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Background: Thousands of micrometeorites fall to the Earth on a daily basis. Most of these meteorites have a rocky composition, but others are mainly composed of iron and nickel. Due to their small size, often ca. 100 μm in diameter, the process of searching for, collecting, and identifying these samples is remarkably tedious. In this work, we introduce a minimally invasive methodology for evaluating the full elemental composition of micrometeorites using optical emission spectroscopy of single particles produced by laser ablation of bulk targets., Results: Bulk meteorite samples were directly ablated within an ablation cell. From few micrograms of ablated matrix, we originated dry aerosols consisting of multielemental particles which were representative of the sample chemistry. SEM images confirmed that the generated particles exhibited spherical geometry. Particles were first optically trapped in air and, then, analyzed by laser-induced breakdown spectroscopy (LIBS). LIBS spectra evidenced compositional differences among samples. For example, Campo de Cielo meteorite featured a high iron content due to its metallic nature whereas LIBS results for Jbilet Winselwan and NWA 869 suggested that pyroxene components dominated the composition of the samples. In contrast, NWA 13739 and Vaca Muerta contained high aluminum intensity, thus indicating that the feldspathic component was dominant, as then verified by XRD. The intra-sample compositional variability were quite satisfactory, as revealed by the RSD data, below 45 %. For quantitative analysis, the percentages of FeO, SiO 2 , Al 2 O 3 , Na 2 O, MgO, TiO 2 , CaO, K 2 O, MnO, SrO, Cr 2 O 3 , and Li 2 O were calculated using CF-LIBS., Significance: This work demonstrates the applicability of laser excitation of individual particles in an optical trap for the multielemental analysis of meteorites. The methodology provides a complete overview of the samples, is capable of classificating them according to their main phases and yield preliminary quantitative information about those phases. Therefore, we present a minimally destructive pathway to be used as the first step in the inspection of these delicate samples. If the particles represent nanostructures inherent to the meteorites, it would constitute a major step in the analysis of extraterrestrial material that may provide fundamental insights into the structure and composition of the original materials at the microscale, a topic that remains an active area of research worldwide., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Moonmilk-type deposits exemplify carbonated Martian analogues existing in the subsurface of Earth, an endokarstic speleothem with a possible biochemical origin composed principally by carbonates, mainly huntite and dolomite. In this work, samples of moonmilk located in Nerja Cave (southern Spain) have been studied by LIBS with the aim of identifying carbon of biogenic origin by establishing a relationship between a molecular emission indicator, CN signal, and the organic carbon content. The characterization of this kind of carbonate deposit with a multiple mineralogical composition has been completed using scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray diffraction techniques for qualitative and semi-quantitative analysis. The information attained from LIBS regarding energy thresholds and time-resolved kinetics of CN emissions provides useful insight into the identification of different molecular emitters, namely organic and inorganic CN, depending on the laser irradiance and time settings conditions. These promising results are of application in the search and identification of biosignatures in upcoming planetary missions with astrobiological purposes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Understanding the past habitable environments of Mars increases the requirement to recognize and examine modern analogs and to evaluate the mechanisms that may preserve biosignatures in them. The phenomenon that originates and preserves possible microbial biosignatures in mineral phases is of particular interest in astrobiology. On Earth, the precipitation of carbonate matrices can be mediated by bacteria. Besides microbialites and other sedimentary structures, carbonate formations can be observed in certain karstic caves. The present work is focused on the remote laser-induced breakdown spectroscopy (LIBS) characterization of cyanobacteria, exploring the possibilities for identification and discrimination on carbonate substrates. For this purpose, the extremophile cyanobacterium Chroococcidiopsis sp. (collected from the Nerja Cave, Malaga, Spain) was analyzed under laboratory-simulated martian conditions in terms of chemical composition and gas pressure. LIBS results related to acquired molecular emission features allowed bacterial differentiation from the colonized mineral substrate. In addition, the limits of detection were estimated with a laboratory-grown culture of the cyanobacterium Microcystis aureginosa . Our results reveal LIBS's capability to detect biological traces under simulated martian conditions. Additionally, the time-resolved analysis of the biological samples demonstrates the selection of optimal temporal conditions as a critical parameter for the preferential acquisition of molecular species in organic material.

