Alessandro De Giacomo

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.

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.

Pulsed laser ablation of a continuously-fed wire in liquid flow for high-yield production of silver nanoparticles

Using wires of defined diameters instead of a planar target for pulsed laser ablation in liquid results in significant increase of ablation efficiency and nanoparticle productivity up to a factor of 15. We identified several competitive phenomena based on thermal conductivity, reflectivity and cavitation bubble shape that affect the ablation efficiency when the geometry of the target is changed. On the basis of the obtained results, this work represents an intriguing starting point for further developments related to the up-scaling of pulsed laser ablation in liquid environments at the industrial level.

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.

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.

Nanoparticle Enhanced Laser-Induced Breakdown Spectroscopy for Microdrop Analysis at subppm Level

In this paper, nanoparticle enhanced laser-induced breakdown spectroscopy (NELIBS) was applied to the elemental chemical analysis of microdrops of solutions with analyte concentration at subppm level. The effect on laser ablation of the strong local enhancement of the electromagnetic field allows enhancing the optical emission signal up to more than 1 order of magnitude, enabling LIBS to quantify ppb concentration and notably decreasing the limit of detection (LOD) of the technique. At optimized conditions, it was demonstrated that NELIBS can reach an absolute LOD of few picograms for Pb and 0.2 pg for Ag. The effect of field enhancement in NELIBS was tested on biological solutions such as protein solutions and human serum, in order to improve the sensitivity of LIBS with samples where the formation and excitation of the plasma are not as efficient as with metals. Even in these difficult cases, a significant improvement with respect to conventional LIBS was observed.

Multi-methodological investigation of kunzite, hiddenite, alexandrite, elbaite and topaz, based on laser-induced breakdown spectroscopy and conventional analytical techniques for supporting mineralogical characterization

Gem-quality alexandrite, hiddenite and kunzite, elbaite and topaz minerals were characterized through a multi-methodological investigation based on EMPA-WDS, LA-ICP-MS, and laser-induced breakdown spectroscopy (LIBS). With respect to the others, the latter technique enables a simultaneous multi-elemental composition without any sample preparation and the detection of light elements, such as Li, Be and B. The criteria for the choice of minerals were: (a) the presence of chromophore elements in minor contents and/or as traces; (b) the presence of light lithophile elements (Li, Be and B); (c) different crystal chemistry complexity. The results show that LIBS can be employed in mineralogical studies for the identification and characterization of minerals, and as a fast screening method to determine the chemical composition, including the chromophore and light lithophile elements.

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 β strand (i.e. Glu16Val) or in loop (Glu18Val) behave in a radically different manner.

Study of the Effect of Water Pressure on Plasma and Cavitation Bubble Induced by Pulsed Laser Ablation in Liquid of Silver and Missed Variations of Observable Nanoparticle Features

In this work the effects of the pressure between 1-150 Bar on pulsed laser ablation in liquids (PLAL) during the production of silver nanoparticles (AgNPs) in water was investigated. The produced NPs are the results of two different well-known stages which are the plasma and the bubble evolution occurring until the generated material is released into the solution. The main aim of this work is to show which roles is played by the variation of water pressure on the laser induced plasma and the cavitation bubble dynamics during the NPs formation. Their implication on the comprehension of the as-produced NPs formation mechanisms is treated. The typical timescales of the different stages occurring in water at different pressures have been studied by optical emission spectroscopy (OES), imaging and shadowgraph experiments. Finally surface plasmon resonance (SPR) spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS) and scanning electron microscopy (SEM) for characterization of the material released in solution, have been used.

Plasma-assisted pulsed laser deposition of titanium dioxide

TiO2 film deposition by PAPLD with biased substrates is investigated into a wide range of laser fluence and oxygen pressure. It is established that plasma of the r.f. discharge excited inside PLD chamber strongly affects the films properties. TiO2 films deposited by PAPLD were found better than those produced by the conventional PLD with regard to their morphology, optical properties, and uniformity. So, at the high values of Knudsen number (lambda) /L < 1 with an r.f. power of 70 Watt, PAPLD markedly improves the TiO2 film stoichiometry for high laser fluence, and the deposition rate increases with it up to 2 A/s.