Sulfur isotope analysis of cinnabar from Roman wall paintings by elemental analysis/isotope ratio mass spectrometry - tracking the origin of archaeological red pigments and their authenticity

The most valuable pigment of the Roman wall paintings was the red color obtained from powdered cinnabar (Minium Cinnabaris pigment), the red mercury sulfide (HgS), which was brought from mercury (Hg) deposits in the Roman Empire. To address the question of whether sulfur isotope signatures can serve as a rapid method to establish the provenance of the red pigment in Roman frescoes, we have measured the sulfur isotope composition (delta(34) S value in parts per thousand VCDT) in samples of wall painting from the Roman city Aventicum (Avenches, Vaud, Switzerland) and compared them with values from cinnabar from European mercury deposits (Almaden in Spain, Idria in Slovenia, Monte Amiata in Italy, Moschellandsberg in Germany, and Genepy in France). Our study shows that the delta(34) S values of cinnabar from the studied Roman wall paintings fall within or near to the composition of Almaden cinnabar; thus, the provenance of the raw material may be deduced. This approach may provide information on provenance and authenticity in archaeological, restoration and forensic studies of Roman and Greek frescoes. Copyright (c) 2010 John Wiley & Sons, Ltd.

Magma generation at the easternmost section of the Hellenic arc: Hf, Nd, Pb and Sr isotope geochemistry of Nisyros and Yali volcanoes (Greece)

Geochemical and petrographical studies of lavas and ignimbrites from the Quaternary Nisyros-Yali volcanic system in the easternmost part of the Hellenic arc (Greece) reveal insight into magma generating processes. A compositional gap between 61 and 68 wt.% SiO2 is recognized that coincides with the stratigraphic distinction between pre-caldera and postcaldera volcanic units. Trace element systematics support the subdivision of Nisyros and Yali volcanic units into two distinct suites of rocks. The variation of Nd and Hf present day isotope data and the fact that they are distinct from the isotope compositions of MORB rule out an origin by pure differentiation and require assimilation of a crustal component. Lead isotope ratios of Nisyros and Yali volcanic rocks support mixing of mantle material with a lower crust equivalent. However, Sr-87/Sr-86 ratios of 0.7036-0.7048 are incompatible with a simple binary mixing scenario and give low depleted mantle extraction ages (< 0.1 Ga), in contrast with Pb model ages of 0.3 Ga and Hf and Nd model ages of ca. 0.8 Ga. The budget of fluid-mobile elements Sr and Pb is likely to be dominated by abundant hydrous fluids characterised by mantle-like Sr isotope ratios. Late stage fluids probably were enriched in CO2, needed to explain the high Th concentrations. The occurrence of hydrated minerals (e.g., amphibole) in the first post-caldera unit with the lowermost Sr-87/Sr-86 ratio of 0.7036 +/- 2 can be interpreted as the result of the increased water activity in the source. The presence of two different plagioclase phenocryst generations in the first lava subsequent to the caldera-causing event is indicative for a longer storage time of this magma at a shallower level. A model capable of explaining these observations involves three evolutionary stages. First stage, assimilation of lower crustal material by a primitive magma of mantle origin (as modelled by Nd-Hf isotope systematics). This stage ended by an interruption in replenishment that led to an increase of crystallization and, hence, an increase in viscosity, suppressing eruption. During this time gap, differentiation by fractional crystallization led to enrichment of incompatible species, especially aqueous fluids, to silica depolymerisation and to a decrease in viscosity, finally enabling eruption again in the third stage. (c) 2005 Elsevier B.V. All rights reserved.

Animal model to compare the effects of suture technique on cross-sectional compliance on end-to-side anastomoses.

