From multi to single-particle analysis: A seasonal spectroscopic study of airborne particulate matter in Zaragoza, Spain.

It is distinguished that deficient outdoor air quality is responsible for substantial health and climate issues. The aim of our study was to investigate the air quality in the city of Zaragoza (Spain) by characterizing atmospheric particulate matter (PM10) during two seasons (winter and spring). PM10 samples were collected in 2022 in quartz filters through a low-volume sampler and chemically analysed by complementary analytical techniques: Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), Laser Induced Breakdown Spectroscopy (LIBS), Raman Spectroscopy (RS) and Field Emission Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (FESEM-EDS). Results have revealed, together with a temperature inversion phenomenon in winter, the presence of both natural (Al, Ca, Mg, Ti, Sr, Fe, etc.) and anthropogenic particles. The latter mainly formed by black carbon with an origin on fossil fuel combustion emissions. Additionally, chemical analyses of PM10 filters showed the presence of three types of microplastics suspended in the air of the city: polyethylene terephthalate (PET), polyamides (PA) and polystyrene (PS). The results obtained from this research are of special interest to take into account for future air quality policies, particularly those with the aim of reducing air pollution in cities.

Evidence of human impact in Antarctic region by studying atmospheric aerosols.

Air quality is a global concerning topic because of its great impact on the environment and health. Because of that, the study of atmospheric aerosols looking for harmful pollutants is rising, as well as the interest in the origin of the contaminants. Depending on the nature and size of the aerosols, some elements can be detected at a great distance from the emission source, even in Antarctica, where this study is conducted. Several samples of PM filters from 2018 to 2019 (Deception Island) and 2019-2020 (Livingston Island) campaigns have been analyzed by three powerful spectroscopic techniques: FESEM (Field Emission Scanning Electron Microscopy), LIBS (Laser Induced Breakdown Spectroscopy), and ICP-MS (Inductively Coupled Plasma Mass Spectrometry). These techniques have allowed us to find some heavy metals in the air of the Antarctic region (Al, Fe, Ti, Ni, Cr, and Mn). Deeper studies on ICP-MS results have confirmed those results and have also provided information on their potential sources. Thus, while Al, Fe, Ti and Mn concentrations can be explained by crustal origin, Ni and Cr presented high values only coherent with important human contribution. The results point out that the Antarctic region is no longer a clean and isolated environment from human pollution.

Characterization of atmospheric aerosols in the Antarctic region using Raman Spectroscopy and Scanning Electron Microscopy.

The non-destructive spectroscopic characterization of airborne particulate matter (PM) was performed to gain better knowledge of the internal structures of atmospheric aerosols at the particle level in the Antarctic region, along with their potential sources. PM and soil samples were collected during the 2016-2017 austral summer season at the surroundings of the Spanish Antarctic Research Station "Gabriel de Castilla" (Deception Island, South Shetland Islands). PM was deposited in a low-volume sampler air filter. Raman spectroscopy (RS) and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDS) were used to determine the elemental and molecular composition of the individual aerosol and soil particles. Filter spectra measured by these techniques revealed long-range atmospheric transport of organic compounds (polystyrene and bacteria), local single and cluster particles made of different kinds of black carbon (BC), exotic minerals (polyhalite, arcanite, niter, ammonium nitrate, syngenite and nitrogen, phosphorus, and potassium (NPK) fertilizer), and natural PM (sea salts, silicates, iron oxides, etc.). In addition to the filter samples, forsterite and plagioclase were discovered in the soil samples together with magnetite. This is the first report of the presence of a microplastic fiber in the Antarctic air. This fact, together with the presence of other pollutants, reflects that even pristine and remote regions are influenced by anthropogenic activities.

Aerosol analysis by micro laser-induced breakdown spectroscopy: A new protocol for particulate matter characterization in filters.

Atmospheric aerosols (particulate matter - PM) affect the air quality and climate, even in remote areas, such as the Antarctic Region. Current techniques for continuous PM monitoring are usually complex, costly, time consuming and do not provide real-time measurements. In this work, based on micro laser-induced breakdown spectroscopy (LIBS), an innovative method with an optical design and multi-elemental scanning imaging, is presented to characterize PM collected in filters from Antarctica. After following a simple protocol and under atmospheric pressure, the new approach allows to obtain a global visualization of the elemental PM composition of the filters with a minimum sample destruction and preparation. For the first time, we were able to map the localization of pollutants in filters at high spatial resolution and speed. This recent method offers a new insight on the characterization of PM, particularly in isolated areas, where no complex equipment and real time measurements are demanded.

Direct determination of Al and Pb in waste printed circuit boards (PCB) by laser-induced breakdown spectroscopy (LIBS): Evaluation of calibration strategies and economic - environmental questions.

Matrix-matching calibration (MMC), two-point calibration transfer (TP CT), one-point and multi-line calibration (OP MLC), single-sample calibration (SSC) and calibration free (CF) were evaluated in order to overcome matrix effects in laser-induced breakdown spectroscopy (LIBS). These calibration strategies were evaluated for direct determination of Al and Pb in waste printed circuit boards (PCB) using direct solids analysis by LIBS. Each strategy has limitations and advantages of its implementation, for the correction of matrix effects, so that it allows elementary determination with adequate accuracy. The MMC and CF proved to be excellent calibration strategies for the determination of strategic (Al) and toxic (Pb) elements by LIBS, with good recoveries (ranging from 80-120%) and low relative standard deviation (RSD%) values. A detailed discussion of the advantages and limitations of each of these five calibration strategies evaluated for LIBS is presented in this study. Lead concentrations in waste PCB samples are 5-12 times higher than established by Directive 2011/65/EU, and the samples analyzed contain between 3 and 55 g kg-1 Al, being an interesting economic and recycling source for this metal.

