Evaluation of volatile chlorinated hydrocarbons distribution along depth profiles in the Ross Sea, Antarctica

The presence and the distribution along depth profiles of volatile chlorinated hydrocarbons (VCHCs) were evaluated in seawater samples collected in the Ross Sea (Southern Ocean, Antarctica) during the 2002-2003 Italian expedition. Sampling areas were located where the Circumpolar Deep Water interacts with the shelf waters that supply the Ross Sea.The VCHCs investigated were: 1,1,1-trichloroethane (C₂H₃Cl₃), tetrachloromethane (CCl₄), trichloroethylene (C₂HCl₃), tetrachloroethylene (C₂Cl₄). The analytical procedure consisted of a liquid-liquid extraction carried out with n-hexane directly in Antarctica, followed by gas chromatographic analysis with electron capture detection carried out in Italy.Concentration levels for the VCHCs analysed ranged from digits to hundreds of ng/L according to the station, depth and substance considered. Important differences in concentration levels between the three stations near the Ross Ice Shelf and the two stations located in the Cape Adare area were observed. In particular the stations situated in the Cape Adare zone, at certain depths, showed a thermal inversion due to the mixing of the Circumpolar Deep Water with the waters generated inside the Ross Sea Basin. The lowest concentration levels were recorded at this temperature increase.     

Tree ring microanalysis by LA–ICP–MS for environmental monitoring: validation or refutation? Two case histories

An empirical approach is presented for validating trace metal profiles in tree rings for use as environmental archives. Concentration profiles of Zn, Cd, Cu, Pb and U in tree rings and lake sediments are compared for assessing the reliability of the former as an environmental proxy. Laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry (LA–ICP–MS) is used for the direct analysis of tree rings. An optimised analytical protocol is devised with particular emphasis on sample preparation and quantification strategy. Significant correlations in the two environmental archives were found for zinc, copper and uranium, while cadmium and lead temporal trends, although showing enrichment in recent years, do not agree with the concentration profiles in lacustrine sediment cores. A chemical model based on metal affinity for hard type ligands present in wood is proposed to explain these results. Moreover, spring and winter wood are analysed separately thanks to the high spatial resolution of laser ablation sampling. As a result, enhanced metal loadings are shown to lead to intraring differences in trace metal concentrations.     

Extendable cohomologies for complex analytic varieties

We introduce a cohomology, called extendable cohomology, for abstract complex singular varieties based on suitable differential forms. Beside a study of the general properties of such a cohomology, we show that, given a complex vector bundle, one can compute its topological Chern classes using the extendable Chern classes, defined via a Chern–Weil type theory. We also prove that the localizations of the extendable Chern classes represent the localizations of the respective topological Chern classes, thus obtaining an abstract residue theorem for compact singular complex analytic varieties. As an application of our theory, we prove a Camacho–Sad type index theorem for holomorphic foliations of singular complex varieties.     

Hard X‐ray‐induced damage on carbon–binder matrix for in situ synchrotron transmission X‐ray microscopy tomography of Li‐ion batteries

The electrode of Li‐ion batteries is required to be chemically and mechanically stable in the electrolyte environment for in situ monitoring by transmission X‐ray microscopy (TXM). Evidence has shown that continuous irradiation has an impact on the microstructure and the electrochemical performance of the electrode. To identify the root cause of the radiation damage, a wire‐shaped electrode is soaked in an electrolyte in a quartz capillary and monitored using TXM under hard X‐ray illumination. The results show that expansion of the carbon–binder matrix by the accumulated X‐ray dose is the key factor of radiation damage. For in situ TXM tomography, intermittent X‐ray exposure during image capturing can be used to avoid the morphology change caused by radiation damage on the carbon–binder matrix.     

Analysis of Cannabinoids and Metabolites in Dried Urine Spots (DUS)

Dried urine spots (DUS) represent a potential alternative sample storage for forensic toxicological analysis. The aim of the current study was to develop and validate a liquid chromatographic tandem mass spectrometric procedure for the detection and quantitative determination of cannabinoids and metabolites in DUS. A two-step extraction was performed on DUS and urine samples. An LC-MS/MS system was operated in multiple reaction monitoring and positive polarization mode. The method was checked for sensitivity, specificity, linearity, accuracy, precision, recovery, matrix effects and carryover. The method was applied to 70 urine samples collected from healthy volunteers and drug addicts undergoing withdrawal treatment. The method was successfully developed for DUS. LODs lower than 2.0 ng/mL were obtained for all the monitored substances. All the validation parameters fulfilled the acceptance criteria either for DUS or urine. Among the real samples, 45 cases provided positive results for at least one compound. A good quali-quantitative agreement was obtained between DUS and urine. A good stability of THC, THCCOOH and THCCOOH-gluc was observed after a 24 h storage, in contrast to previously published results. DUS seems to provide a good alternative storage condition for urine that should be checked for the presence of cannabinoids and metabolites.     