Owing to the exceedingly small mass involved, complete elemental characterization of single nanoparticles demands a highly precise control of signal background and noise sources. LIBS has demonstrated remarkable merits for this task, providing a unique tool for the multielemental analysis of particles on the attogram-picogram mass scale. Despite this outstanding sensitivity, the air plasma acting as a heat source for particle dissociation and excitation is a meddling agent, often limiting the acquisition of an accurate sample signature. Although thermal effects associated with ultrashort laser pulses are known to be reduced when compared to the widely used nanosecond pulse duration regime, attempts to improve nanoinspection performance using ultrafast excitation have remained largely unexplored. Herein, picosecond laser pulses are used as a plasma excitation source for the elemental characterization of single nanoparticles isolated within optical traps in air at atmospheric pressure. Results for picosecond excitation of copper particles lead to a mass detection limit of 27 attogram, equivalent to single particles 18 nm in diameter. Temporally and wavelength-resolved plasma imaging reveals unique traits in the mechanism of atomic excitation in the picosecond regime, leading to a deeper understanding of the interactions occurring in single nanoparticle spectroscopy.

In this work, a geological sample of great astrobiological interest was studied through analytical techniques that are currently operating in situ on Mars and others that will operate in the near future. The sample analyzed consisted of an oncoid, which is a type of microbialite, collected in the Salar Carachi Pampa, Argentina. The main peculiarity of microbialites is that they are organo-sedimentary deposits formed by the in situ fixation and precipitation of calcium carbonate due to the growth and metabolic activities of microorganisms. For this reason, the Carachi Pampa oncoid was selected as a Martian analog for astrobiogeochemistry study. In this sense, the sample was characterized by means of the PIXL-like, SuperCam-like and SHERLOC-like instruments, which represent instruments on board the NASA Perseverance rover, and by means of RLS-like and MOMA-like instruments, which represent instruments on board the future ESA Rosalind Franklin rover. It was possible to verify that the most important conclusions and discoveries have been obtained from the combination of the results. Likewise, it was also shown that Perseverance rover-like remote-sensing instruments allowed a first detailed characterization of the biogeochemistry of the Martian surface. With this first characterization, areas of interest for in-depth analysis with Rosalind Franklin-like instruments could be identified. Therefore, from a first remote-sensing elemental identification (PIXL-like instrument), followed by a remote-sensing molecular characterization (SuperCam and SHERLOC-like instruments) and ending with an in-depth microscopic analysis (RLS and MOMA-like instruments), a wide variety of compounds were found. On the one hand, the expected minerals were carbonates, such as aragonite, calcite and high-magnesium calcite. On the other hand, unexpected compounds consisted of minerals related to the Martian/terrestrial surface (feldspars, pyroxenes, hematite) and organic compounds related to the past biological activity related to the oncoid (kerogen, lipid biomarkers and carotenes). Considering samples resembling microbialites have already been found on Mars and that one of the main objectives of the missions is to identify traces of past life, the study of microbialites is a potential way to find biosignatures protected from the inhospitable Martian environment. In addition, it should be noted that in this work, further conclusions have been obtained through the study of the results as a whole, which could also be carried out on Mars., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Jennifer Huidobro reports article publishing charges was provided by University of the Basque Country. Jennifer Huidobro reports equipment, drugs, or supplies was provided by University of the Basque Country., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Over the past two decades, a considerable expansion of malaria interventions has occurred at the national level in Angola, together with cross-border initiatives and regional efforts in southern Africa. Currently, Angola aims to consolidate malaria control and to accelerate the transition from control to pre-elimination, along with other country members of the Elimination 8 initiative. However, the tremendous heterogeneity in malaria prevalence among Angolan provinces, as well as internal population movements and migration across borders, represent major challenges for the Angolan National Malaria Control Programme. This review aims to contribute to the understanding of factors underlying the complex malaria situation in Angola and to encourage future research studies on transmission dynamics and population structure of Plasmodium falciparum, important areas to complement host epidemiological information and to help reenergize the goal of malaria elimination in the country., (© 2022. The Author(s).)

