In this paper the use of metallic nanoparticles (NPs) for improving Laser Induced Breakdown Spectroscopy (LIBS) is discussed. In the case of conductors an emission signal enhancement up to 1-2 orders of magnitude was obtained depositing NPs on the sample surface by drying a micro-drop of colloidal solution. The basic mechanisms of Nanoparticle Enhanced LIBS (NELIBS) were studied and the main causes of this significantly large enhancement were found to be related to the effect of NPs on the laser ablation process, in terms of a faster and more efficient production of seed electrons with respect to conventional LIBS. The characteristics of NELIBS-produced plasma were investigated by emission spectroscopy and spectrally resolved images. In spite of similar plasma parameters, the NELIBS plasma was found to have larger emission volume and longer persistence than the LIBS one. A method to determine NP concentration and size was also proposed, which involved depositing NPs on non-interacting substrates, and proved the feasibility of LIBS as a fast detection tool for a preliminary characterization of NPs. © 2014 Elsevier B.V.

In this paper emission spectra of the plasma produced by laser-matter interaction are discussed in terms of the correlation between the elementary plasma processes and the evolution of plasma parameters during the expansion. Three main stages have been identified and discussed in details: high density plasma, near equilibrium plasma and non-equilibrium plasma including molecular formation. In order to develop a comprehensive point of view on the correlation between plasma mechanisms and spectral emission features several concepts already discussed and elucidated in the plasma science have been adapted to the description of the laser induced plasma and to its ionizing and recombining character.

This paper presents an evaluation of Laser Induced Breakdown Spectroscopy (LIBS) as a technique for gathering data relevant to Solar System geophysics. Two test cases were demonstrated: elemental analysis of chondrules in a chondrite meteorite, and space- resolved analysis of the interface between kamacite and taenite crystals in an octahedrite iron meteorite. In particular most major and minor elements (Fe, Mg, Si, Ti, Al, Cr, Mn, Ca, Fe, Ni, Co) in Sahara 98222 (chondrite) and its chondrules, as well as the profile of Ni content in Toluca (iron meteorite), were determined with the Calibration Free (CF) method. A special attention was devoted to exploring the possibilities offered by variants of the basic technique, such as the use of Fe I Boltzmann distribution as an intensity calibration method of the spectroscopic system, and the use of spatially resolved analysis. © 2014 Elsevier B.V. All rights reserved.

A modified version of the calibration-free (CF) method was applied to the analysis of a set of archaeological brooches made of various copper-based alloys and coming from the archaeological site of Egnatia (Apulia, Southern Italy). The developed methodology consists in determining the plasma temperature by reversing the set of equations employed in the usual CF algorithm, and it is thus referred to as "inverse method". The plasma temperature is determined for one certified standard, by using its known elemental composition as an input data, and then applied to the set of unknown samples to evaluate their composition in a CF mode. The feasibility of such an approach is demonstrated by comparing the results obtained with classical LIBS (drawing calibration lines with a series of matrix-matched certified standards) and with independent measurements performed with a conventional technique (LA-ICP-MS). © 2014 Elsevier B.V.

In this work, different theories for the determination of the electron density in Laser-Induced Breakdown Spectroscopy (LIBS) utilizing the emission lines belonging to the hydrogen Balmer series have been investigated. The plasmas were generated by a Nd:Yag laser (1064 nm) pulsed irradiation of pure hydrogen gas at a pressure of 2 · 104 Pa. Ha?, H?, H?, H?, and Balmer lines were recorded at different delay times after the laser pulse. The plasma electron densitywas evaluated through themeasurement of the Stark broadenings and the experimental results were compared with the predictions of three theories (the Standard Theory as developed by Kepple and Griem, the Advanced Generalized Theory by Oks et al., and the method discussed by Gigosos et al.) that are commonly employed for plasma diagnostics and that describe LIBS plasmas at different levels of approximations. A simple formula for pure hydrogen plasma in thermal equilibriumwas also proposed to infer plasma electron density using the H? line. The results obtained showed that at high hydrogen concentration, the H? line is affected by considerable self-absorption. In this case, it is preferable to use the H? line for a reliable calculation of the electron density. © 2013 Elsevier B.V. All rights reserved.