Laser-induced breakdown spectroscopy; LIBS; liquid; plasma; laser ablation;AQUEOUS-SOLUTIONS; VEGETABLE-OILS; WASTE-WATER; LIBS; METALS; ELEMENTS; SODIUM; PLASMA; PULSE; ACIDS

We studied changes in laser-induced breakdown spectroscopy (LIBS) signal intensity with the thickness of a liquid layer placed on a solid substrate, where an easily evaporating methanol sample was used. For a certain optimal liquid film thickness we obtained a manifold increase of the LIBS signal from methanol. Progressive liquid film thinning leads to a reduction and a successive disappearance of laser-induced splashes; the latter condition drastically reduces the sample consumption and allows measurements to be repeated many times on a single liquid droplet. In following, we developed two methods for actively controlled deformation, i.e., thinning of a liquid droplet (volume similar to 10 ml) prior to its sampling by LIBS. Control of the droplet's height was achieved on a Si-SiO2 wafer substrate by electro-wetting in the case of water solutions or by target rotation in the case of viscous liquids. The chosen substrate also has the advantages of low cost, easy manipulation, and very high purity, thus minimizing interference with analytes. Through the droplet deformation, in a single-pulse excitation at moderate laser energy (70 mJ), we clearly detected Fe and Mn in peanut oil, which represent trace elements in edible oils (similar to 1 part per billion), according to results published in the literature.

Laser induced breakdown spectroscopy LIBS; Plasma; Calibration; Matrix effect; Particles;INDUCED BREAKDOWN SPECTROSCOPY; ELEMENTAL ANALYSIS; QUANTITATIVE-ANALYSIS; SAMPLES; NORMALIZATION; PARAMETERS; AEROSOLS; LIBS

The laser induced plasma spectroscopy was applied on particles attached on substrate represented by a silica wafer covered with a thin oil film. The substrate itself weakly interacts with a ns Nd:YAG laser (1064 nm) while presence of particles strongly enhances the plasma emission, here detected by a compact spectrometer array. Variations of the sample mass from one laser spot to another exceed one order of magnitude, as estimated by on-line photography and the initial image calibration for different sample loadings. Consequently, the spectral lines from particles show extreme intensity fluctuations from one sampling point to another, between the detection threshold and the detector's saturation in some cases. In such conditions the common calibration approach based on the averaged spectra, also when considering ratios of the element lines i.e. concentrations, produces errors too large for measuring the sample compositions. On the other hand, intensities of an analytical and the reference line from single shot spectra are linearly correlated. The corresponding slope depends on the concentration ratio and it is weakly sensitive to fluctuations of the plasma temperature inside the data set. A use of the slopes for constructing the calibration graphs significantly reduces the error bars but it does not eliminate the point scattering caused by the matrix effect, which is also responsible for large differences in the average plasma temperatures among the samples. Well aligned calibration points were obtained after identifying the couples of transitions less sensitive to variations of the plasma temperature, and this was achieved by simple theoretical simulations. Such selection of the analytical lines minimizes the matrix effect, and together with the chosen calibration approach, allows to measure the relative element concentrations even in highly unstable laserinduced plasmas. (C) 2017 Elsevier B.V. All rights reserved.

QUANTITATIVE-ANALYSIS; WASTE-WATER; SURFACE; ABLATION; DROPLET; LIBS; SUBSTRATE; SODIUM; DIESEL; OIL

Droplets of organic liquids on aluminum substrate were probed by an Nd:YAG laser, both in a steady state and during rotation at speeds 18-150 rpm. Rotation transforms the droplet into film, which estimated thickness at high speeds was below 3 mu m and 20 mu m for diesel and peanut oil, respectively. Line intensities from the liquid (C I) and the support (Al I) material were tracked as a function of the film thickness and the laser energy. By film thinning, the line intensities from liquid sample were enhanced up to a factor 100x; simultaneously, the LIBS signal fluctuations were reduced 5-10 times with respect to the steady droplet. In certain experimental conditions, the line intensities from the support material become very weak with respect to the C I line, indicating an efficient screening of the substrate by highly excited plasma from the liquid layer. At a fixed rotation speed, there is a laser energy threshold, dependent on the liquid thickness, above which the LIBS signal becomes stable. Here, we discuss the relative processes and optimization of the experimental conditions for the LIBS measurements frome one laser shot to another.