OBJECTIVE: An animal model has been developed to compare the effects of suture technique on the luminal dimensions and compliance of end-to-side vascular anastomoses. METHODS: Carotid and internal mammalian arteries (IMAs) were exposed in three pigs (90 kg). IMAs were sectioned distally to perform end-to-side anastomoses on carotid arteries. One anastomosis was performed with 7/0 polypropylene running suture. The other was performed with the automated suture delivery device (Perclose/Abbott Labs Inc.) that makes a 7/0 polypropylene interrupted suture. Four piezoelectric crystals were sutured on toe, heel and both lateral sides of each anastomosis to measure anastomotic axes. Anastomotic cross-sectional area (CSAA) was calculated with: CSAA = pi x mM/4 where m and M are the minor and major axes of the elliptical anastomosis. Cross-sectional anastomotic compliance (CSAC) was calculated as CSAC=Delta CSAA/Delta P where Delta P is the mean pulse pressure and Delta CSAA is the mean CSAA during cardiac cycle. RESULTS: We collected a total of 1200000 pressure-length data per animal. For running suture we had a mean systolic CSAA of 26.94+/-0.4 mm(2) and a mean CSAA in diastole of 26.30+/-0.5 mm(2) (mean Delta CSAA was 0.64 mm(2)). CSAC for running suture was 4.5 x 10(-6)m(2)/kPa. For interrupted suture we had a mean CSAA in systole of 21.98+/-0.2 mm(2) and a mean CSAA in diastole of 17.38+/-0.3 mm(2) (mean Delta CSAA was 4.6+/-0.1 mm(2)). CSAC for interrupted suture was 11 x 10(-6) m(2)/kPa. CONCLUSIONS: This model, even with some limitations, can be a reliable source of information improving the outcome of vascular anastomoses. The study demonstrates that suture technique has a substantial effect on cross-sectional anastomotic compliance of end-to-side anastomoses. Interrupted suture may maximise the anastomotic lumen and provides a considerably higher CSAC than continuous suture, that reduces flow turbulence, shear stress and intimal hyperplasia. The Heartflo anastomosis device is a reliable instrument that facilitates performance of interrupted suture anastomoses.

Urinary analysis of 16(5alpha)-androsten-3alpha-ol by gas chromatography/combustion/isotope ratio mass spectrometry: implications in anti-doping analysis.

We present a method for the analysis of urinary 16(5alpha)-androsten-3alpha-ol together with 5beta-pregnane-3alpha,20alpha-diol and four testosterone metabolites: androsterone (Andro), etiocholanolone (Etio), 5alpha-androstane-3alpha,17beta-diol (5alphaA), 5beta-androstane-3alpha,17beta-diol (5betaA) by means of gas chromatography/combustion/isotopic ratio mass spectrometry (GC/C/IRMS). The within-assay and between-assay precision S.D.s of the investigated steroids were lower than 0.3 and 0.6 per thousand, respectively. A comparative study on a population composed of 20 subjects has shown that the differences of the intra-individual delta(13)C-values for 16(5alpha)-androsten-3alpha-ol and 5beta-pregnane-3alpha,20alpha-diol are less than 0.9 per thousand. Thereafter, the method has been applied in the frame of an excretion study following oral ingestion of 50 mg DHEA initially and oral ingestion of 50mg pregnenolone 48 h later. Our findings show that administration of DHEA does not affect the isotopic ratio values of 16(5alpha)-androsten-3alpha-ol and 5beta-pregnane-3alpha,20alpha-diol, whereas the isotopic ratio values of 5beta-pregnane-3alpha,20alpha-diol vary by more 5 per thousand upon ingestion of pregnenolone. We have observed delta(13)C-value changes lower than 1 per thousand for 16(5alpha)-androsten-3alpha-ol, though pregnenolone is a precursor of the 16-ene steroids. In contrast to 5beta-pregnane-3alpha,20alpha-diol, the 16-ene steroid may be used as an endogenous reference compound when pregnenolone is administered.

Middle and Late Jurassic carbon stable-isotope stratigraphy and radiolarite sedimentation of the Umbria-Marche basin (Central Italy)

