Combined micro X-ray fluorescence and micro computed tomography for the study of extraterrestrial volcanic rocks. The case of North West Africa (NWA) 8657: A shergottite martian meteorite.

The combined potentiality of benchtop micro X-ray fluorescence spectroscopy (µ-XRF) and micro computed tomography (µ-CT) has been applied to describe microstructures, type and distribution of mineralogical phases as well as geological constraints on the history of the North West Africa (NWA) 8657 shergottite Martian meteorite. The 3D rendering of the sample was used to compute its vesiculation, infer the presence of cracks and reveal different shapes in its crystal habits including subhedral pyroxene phases and rounded sulphide and/or sulphates minerals. Phase discrimination was achieved by comparing chemical information about element distribution with mineral classes segmented as a function of their relative density. In particular, the relationships between the plagioclase/maskelynite phase and other minerals such as Ca-phosphates, the chemical zoning of Ca-pyroxenes and maskelynite and the presence of S-bearing phases in the form of K-sulphates and Fe-sulphides were revealed, which allowed reconstructing satisfactorily meteorite history. The successful performance of the combined approach used in this work shows promising for further application to other types of meteorites.

Macro-classification of meteorites by portable energy dispersive X-ray fluorescence spectroscopy (pED-XRF), principal component analysis (PCA) and machine learning algorithms.

The research on meteorites from hot and cold deserts is gaining advantages from the recent improvements of portable technologies such as X-ray fluorescence spectroscopy (XRF). The main advantages of portable instruments include the fast recognition of meteorites through their classification in macro-groups and discrimination from materials such as industrial slags, desert varnish covered rocks and iron oxides, named "meteor-wrongs". In this study, 18 meteorite samples of different nature and origin were discriminated and preliminarily classified into characteristic macro-groups: iron meteorites, stony meteorites and meteor-wrongs, combining a portable energy dispersive XRF instrument (pED-XRF), principal component analysis (PCA) and some machine learning algorithms applied to the XRF spectra. The results showed that 100% accuracy in sample classification was obtained by applying the cubic support vector machine (CSVM), fine kernel nearest neighbor (FKNN), subspace discriminant-ensemble classifiers (SD-EC) and subspace discriminant KNN-EC (SKNN-EC) algorithms on standardized spectra.

Application of micro X-ray fluorescence and micro computed tomography to the study of laser cleaning efficiency on limestone monuments covered by black crusts.

Laser cleaning is widely used to remove black crusts from weathered limestone monuments. The cleaning efficiency is commonly tested using conventional analytical techniques, which do not allow to analyze the same sample before and after the treatment. In this paper, micro computed tomography (µ-CT) and micro X-ray fluorescence spectroscopy (µ-XRF) techniques were used for the first time to evaluate the laser cleaning efficiency on two different encrusted quoins collected from a limestone monument. Analyses were carried out non-destructively on the same portion of the two lithotypes before and after the treatment. µ-XRF confirmed the presence of gypsum in the black crust, and showed a marked decrease of S and other typical elements after laser cleaning of both samples. µ-CT clearly showed the different structure of limestone before and after cleaning and the crust portion removed by the laser. The combination of the two techniques allowed to assess that, even if the two samples had a similar chemical composition, their response to laser cleaning was different on dependence of their different fabric/structure. In fact, in one sample calcium sulphate was still partially retained also after the black crust removal, whereas in the other sample the sulphate layer was almost completely ablated due to its more compact structure. In both cases, laser cleaning operation was shown not to cause any structural modification or mechanical damage of the original stone material. In conclusion, the use of these novel techniques appears very promising for studying the effects of laser ablation on rock samples in order to set the best working conditions for their cleaning.

Amyloid transition of ubiquitin on silver nanoparticles produced by pulsed laser ablation in liquid as a function of stabilizer and single-point mutations.

