Francisco J. Fortes

Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is an atomic emission spectroscopy. Atoms are excited from the lower energy level to high energy level when they are in the high energy status. The conventional excitation energy source can be a hot flame, light or high temperature plasma. The excited energy that holds the atom at the higher energy level will be released and the atom returns to its ground state eventually. The released energy is welldefined for the specific excited atom, and this characteristic process utilizes emission spectroscopy for the analytical method. LIBS employs the laser pulse to atomize the sample and leads to atomic emission. Compared to the conventional flame emission spectroscopy, LIBS atomizes only the small portion of the sample by the focused laser pulse, which makes a tiny spark on the sample. Because of the short-life of the spark emission, capturing the instant light is a major skill to collect sufficient intensity of the emitting species. Three major parts of the LIBS system are a pulse laser, sample, and spectrometer. Control system is usually needed to manage timing and the spectrum capturing. Figure 1 illustrates those three major components and a computer in the conventional LIBS.

In situ analytical assessment and chemical imaging of historical buildings using a man-portable laser system.

In this work, the capability of laser-induced breakdown spectrometry for the in situ analytical assessment and chemical mapping of the façade of the cathedral of Malaga (Spain) has been demonstrated. The task required the use of a portable laser analyzer that allowed real-time spectral acquisitions in the field. A man-portable laser, based on a Q-switched Nd:YAG laser operating at its fundamental wavelength, has been utilized to generate a LIBS plasma of the sample surface. A chemical characterization of the different materials employed in the construction of this building has been performed. The purpose of this study was to use LIBS spectrochemical analysis to qualitatively discriminate between sandstone, limestone, marble, and cement mortar, which are the main components used in this class of historical monument. The field analysis was performed in two zones: the northern façade and the “girola”; the total areas of analysis of the two regions were 250 m2 and 650 m2, respectively. Chemical images of Si/Ca and Ca/Mg ratios from both parts of the building were generated. During the measurement campaign, a protocol of analysis was chosen so as to achieve an accurate description of the building materials with respectable spatial resolutions.

Real time and in situ determination of lead in road sediments using a man-portable laser-induced breakdown spectroscopy analyzer

In situ, real time levels of lead in road sediments have been measured using a man-portable laser-induced breakdown spectroscopy analyzer. The instrument consists of a backpack and a probe housing a Q-switched Nd:YAG laser head delivering 50 mJ per pulse at 1064 nm. Plasma emission was collected and transmitted via fiber optic to a compact cross Czerny-Turner spectrometer equipped with a linear CCD array allocated in the backpack together with a personal computer. The limit of detection (LOD) for lead and the precision measured in the laboratory were 190 microg g(-1) (calculated by the 3 sigma method) and 9% R.S.D. (relative standard deviation), respectively. During the field campaign, averaged Pb concentration in the sediments were ranging from 480 microg g(-1) to 660 microg g(-1) depending on the inspected area, i.e. the entrance, the central part and the exit of the tunnel. These results were compared with those obtained with flame-atomic absorption spectrometry (flame-AAS). The relative error, expressed as [100(LIBS result-flame AAS result)/(LIBS result)], was approximately 14%.

Spectrochemical study for the in situ detection of oil spill residues using laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) has been used to identify the differences or similarities between crude oil and fuel residues. Firstly, a man portable LIBS analyzer was used for the on-site environmental control and analysis of the oil spill from The Prestige. An exhaustive analysis of crude oil and oil spill residues (collected during the field campaign in the Galician Coast) was performed in the laboratory. Characteristics elements in petroleum such as C, H, N, O, Mg, Na, Fe and V were detected. In addition, contributions from Ca, Si and Al in the composition of residues have been found. The use of intensity ratios of line and band emissions in the original fuel (crude oil) and in the aged residues allowed a better characterization of the samples than the simple use of peak intensities. The chemical composition between the crude oil and the fuel residues was found completely different. As well, a statistical method was employed in order to discriminate residues. Although significant differences were observed, no conclusions in terms of age and provenance could be reached due to the unknowledgment in the origin of the samples.

Multielemental analysis of prehistoric animal teeth by laser-induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

Laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA) inductively coupled plasma (ICP) mass spectrometry (MS) were utilized for microspatial analyses of a prehistoric bear (Ursus arctos) tooth dentine. The distribution of selected trace elements (Sr, Ba, Fe) was measured on a 26 mm×15 mm large and 3 mm thick transverse cross section of a canine tooth. The Na and Mg content together with the distribution of matrix elements (Ca, P) was also monitored within this area. The depth of the LIBS craters was measured with an optical profilometer. As shown, both LIBS and LA-ICP-MS can be successfully used for the fast, spatially resolved analysis of prehistoric teeth samples. In addition to microchemical analysis, the sample hardness was calculated using LIBS plasma ionic-to-atomic line intensity ratios of Mg (or Ca). To validate the sample hardness calculations, the hardness was also measured with a Vickers microhardness tester.