A continuous carbon isotope curve from Middle-Upper Jurassic pelagic carbonate rocks was acquired from two sections in the southern part of the Umbria-Marche Apennines in central Italy. At the Colle Bertone section (Terni) and the Terminilletto section (Rieti), the Upper Toarcian to Bajocian Calcari e Marne a Posidonia Formation and the Aalenian to Kimmeridgian Calcari e Marne a Posidonia and Calcari Diasprigni formations were sampled, respectively. Biostratigraphy in both sections is based on rich assemblages of calcareous nannofossils and radiolarians, as well as some ammonites found in the upper Toarcian-Bajocian interval. Both sections revealed a relative minimum of delta(13)C(PDB) close to + 2 parts per thousand in the Aalenian and a maximum around 3.5 parts per thousand in early Bajocian, associated with an increase in visible chert. In basinal sections in Umbria-Marche, this interval includes the very cherry base of the Calcari Diasprigni Formation (e.g. at Valdorbia) or the chert-rich uppermost portion of the Calcari a Posidonia (e.g at Bosso). In the Terminilletto section, the Bajocian-early Barthonian interval shows a gradual decrease in delta(13)C(PDB) values and a low around 2.3 parts per thousand. This part of the section is characterised by more than 40 m of almost chart-free limestones and correlates with a recurrence of limestone-rich facies in basinal sections at Valdorbia. A double peak with values of delta(13)C(PDB) around + 3 parts per thousand was observed in the Callovian and Oxfordian, constrained by well preserved radiolarian faunas. The maxima lie in the Callovian and the middle Oxfordian, and the minimum between the two peaks should be near the Callovian/Oxfordian boundary. In the Terminilletto section, visible chert increases together with delta(13)C(PDB) values from the middle Bathonian and reaches peak values in the Callovian-Oxfordian. In basinal sections in Umbria-Marche, a sharp increase in visible chert is observed at this level within the Calcari Diasprigni. A drop of delta(13)C values towards + 2 parts per thousand occurs in the Kimmeridgian and coincides with a decrease of visible chert in outcrop. The observed delta(13)C positive anomalies during the early Bajocian and the Callovian-Oxfordian may record changes in global climate towards warmer, more humid periods characterised by increased nutrient mobilisation and increased carbon burial. High biosiliceous (radiolarians, siliceous sponges) productivity and preservation appear to coincide with the delta(13)C positive anomalies, when the production of platform carbonates was subdued and ceased in many areas, with a drastic reduction of periplatform ooze input in many Tethyan basins. The carbon and silica cycles appear to be linked through global warming and increased continental weathering. Hydrothermal events related to extensive rifting and/or accelerated oceanic spreading may be the endogenic driving force that created a perturbation of the exogenic system (excess CO2 into the atmosphere and greenhouse conditions) reflected by the positive delta(13)C shifts and biosiliceous episodes.

Mise en place d'un cathéter veineux central chez l'adulte. 2. Technique détaillée [The central vein catheterization. 2. Procedure, step by step]

La pose d'un cathéter veineux central peut se faire par plusieurs abords. La connaissance de l'anatomie, du matériel, la maîtrise des détails de la procédure pour chaque type d'abord et une attention particulière à l'asepsie sont des prérequis importants pour limiter les risques de complications et pour donner une information complète et exhaustive au patient. Cet article peut être utilisé comme base pour le développement d'une check-list, utile pour les médecins qui doivent procéder à la pose d'un cathéter veineux central mais qui ne possèdent pas encore une maîtrise du geste. Several approaches exist for central vein catheterization. Mastery of the various steps of this procedure and understanding of the basics of asepsis are critical to prevent any complication. They also built the basis for an exhaustive communication with the patient, to obtain an informed consent. This article can in addition be used to develop a checklist in order to (self-)assess competence in procedural skills

Assessing sedimentary evolution by means of Sr-isotope ratios : 3 case studies on the Caribbean plate : (Cretaceous: Nicoya Peninsula, Costa Rica, Tertiary: Hess Rise, and La Désirade, Guadeloupe, France)

