyclodextrin weakly enhanced antibiotic yields. As the stimulation of antibiotic production could be because of spiramycin complexation with cyclodextrins with effects on antibiotic stability and/or efflux, we analyzed the possible formation of complexes by physical−chemical methods. The results of Job plot experiment highlighted the formation of a nonhost@guest complex methyl-β-cyclodextrin@ spiramycin I in the stoichiometric ratio of 3:1 while they excluded the formation of complex between spiramycin I and α- orβ-cyclodextrin. Fourier-transform infrared spectroscopy measurements were then carried out to characterize the methyl-β-cyclodextrin@spiramycin I complex and individuate the chemical groups involved in the binding mechanism. These findings may help to improve the spiramycin fermentation process, providing at the same time a new device for better delivery of the antibiotic at the site of infection by methyl-β-cyclodextrin complexation, as it has been well-documented for other bioactive molecules.

In this study for the first time the bulk chemical composition of Sicilian amber (simetite) was determined using pyrolysis-gas chromatography-mass spectrometry with thermally assisted hydrolysis and methylation (Py(THM)-GC-MS). The results evidenced that the polymer fraction of Sicilian amber is based on a polylabdanoid structure with an enantio configuration, mainly including ozic acid and biformene. In addition, numerous monocydic and bicyclic terpene degradation products could be detected. At higher retention times several characteristic compounds were found. Very low amounts of succinic acid could be revealed. The chemical data allowed to classify simetite as a Class 1c resinite and to suggest a botanical origin from Fabaceae. (C) 2015 Elsevier B.V. All rights reserved.

The city of Lecce (Puglia, Italy) known internationally thank s to the local stone handicraft and to the precious historical and artistic monuments, owes its title of "Cradle of the Baroque" to two types of rock: pietra leccese and carparo. These two rocks belong to the group of miocenic limestone and of quaternary limestone, respectively. The formation of soil of Puglia dates to the quaternary and tertiary periods and soil is characterized by limestone with chemical and physical characteristics very different from each other and with satisfactory colors. Thanks to their quality pietra leccese and carparo were the materials mostly used by local artisans for the construction of buildings located in Salento peninsula (Puglia-Southern Italy) since ancient times. The complex baroque architecture of the city of Lecce was also produced: significant examples are the pinnacles, the decorations, the capitals, the statues that decorate the facades of the baroque buildings of the city of Lecce. In these buildings, public or private, laic or religious, the bricks of the facades sometimes were left untreated, more often were finished with inorganics or organics for aesthetic, hygienic or protective purposes. Knowledge of the finish materials applied on the facades of these buildings is important to plan a correct restoration and to preserve the cultural heritage and the tourism of the city. However, there are several difficulties such as the scarcity of written sources, since the finishing techniques used in the past were jealously preserved by artisans, and, mainly for organics, the phenomena of alteration and degradation that inhibit the identification of the techniques employed. A multidisciplinary research, which involved the study of the few written and oral sources, has allowed the identification of some organic products, which possibly were applied by the artisans of Salento on the surface of the buildings constructed between the 1600 and 1900 centuries: among these products, there are also natural materials whose usage was not hyphotesized before on cultural stone heritage. In the present work laboratory specimens of pietra leccese and carparo, treated according to the already known and knewly discovered recipes and subjected to natural and artificial aging, have been studied, through the use of optical, colorimetric, spectroscopic and chromatographic techniques; the employed analytical methods were of great help to the identification of molecular markers, characteristic of the various organic substances, and to the characterization of methods, used in the past on the facades of baroque buildings of Lecce, revealing some secrets of the ancient artisans of Salento.

A multidisciplinary research was conducted by the University of Salento in collaboration with the Lecce Provincial Museum, in order to study different forms of art widespread in the Salento peninsula (Southern Italy) very valuable from an artistic point of view and important as driving force for the tourism of the area. In this research, the archaeometrical analysis was used to study the first cycle of paintings of the church of Santa Maria delle Cerrate, an italo-greek monastery located in the country about 15 km north-east of Lecce, probably built in the 12th century. Microscopic, chromatographic and spectrometric techniques were used: optical microscopy was used to study samples and the relevant stratigraphy, micro-Raman Spectroscopy to identify pigments and Gas Chromatography with Mass Spectrometric Detection to investigate the techniques masters used to decorate the monastery church. Further information on organic and inorganic materials present in the samples were obtained from Fourier transform infrared analysis in attenuated total reflectance. Materials and techniques were clearly ascertained, and, interestingly, pigments were applied both by fresco and egg-based tempera. Among the various pigments detected, the identification of both lapis lazuli and lead white opened new perspectives both from the historical and conservative points of view. Copyright © 2013 John Wiley & Sons, Ltd.

Several analytical techniques are actually employed for the study of Cultural Heritage and permit to identify production methodologies, constituent materials, degradation products, dating and provenance of the objects examined; elemental analyses provide precious information to archaeologists, art historians, restorers and analysts, opening a door into the past. Those techniques capable of ensuring versatility of application, sensitivity and non-destructive or micro-invasive analysis are generally requested. Laser ablation–inductively coupled plasma–mass spectrometry (LA-ICPMS), by virtue of its effective lateral resolution, sensitivity to most elements and capacity of outdoing limitations due to the low quantity of accessible samples, fulfils these requirements. Multivariate statistical techniques applied to the elemental data permit classification and provenance of artistic objects and allow to confute or confirm historical hypotheses. In the present work several case studies, addressed recently by the authors concerning objects of artistic and historical value, are outlined: pottery and glazes of Vesuvian area (Campania, Italy), fibulae of Egnatia (Puglia, Italy), inks of painting of Sant’Irene by Giuseppe Verrio and lime mortars from Siponto (Puglia, Italy). For each of the presented activity, results, advantages and drawbacks of the LA-ICPMS were discussed.

Spawning patterns of European anchovy were investigated in the eastern Ligurian Sea (NW Mediterranean) by using otolith microchemistry. Otolith cores of 1-year-old anchovies showed a homogeneous chemical composition, while those of 2 years old anchovies separated into five different groups. This suggests the occurrence of single vs. multiple spawning areas related to the two annual cohorts. Patterns of core microchemistry of 2 years old anchovies support the hypothesis of different spawning areas, possibly characterised by different salinity regimes, in the eastern Ligurian Sea (e.g. typical marine habitats like shelf edges vs. lower salinity locations like river mouths). Results suggest that: (1) stocks of European anchovy could depend on different spawning areas characterised by different environmental conditions; (2) patterns may change from year to year, and this could affect the annual risk of stock fluctuations or collapse; and (3) the use of otolith microchemistry is a promising approach for investigating spawning patterns of European anchovy. © 2012 Elsevier B.V.