In the present paper, confined dry Cu nanoaerosols of controlled particle size are inspected under a time-resolved LIBS scheme to explore the effect of laser-particulate matter interaction upon the detection capability of airborne nanoparticulate material. Optically catapulted streams probed showed linear intensity vs mass correlation and similar signal stability which is linked to the seeding effect caused by smaller particles yielding hotter, albeit shorter plasmas. Seeding effect is demonstrated by hyperspectral time-resolved aerosol inspection, which exposes both, the interaction between multiple plasma nuclei and the discrete nature of the laser-particle interaction. Observed population/exhaustion cycles at the focal volume of the inspection laser explained the uncertainty values characteristic of LIBS inspection of aerosols. A thorough inspection of the emission in time evidenced a significantly different evolution of the intensity profile for commonly monitored Cu lines owed not only to the nature of the monitored transit and pulse energy, but also to particle size. These results suggest that the experimental settings for quantitative ultrafine aerosol inspection need to be tuned according to the target particle size and the particle density of the aerosol as seeding effects facilitates signal saturation, therefore this effect simultaneously contributes to and detracts from the analytical performance of LIBS on nanometric aerosols., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In the present work, the authors introduce a shape-specific methodology for evaluating the full elemental composition of single micro- and nanoparticles fabricated by laser ablation of bulk targets. For this purpose, bronze samples were directly ablated within an ablation cell, originating dry aerosols consisting of multielemental particles. The in situ generated particles were first optically trapped using air at atmospheric pressure as medium and, then, probed by laser-induced breakdown spectroscopy (LIBS). A key aspect of this technology is the circumvention of possible material losses owing to transference into the inspection instrument while providing the high absolute sensitivity of single-particle LIBS analysis. From the results, we deepen the knowledge in laser-particle interaction, emphasizing fundamental aspects such as matrix effects and polydispersity during laser ablation. The dual role of air as the atomization and excitation source during the laser-particle interaction is discussed on the basis of spectral evidences. Fractionation was one of the main hindrances as it led to particle compositions differing from that of the bulk material. To address possible preferential ablation of some species in the laser-induced plasma, two fluence regimes were used for particle production, 23 and 110 J/cm 2 . LIBS analysis revealed a relationship between chemical composition of the individual particles and their sizes. At 110 J/cm 2 , 65% of the dislodged particles were distributed in the range of 100-500 nm, leading to a higher variability of the LIBS spectra among the inspected nanoparticles. In contrast, at 23 J/cm 2 , around 30% of the aerosolized particles were larger than 1 μm. At this regime, the composition better resembled the bulk material. Therefore, we present a pathway to evaluate how adequate the fabrication parameters are toward yielding particles of a specific morphology while preserving compositional resemblance to the parent bulk sample.

Simultaneous detection of multiple constituents in the characterization of state-of-the-art nanomaterials is an elusive topic to a majority of the analytical techniques covering the field of nanotechnology. Optical catapulting (OC) and optical trapping (OT) have recently been combined with laser-induced breakdown spectroscopy (LIBS) to provide single-nanoparticle resolution and attogram detection power. In the present work, the multielemental capabilities of this approach are demonstrated by subjecting two different types of nanometric ferrite particles to LIBS analysis. Up to three metallic elements in attogram quantities are consistently detected within single laser events. Individual excitation efficiency for each species is quantified from particle spectra showing an exponential correlation between photon production and the energy of the upper level of the monitored atomic line. Moreover, a new sampling strategy based in skimmer-like 3D printed cones that allows for thin dry nanoparticle aerosols to be formed via optical catapulting is introduced. Enhanced sampling resulted in an increase of the sampling throughput by facilitating stable atmospheric-pressure optical trapping of individual particles and spectroscopic chemical characterization within a short timeframe.