The understanding of sedimentary evolution is intimately related to the knowledge of the exact ages of the sediments. When working on carbonate sediments, age dating is commonly based on paleontological observations and established biozonations, which may prove to be relatively imprecise. Dating by means of strontium isotope ratios in marine bioclasts is the probably best method in order to precisely date carbonate successions, provided that the sample reflects original marine geochemical characteristics. This requires a precise study of the samples including its petrography, SEM and cathodoluminescence observations, stable carbon and oxygen isotope geochemistry and finally the strontium isotope measurement itself. On the Nicoya Peninsula (Northwestern Costa Rica) sediments from the Piedras Blancas Formation, Nambi Formation and Quebrada Pavas Formation were dated by the means of strontium isotope ratios measured in Upper Cretaceous Inoceramus shell fragments. Results have shown average 87Sr/86Sr values of 0.707654 (middle late Campanian) for the Piedras Blancas Formation, 0.707322 (Turonian-Coniacian) for the Nambi Formation and 0.707721 (late Campanian-Maastrichtian) for the Quebrada Pavas Formation. Abundant detrital components in the studied formations constitute a difficulty to strontium isotope dating. In fact, the fossil bearing sediments can easily contaminate the target fossil with strontium mobilized form basalts during diagenesis and thus the obtained strontium isotope ratios may be influenced significantly and so will the obtained ages. The new and more precise age assignments allow for more precision in the chronostratigraphic chart of the sedimentary and tectonic evolution of the Nicoya Peninsula, providing a better insight on the evolution of this region. Meteor Cruise M81 dredged shallow water carbonates from the Hess Rise and Hess Escarpment during March 2010. Several of these shallow water carbonates contain abundant Larger Foraminifera that indicates an Eocene-Oligocene age. In this study the strontium isotope values ranging from 0.707847 to 0.708238 can be interpreted as a Rupelian to Chattian age of these sediments. These platform sediments are placed on seamounts, now located at depths reaching 1600 m. Observation of sedimentologic characteristics of these sediments has helped to resolve apparent discrepancies between fossil and strontium isotope ages. Hence, it is possible to show that the subsidence was active during early Miocene times. On La Désirade (Guadeloupe France), the Neogene to Quaternary carbonate cover has been dated by microfossils and some U/Th-ages. Disagreements subsisted in the paleontological ages of the formations. Strontium isotope ratios ranging from 0.709047 to 0.709076 showed the Limestone Table of La Désirade to range from an Early Pliocene to Late Pliocene/early Pleistocene age. A very late Miocene age (87Sr/86Sr =0.709013) can be determined to the Detrital Offshore Limestone. The flat volcanic basement had to be eroded by wave-action during a long-term stable relative sea-level. Sediments of the Table Limestone on La Désirade show both low-stand and high-stand facies that encroach on the igneous basement, implying deposition during a major phase of subsidence creating accommodation space. Subsidence is followed by tectonic uplift documented by fringing reefs and beach rocks that young from the top of the Table Limestone (180 m) towards the present coastline. Strontium isotope ratios from two different fringing reefs (0.707172 and 0.709145) and from a beach rock (0.709163) allow tentative dating, (125ky, ~ 400ky, 945ky) and indicate an uplift rate of about 5cm/ky for this time period of La Désirade Island. The documented subsidence and uplift history calls for a new model of tectonic evolution of the area.

Major, minor, trace element, Sm-Nd and Sr isotope compositions of mafic rocks from the earliest oceanic crust of the Alpine Tethys

Recent isotopic and biochronologic dating has demonstrated that the Gets nappe contains remnants of the oldest part of the oceanic crust of the Alpine Tethys. The ophiolites are associated with deep sea sediments, platform carbonates and continental crustal elements suggesting a transitional environment between continental and oceanic crust. Therefore, the ophiolites from the Gets nappe provide the opportunity to assess the nature of mantle source and the magma evolution during the final rifting stage of the European lithosphere. Trace clement analyses of mafic rocks can he divided into two sets: (1) P, Zr and Y contents are consistent with those of mid-ocean ridge basalts and REE patterns have a P-MORB affinity. (2) P,Zr Ti and Y contents are compatible with within-plate basalts and are characterized by REE spectra similar to that of T-MORB. Both have Nd isotopic compositions similar to those of synrift magma of the Red Sea and to the Rhine Graben. The model ages are in agreement with an LREE-enriched subcontinental mantle source derived from depleted mantle 800 to 900 Ma ago. Minor, trace element and Sm-Nd compositions suggest that these rocks are basaltic relies of an earliest stage of oceanic spreading i.e. an embryonic ocean. Comparison between REE patterns, Nd and Sr isotope compositions, isotopic and biochronologic ages from different Alpine Tethys ophiolites shows that samples with enriched LREE are from the older ophiolitic suites and are relies of the embryonic ocean floor. Later phases of ocean spreading are characterized by basalts that are depleted in LREE.