Evaluating the use of standoff LIBS in architectural heritage: surveying the Cathedral of Málaga

Laser-induced breakdown spectroscopy (LIBS) is a cutting-edge technology which offers appealing features for its application in the field of the cultural heritage. It is a proven technology for the fast and simultaneous detection of major and trace elements with minimal destructiveness, using easily compactable instrumentation into movable platforms for the in situ and standoff chemical analysis of objects in real time. In the present work, a standoff LIBS sensor has been used for surveying the Cathedral of Malaga. The spectroscopic measurements were gathered in situ although from an averaged distance of 35 m. A comprehensive characterization of the materials composing the main facade as well as identification of the noticeable pollutants at their surfaces has been performed. The standoff LIBS results have fitted neatly with the mineralogical analysis of all the stones assayed. The large emissions of Si, Al, Ca and Mg have confirmed that the structure was almost entirely built using sandstone. In turn, the sensitivity to carbonate chemistry has demonstrated the capability of standoff LIBS for coherently classifying different marbles, thus allowing the identification of their origins. Standoff LIBS has also allowed the detection of pollutants such as Si, Ca, Mg, Fe, Al, Ba and Sr, originating from natural sources such as the transport of re-suspended dust and atmospheric particulate matter related to marine aerosols. In addition, trace elements such as Ti, Pb and Mn from exhausts of gasoline and diesel engines are also involved in the pollution triggering of materials. To obtain all these findings, scaffolding or other intrusive facilities have not been required.

Elemental analysis of materials in an underwater archeological shipwreck using a novel remote laser-induced breakdown spectroscopy system

LIBS analysis of submerged materials in an underwater archeological site has been performed for the first time. A fiber-optics-based remote instrument was designed for the recognition and identification of archeological assets in the wreck of the Bucentaure (Bay of Cadiz, South of Spain). The LIBS prototype featured both single-pulse (SP-LIBS) and multi-pulse excitation (MP-LIBS). The use of multi-pulse excitation allowed an increased laser beam energy (up to 95 mJ) transmitted through the optical fiber. This excitation mode results in an improved performance of the equipment in terms of extended range of analysis (to a depth of 50 m) and a broader variety of samples to be analyzed (i.e., rocks, marble, ceramics and concrete). Compared to single-pulse, an intensity enhancement factor of 15× was observed at the same irradiance value, 1.89 GW/cm(2). Thus, a longer pulse duration promotes the heating and melting of the sample, resulting in a greater mass ablated. As a consequence of the optimization of experimental conditions performed in laboratory, underwater characterization of ancient pottery was achieved.

A study of underwater stand-off laser-induced breakdown spectroscopy for chemical analysis of objects in the deep ocean

In this work, we demonstrate for the first time the feasibility of stand-off laser induced breakdown spectroscopy (ST-LIBS) for the analysis of distant submerged objects. The applicability of underwater stand-off LIBS is highly challenging since it involves the delivery of a focused laser pulse toward the distant target through the aqueous media and then the transmission of the light emitted by the laser-induced plasma back to the detection system. Experiments were designed to gain fundamental knowledge regarding LIBS analysis in an underwater open-path configuration. Samples were analyzed at distances up to 80 cm from the sensor at a solid–water interface. Effective plasma formation was achieved using dual pulse excitation with Nd:YAG laser pulses at 532 nm. Intense and well resolved emission signals were observed with interpulse delay times close to 500 μs, whereas the lifetime of the laser-induced plasma was only a few μs. The effect of water temperature and the influence of the underwater optical path on the LIBS signal have also been evaluated.

Effect of Pulse Duration in Multi-Pulse Excitation of Silicon in Laser-Induced Breakdown Spectroscopy (LIBS)

The aim of this study is to investigate the mechanisms responsible for the increase in ablated mass and signal enhancement observed on multi-pulse excitation. Several experiments were designed to obtain evidence that confirms the laser–sample and/or laser–plasma interaction, with special attention to the role of the pulse width on these effects. A train of pulses, with a separation of a few microseconds between pulses, was used for laser-induced breakdown spectroscopy (LIBS) analysis. The signal emission of Si was improved by an enhancement factor of about 60 compared to conventional single-pulse LIBS (SP-LIBS). The number of spikes, their amplitude, and their pulse duration were found to be variable for different Q-switch delays. A temporal study was performed to determine whether or not a laser–plasma interaction took place. The effect of pulse width (as responsible of laser–sample interaction) was also evaluated. The results demonstrate that, although both interactions contribute to the observed effect, the process is predominantly governed by the pulse width.

Multi-Pulse Excitation for Underwater Analysis of Copper-Based Alloys Using a Novel Remote Laser-Induced Breakdown Spectroscopy (LIBS) System.

In this work, the use of multi-pulse excitation has been evaluated as an effective solution to mitigate the preferential ablation of the most volatile elements, namely Sn, Pb, and Zn, observed during laser-induced breakdown spectroscopy (LIBS) analysis of copper-based alloys. The novel remote LIBS prototype used in this experiments featured both single-pulse (SP-LIBS) and multi-pulse excitation (MP-LIBS). The remote instrument is capable of performing chemical analysis of submersed materials up to a depth of 50 m. Laser-induced breakdown spectroscopy analysis was performed at air pressure settings simulating the conditions during a real subsea analysis. A set of five certified bronze standards with variable concentration of Cu, As, Sn, Pb, and Zn were used. In SP-LIBS, signal emission is strongly sensitive to ambient pressure. In this case, fractionation effect was observed. Multi-pulse excitation circumvents the effect of pressure over the quantitative analysis, thus avoiding the fractionation phenomena observed in single pulse LIBS. The use of copper as internal standard minimizes matrix effects and discrepancies due to variation in ablated mass.