Underwater sediment analyses by laser induced breakdown spectroscopy and calibration procedure for fluctuating plasma parameters

Laser Induced Breakdown Spectroscopy (LIBS) was applied on sediments directly under water. The aim of the research was to develop a method for measuring the sediment elemental composition, including minor elements, which could be implemented in-situ. The plasma was generated by a double-pulse, Q-Switched Nd:YAG laser operated at 1064 nm. For signal detection, both ICCD and non-gated, compact detectors were used. The major difficulties in underwater sediment analyses are related to the natural and laser induced surface roughness, and to the sample softness. The latter is responsible for the formation of particle clouds above the surface, which scatter both the laser and plasma radiation, and often results in breakdown formation above the analyzed surface. In such cases, a broad sonoluminescence emission from water, formed during the gas bubble collapse was sometimes registered. Under optimized experimental conditions, even by using a non-gated detector and single shot acquisition, it was possible to detect several minor sediment constituents, such as titanium, barium, manganese and others. A crude estimation of the Limit of Detection (LODs) for these elements was performed by underwater measurements on certified soils/sediments. Due to strong shot-to-shot fluctuations in the plasma temperature, well correlated calibration curves, aimed for quantitative analyses, could only be obtained after applying an appropriate data processing procedure. The latter selects automatically only the spectra characterized by similar plasma parameters, which are related to their continuum spectral distribution. Application of such a procedure improves the measurement accuracy also in other surroundings and on samples different from the ones analyzed here.     

Analysis of fresco by laser induced breakdown spectroscopy

The laser-based techniques have been shown to be a very powerful tool for artworks characterization and are used in the field of cultural heritage for the offered advantages of minimum invasiveness, in situ applicability and high sensitivity. Laser induced breakdown spectroscopy, in particular, has been applied in this field to many different kinds of ancient materials with successful results. In this work, a fragment of a Roman wall painting from the archaeological area of Pompeii has been investigated by LIBS. The sample elemental composition resulting from LIBS measurements suggested the presence of certain pigments. The ratio of the intensities of different lines related to some characteristic elements is proposed as an indicator for pigment recognition.     

Multivariate Reversed Hazard Rates and Inactivity Times of Systems

Methodology and Computing in Applied Probability - The family of the multivariate conditional hazard rate functions often reveals to be a convenient tool to describe the joint probability...     

Laser ablation of copper based alloys by single and double pulse laser induced breakdown spectroscopy

Single and double pulse laser induced breakdown spectroscopy was applied to the analysis of copper based alloys samples, in order to investigate the material ablation process under two different experimental conditions. An Nd:YAG laser, emitting at the fundamental wavelength (1064 nm) for a fixed value of total energy with the same pulse width, has been used for both set-up configurations. Certified samples of copper based alloys were examined in order to investigate the effect of their different compositions on the ablation process efficiency. The craters produced by the laser on the samples surfaces were measured by a contact profilometer in order to evaluate the mass of ablated material. In this respect the differences in behaviour of the single and the double pulse ablation for Laser Induced Breakdown Spectroscopy (LIBS), respectively, have been considered. The dependence, under the same experimental conditions, of the LIBS background emission of the different ablated masses of the material has also been investigated, by looking for normalization algorithms for quantitative data reduction.The behaviour of some peculiar intensity ratios, suitable for building calibration curves, has been studied in order to evaluate the trend in fractionated evaporation on going from the single pulse to the double pulse technique. PACS 52.70.-m; 52.50.Jm; 42.62.Fi     

The Torsional Barriers of 2‐Hydroxy‐ and 2‐Fluorobiphenyl: Small but Measurable

By making use of a novel diastereotopicity probe, namely C(CF₃)₂OH, it has been possible to measure by very low temperature ¹⁹F NMR spectroscopy the elusive aryl–aryl rotation barriers of biphenyls bearing an OH or F group in one ortho position. The experimental values (5.4 and 4.4 kcal mol^?1, respectively) are matched by those from ab initio calculations (5.3 and 4.3 kcal mol^?1, respectively).     

Influence of laser wavelength on LIBS diagnostics applied to the analysis of ancient bronzes

In this work the influence of laser wavelength upon the analytical results obtained from applying LIBS diagnostics to bronzes was investigated theoretically and experimentally at 1,064 nm and 355 nm. The laser ablation process was modeled for a set of reference samples of quaternary Cu/Sn/Pb/Zn alloys and the difference between plume composition and known target stoichiometry was estimated for both of the wavelengths considered. LIBS measurements were performed on the same set of reference samples and under the same experimental conditions to validate the model at different wavelengths. Results from the application of the model to calculate sample optical properties during laser irradiation, absorption in the plasma and plasma temperature are also presented.     

Comparisons of series and parallel systems with components sharing the same copula

The paper is devoted to study stochastic comparisons of series and parallel systems with vectors of component lifetimes sharing the same copula. We show that, under some conditions on the common copula, the series system with heterogeneous components is worse than the series system with homogeneous components having a common reliability function, which is equal to the average of the reliability functions of the heterogeneous components. However, we show that this property is not necessarily true for arbitrary copulas. We obtain similar properties for parallel systems and for general coherent systems. For these purposes, we introduce in our analysis the notion of the mean function of a copula. Copyright © 2009 John Wiley & Sons, Ltd.     

Usual and stochastic tail orders between hitting times for two Markov chains

We consider time‐homogeneous Markov chains with state space E_k≡{0,1,…,k} and initial distribution concentrated on the state 0. For pairs of such Markov chains, we study the Stochastic Tail Order and the stochastic order in the usual sense between the respective first passage times in the state k . On this purpose, we will develop a method based on a specific relation between two stochastic matrices on the state space E_k . Our method provides comparisons that are simpler and more refined than those obtained by the analysis based on the spectral gaps. Copyright © 2016 John Wiley & Sons, Ltd.     

Approximations and bounds for a generalized optimal stopping problem

We study a finite-horizon nonstationary Markovian decision problem, that can be interpreted as generalized optimal stopping and whose solution via the usual dynamic programming is in most practical cases not feasible from a computational point of view. Under certain assumptions, most importantly stochastic monotonicity, upper and lower bounds are obtained for optimal values and decisions using a reduced dynamic programming. From this, a suboptimal policy is derived with an upper bound on its suboptimality. Computational aspects and a particular application from optimal exploratory oil drilling are discussed.

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Zusammenfassung In der Arbeit wird ein nichtstationäres Markowsches Entscheidungsproblem mit endlichem Planungshorizont betrachtet, das als verallgemeinertes Stopp-Problem interpretiert werden kann. Die numerische Lösung des Problems mit Hilfe der üblichen Methode der dynamischen Optimierung ist in der Regel zu rechenaufwendig. Es wird deshalb eine Methode der approximativen Lösung des Problems (mit gewissen Einschränkungen) vorgeschlagen, und es werden obere und untere Schranken für den Optimalwert hergeleitet. Ferner wird eine suboptimale Politik mit einer oberen Schranke für die Suboptimalität angegeben. Abschließend wird ein praktisches Anwendungsbeispiel (optimale Versuchsbohrungen nach Öl) diskutiert, an dem auch rechentechnische Aspekte des entwickelten Lösungsverfahrens erläutert werden.

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Research partially supported by the Consiglio Nazionale delle Ricerche (CNR), Italy, through contract n.80.02343.01 and through GNAFA.