Current trends in nanoengineering are bringing along new structures of diverse chemical compositions that need to be meticulously defined in order to ensure their correct operation. Few methods can provide the sensitivity required to carry out measurements on individual nano-objects without tedious sample pre-treatment or data analysis. In the present study, we introduce a pathway for the elemental identification of single nanoparticles (NPs) that avoids suspension in liquid media by means of optical trapping and laser-induced plasma spectroscopy. We demonstrate spectroscopic detection and identification of individual 25(±3.7) to 70(±10.5) nm in diameter Cu NPs stably trapped in air featuring masses down to 73±35 attograms. We found an increase in the absolute number of photons produced as size of the particles decreased; pointing towards a more efficient excitation of ensembles of only ca. 7×10 5 Cu atoms in the onset plasma., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© The Author(s) 2016.)

The diagnosis of drowning can be extremely difficult, especially when the typical morphological signs of drowning are not present, or when the body is in an advanced stage of putrefaction. The main aim of this work is to demonstrate the applicability of laser-induced breakdown spectroscopy (LIBS) to the diagnosis of seawater drowning. Ten teeth samples were selected from eight medico-legal autopsies. A Nd:YAG laser operating at its fundamental wavelength (1,064 nm) was used to generate microplasmas at the sample surface. Strontium (Sr) concentration in tooth samples has been found to be a key factor for the diagnosis of seawater drowning. Spectral differences between the dentin and the enamel were observed. Greater Sr abundance was located in the dentin, with relative standard deviations in the range of 30 to 35%. In addition, chemical images were generated to study the spatial distribution of Sr along the piece. In all cases, Sr content was higher when the cause of the individual death was drowning. A blind experiment was performed to exclude the possibility that the increase of Sr is due to passive diffusion in the blood. The detection of Sr as well as the determination of its distribution by LIBS in dentin seems to be a promising complementary tool for the diagnosis of death by seawater drowning.

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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.

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., (Copyright © 2010 Elsevier B.V. All rights reserved.)

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%.

This paper reports the development and field testing of a man-portable instrument based on laser-induced breakdown spectrometry (LIBS) for inspection and analysis of speleothems. The 50 mJ of a Q-switched Nd:YAG laser operating at 1064 nm was used to generate a plasma on the sample. Plasma emission was then guided using a fiber-optic cable to a 1/10 m spectrometer equipped with a charge-coupled device (CCD) array detector. Plasma light was automatically processed in order to obtain surface and in-depth information from the speleothems. A field campaign in the interior of Nerja Cave (a large karstic formation in the South of Spain) has been carried out, aimed at evaluating the analytical performance of the instrument when operating in an unfriendly environment. Identification analysis of the speleothems' alteration layers and depth profiles of Sr and Ca is carried out and reported.

Improvement in depth profiling capabilities of laser-induced breakdown spectrometry (LIBS) for multilayered samples has been attempted. For this purpose, in a typical LIBS experiment, an optical restriction consisting of a pinhole placed between the dichroic mirror and the collecting lenses has been used. This new optical approach allows observing only the light emission coming from the central region of the plume. The microplasma was created on the sample by a pulsed Nd:YAG laser operating at 1064 nm with a homogeneous distribution of energy across the beam. Light emitted by the microplasma was detected with an intensified charge-coupled device (iCCD) multichannel detector. The effect of pinhole diameter and the delay time influence on depth analysis have been assessed. An ablation range of only a few nanometers per pulse has been achieved. Depth profiles of various metals (Cr, Ni, Cu) from multilayered samples have been generated by LIBS and depth resolution at different delay times using various pinhole diameters have been calculated and compared.

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 m(2) and 650 m(2), 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.