INDUCED PLASMA; LIGHT-BEAMS; AIR; WATER; PARTICLES; VAPORIZATION; CONSTITUENTS; SPECTROMETRY; CLOUDS

Nanosecond laser-induced breakdown spectroscopy has been examined for the analysis of suspended matter in a free stream of air. The real-time monitoring of this scenario poses major challenges for an accurate categorization due to its changing characteristics such as composition, size, and density of particles. The effects of particle size and matrix in the optical emission responses registered from such scenarios have been evaluated. Distant (10 m) plasmas of saline solutions, containing either NaCl or Na2SO4 at different concentrations, have been induced by nanosecond laser pulses at a wavelength of 1064 nm. The effects of the droplet size and its concentration on differences in the laser-induced breakdown probability, the intensity of the characteristic lines, and the plasma emission continuum have been discussed. The quantification of sodium in distant water droplets has been proved. However, an initial knowledge on the average droplet size is required. The average droplet size could be determined from the slope of H I and O I lines versus the continuum plasma emission, which is only weakly influenced by the salt content in the droplets. (C) 2017 Optical Society of America.

Cultural heritage; Laser scanners; Fiber Bragg grating sensor; Laser-induced fluorescence; Laser-induced breakdown spectroscopy;INDUCED BREAKDOWN SPECTROSCOPY; PLASMA PARAMETERS; FLUORESCENCE

The recent development of laser scanners in environmental diagnostics made possible to implement their prototypes for remote characterization of cultural heritage (CH) surfaces. Specific data analysis algorithms have been developed to handle large data set acquired in high resolution operation. Non-invasive, or at least micro-invasive methodologies applied on real CH targets have shown the possibility to obtain information on surface appearance, morphology and composition. The added value of optical and spectroscopic integrated sensors is discussed for some significant case studies addressed both to a deep knowledge of the artifacts (materials and methods of realization) and to their structural characterization.

SINGLE-PULSE; CAVITATION BUBBLE; ABLATION; CERAMICS; WATER; NANOPARTICLES; LIQUID; DYNAMICS; SPECTRA; METALS

The goal of this study was to investigate whether a secondary plasma can be formed on a non-metallic target under water and to give insight into the related processes. The material of choice here was alumina, since its physical, thermal and mechanical properties are substantially different from those of pure Al, only for which secondary plasma formation was recently demonstrated. To achieve this, plasma and bubble formation on alumina under water after single pulse laser excitation were studied using fast photography, shadowgraphy, Schlieren and LIBS techniques. The results show that the secondary plasma caused by backward heating of the target and successive slow target evaporation into the growing vapour bubble also occurs for alumina. The secondary plasma formed on alumina involves only a narrow interaction region on the target resulting in an almost spherical plume shape. In contrast, on thermally conductive and easily melting/evaporating aluminium, the secondary plasma is intense, with a large volume which is flattened on the target surface. Inside the expanded bubble above the alumina target, glowing particles were not observed. Due to less efficient secondary plasma formation on alumina compared to aluminium, its optical emission only slightly increases at a delay of 400 ns from the laser pulse but emission persists during three bubble cycles with a total duration of about 650 ms. The LIBS spectra related to the secondary plasma are almost free from any continuum component and show narrow emission lines from low excited states. Here we discuss the observed differences in the plasma's spatial, temporal and spectral evolution on the two considered target materials. The obtained results indicate that under water a secondary plasma might be formed on very different materials and that its detection produces a good quality LIBS signal from single pulse excitation using a commercial nanosecond laser source.