The interaction of nanoparticles with proteins has emerged as a key issue in addressing the problem of nanotoxicity. We investigated the interaction of silver nanoparticles (AgNPs), produced by laser ablation with human ubiquitin (Ub), a protein essential for degradative processes in cells. The surface plasmon resonance peak of AgNPs indicates that Ub is rapidly adsorbed on the AgNP surface yielding a protein corona; the Ub-coated AgNPs then evolve into clusters held together by an amyloid form of the protein, as revealed by binding of thioflavin T fluorescent dye. Transthyretin, an inhibitor of amyloid-type aggregation, impedes aggregate formation and disrupts preformed AgNP clusters. In the presence of sodium citrate, a common stabilizer that confers an overall negative charge to the NPs, Ub is still adsorbed on the AgNP surface, but no clustering is observed. Ub mutants bearing a single mutation at one edge ß strand (i.e. Glu16Val) or in loop (Glu18Val) behave in a radically different manner.

Collinear double pulse laser ablation in water for the production of silver nanoparticles.

Experiments of collinear Double Pulse Laser Ablation in Liquid (DP-LAL) were carried out for studying the production mechanisms of nanoparticles (NPs) in water, which revealed the fundamental role of the cavitation bubble dynamics in the formation of aqueous colloidal dispersions. In this work, DP-LAL was used to generate silver nanoparticles (AgNPs) from a silver target submerged in water at atmospheric pressure and room temperature, by using the second harmonic (532 nm) of two Nd:YAG lasers. The second laser pulse was shot at different delay times (i.e. interpulse delay) during the bubble temporal evolution of the first laser induced bubble. Optical Emission Spectroscopy, Shadowgraph Images, Surface Plasmon Resonance absorption spectroscopy and Dynamic Light Scattering were carried out to study the behaviour of laser-induced plasma and cavitation bubbles during the laser ablation in liquid, to monitor the generation of AgNPs under different conditions, and for characterization of NPs. The results of DP-LAL were always compared with the corresponding ones obtained with Single Pulse Laser Ablation in Liquid (SP-LAL), so as to highlight the peculiarities of the two different techniques.

Monitoring of Cr, Cu, Pb, V and Zn in polluted soils by laser induced breakdown spectroscopy (LIBS).

Laser Induced Breakdown Spectroscopy (LIBS) is a fast and multi-elemental analytical technique particularly suitable for the qualitative and quantitative analysis of heavy metals in solid samples, including environmental ones. Although LIBS is often recognised in the literature as a well-established analytical technique, results about quantitative analysis of elements in chemically complex matrices such as soils are quite contrasting. In this work, soil samples of various origins have been analyzed by LIBS and data compared to those obtained by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The emission intensities of one selected line for each of the five analytes (i.e., Cr, Cu, Pb, V, and Zn) were normalized to the background signal, and plotted as a function of the concentration values previously determined by ICP-OES. Data showed a good linearity for all calibration lines drawn, and the correlation between ICP-OES and LIBS was confirmed by the satisfactory agreement obtained between the corresponding values. Consequently, LIBS method can be used at least for metal monitoring in soils. In this respect, a simple method for the estimation of the soil pollution degree by heavy metals, based on the determination of an anthropogenic index, was proposed and determined for Cr and Zn.

Laser induced breakdown spectroscopy for elemental analysis in environmental, cultural heritage and space applications: a review of methods and results.

Analytical applications of Laser Induced Breakdown Spectroscopy (LIBS), namely optical emission spectroscopy of laser-induced plasmas, have been constantly growing thanks to its intrinsic conceptual simplicity and versatility. Qualitative and quantitative analysis can be performed by LIBS both by drawing calibration lines and by using calibration-free methods and some of its features, so as fast multi-elemental response, micro-destructiveness, instrumentation portability, have rendered it particularly suitable for analytical applications in the field of environmental science, space exploration and cultural heritage. This review reports and discusses LIBS achievements in these areas and results obtained for soils and aqueous samples, meteorites and terrestrial samples simulating extraterrestrial planets, and cultural heritage samples, including buildings and objects of various kinds.

Experimental and theoretical investigation of laser-induced plasma of a titanium target.

We present a theoretical approach to interpreting optical emission spectroscopy measurements for nonequilibrium conditions. In this approach both the fluid dynamics and the kinetics of laser-induced plasma are taken into account, and the results obtained by the numerical model are applied to the spectroscopic observation of the plasma induced by the interaction between a KrF laser and a metallic Ti target. We have generalized the theoretical method to calculate the initial conditions for the plume expansion that show the best agreement with experimental results.