Quantum Monte Carlo simulation of the high-pressure molecular-atomic crossover in fluid hydrogen

A first-order liquid-liquid phase transition in high-pressure hydrogen between molecular and atomic fluid phases has been predicted in computer simulations using ab initio molecular dynamics approaches. However, experiments indicate that molecular dissociation may occur through a continuous crossover rather than a first-order transition. Here we study the nature of molecular dissociation in fluid hydrogen using an alternative simulation technique in which electronic correlation is computed within quantum Monte Carlo methods, the so-called coupled electron-ion Monte Carlo method. We find no evidence for a first-order liquid-liquid phase transition.     

Transverse and soliton instabilities due to counterpropagation through a reflection grating in Kerr media

Transverse instabilities are shown to accompany counterpropagation of optical beams through reflection gratings in Kerr media. The instability threshold of continuous waves is analytically derived, and it is shown that the presence of the grating broadens and narrows the stability region of plane waves in focusing and defocusing media, respectively. Furthermore, counterpropagating soliton stability is numerically investigated and compared with the transverse modulation instability analysis, revealing an underlying physical link.     

A unifying theoretical and algorithmic framework for least squares methods of estimation in diffusion tensor imaging

A unifying theoretical and algorithmic framework for diffusion tensor estimation is presented. Theoretical connections among the least squares (LS) methods, (linear least squares (LLS), weighted linear least squares (WLLS), nonlinear least squares (NLS) and their constrained counterparts), are established through their respective objective functions, and higher order derivatives of these objective functions, i.e., Hessian matrices. These theoretical connections provide new insights in designing efficient algorithms for NLS and constrained NLS (CNLS) estimation. Here, we propose novel algorithms of full Newton-type for the NLS and CNLS estimations, which are evaluated with Monte Carlo simulations and compared with the commonly used Levenberg-Marquardt method. The proposed methods have a lower percent of relative error in estimating the trace and lower reduced chi2 value than those of the Levenberg-Marquardt method. These results also demonstrate that the accuracy of an estimate, particularly in a nonlinear estimation problem, is greatly affected by the Hessian matrix. In other words, the accuracy of a nonlinear estimation is algorithm-dependent. Further, this study shows that the noise variance in diffusion weighted signals is orientation dependent when signal-to-noise ratio (SNR) is low (相似文献   

ARDESIA: A fast silicon drift detector X-ray spectrometer for synchrotron applications

ARDESIA, a four-channel X-ray spectrometer based on silicon drift detectors (SDDs), is presented. It has been developed for synchrotron applications targeting especially X-ray fluorescence (XRF) and X-ray absorption spectroscopy (XAS) with good energy resolution at high count rates (a few Mcps per second). The main target applications are XRF and XAFS techniques. The system features a 2 × 2 monolithic array of 5-mm-pitch SDDs cooled with a double Peltier scheme and coupled to a four-channel CUBE charge preamplifier. Different digital pulse processors allowing operation in Mcps per second count rates are employed. The results of preliminary characterization measurements performed at both the LNF DAΦNE-Light DXR1 beamline and the ESRF LISA BM-08 are reported, in particular, XRF measurements on low atomic number elements (down to the Carbon K-line, 270 eV) and extended X-ray absorption fine structure of trace materials in pyrite.     

Twisted Lorentzian manifolds: a characterization with torse-forming time-like unit vectors

Robertson–Walker and generalized Robertson–Walker spacetimes may be characterized by the existence of a time-like unit torse-forming vector field, with other constrains. We show that Twisted manifolds may still be characterized by the existence of such (unique) vector field, with no other constrain. Twisted manifolds generalize RW and GRW spacetimes by admitting a scale function that depends both on time and space. We obtain the Ricci tensor, corresponding to the stress–energy tensor of an imperfect fluid.