Laser-Induced Breakdown Spectroscopy (LIBS) for Monitoring the Formation of Hydroxyapatite Porous Layers.

Laser-induced breakdown spectroscopy (LIBS) is applied to characterize the formation of porous hydroxyapatite layers on the surface of 0.8CaSiO3-0.2Ca3(PO4)2 biocompatible eutectic glass immersed in simulated body fluid (SBF). Compositional and structural characterization analyses were also conducted by field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), and micro-Raman spectroscopy.

Multiple response optimization of laser-induced breakdown spectroscopy parameters for multi-element analysis of soil samples.

Laser-induced breakdown spectroscopy (LIBS) is an emerging analytical technique to perform elemental analysis in natural samples independent of their physical state (solid, liquid, or gaseous). Due to its instrumental features, LIBS shows promising potential to perform analysis in situ and in environments at risk. Since the analytical performance of LIBS strongly depends on the choice of experimental conditions, each particular application needs a specific instrumental adjustment. The present study evaluated three LIBS instrumental parameters regarding their influences on signal-to-noise ratio (SNR) of seven elements in soil samples: laser pulse energy, delay time, and integration time gate. A multivariate technique was used due to the significant interaction among the evaluated parameters. Subsequently, to optimize LIBS parameters for each individual element response, a method for multiple response optimization was used. With only one simple screening design, it was possible to obtain a good combination among the studied parameters in order to simultaneously increase the SNR for all analytes. Moreover, the analysis of individual response for elements is helpful to understand their physical behavior in the plasma and also how they are embedded in the sample matrix.

Removal of chromium (III) by using coal as adsorbent.

The adsorption of Cr(III) by two different coal varieties from Lakhra and Thar coalfields (Pakistan) have been studied in batch mode. The effect of adsorbent dose, pH, contact time and agitation speed on the adsorption of Cr(III) by both the coals were investigated. Adsorption equilibrium was achieved in 40-50 min. The Langmuir, Freundlich and Temkin adsorption isotherms were used to elucidate the observed sorption phenomena. The maximum Cr(III) removal was 2.61 mg of Cr(III) per gram of LC (Lakhra coal) and 2.55 mg of Cr(III) per gram of TC (Thar coal) as evaluated from Langmuir isotherm. The heat of sorption was in the range 3.75-3.87 kJ/mol as evaluated from Temkin isotherm. Best results were obtained at pH>5. It is proposed that low rank coals of Pakistan can be used for removal of toxic metals like Cr(III) from industrial effluents/waste waters.

Strategies for the identification of urinary calculus by laser induced breakdown spectroscopy.

The present work studies two different strategies to identify urinary calculus. On one hand, (linear or parametric and rank or non-parametric) correlation methods using a mu-LIBS system are studied. On the other hand, elemental ratios of reference materials are determined by using a higher-energy laser and an Echelle spectrograph with an ICCD camera, although without microscope. A data-treatment method was applied for each system and real samples of kidney stones--previously analyzed by IR spectroscopy--were used for reliable evaluation of two identification strategies.

Bioaerosols chemometric characterization by laser-induced fluorescence: air sample analysis.

A laser-induced fluorescence (LIF) system was optimized using a solution of Micrococcus luteus in ethanol/water 50% (v/v) to obtain spectra in the gas phase of 46 bioaerosols. Experimental designs such as Plackett-Burman and factorial design were applied. The fluorescence spectra were treated chemometrically by principal component analysis, linear discriminant analysis and hierarchical cluster analysis to classify the microorganisms according to family, morphology and gram. The best results were obtained using LDA. The method was applied to air samples and the LIF results allowed to characterize bioaerosols reliability. The robustness of the technique was demonstrated by the identification of many bacteria.

Bacteria spectra obtained by laser induced fluorescence.

Laser-induced fluorescence technique (LIF) is described for getting bacteria spectra in the liquid phase. An excimer laser pumping a dye-laser and a doubly frequency laser have been used, exciting the bacteria to 290 nm, and using a monochromator, 600 lines/mm grating, with a CCD to measure and obtain the fluorescence spectra. In this study, a laser induced fluorescence system to measure certain bioaerosols (bacteria) was optimised. Finally, a small bacteria fluorescence spectra collection is presented.

Laser-induced breakdown spectroscopy for quantitative spectrochemical analysis of geological materials: effects of the matrix and simultaneous determination.

A microscopic laser-induced breakdown spectrometer was used to evaluate the analytical matrix effect commonly observed in the analysis of geological materials. Samples were analyzed in either the powder or pressed pellet forms. Calibration curves of a number of iron and aluminum compounds showed a linear relationship between the elemental concentration and peak intensity. A direct determination of elemental content can thus be made from extrapolation on these calibration curves. To investigate matrix effects, synthetic model samples were prepared from various iron and aluminum compounds spiked with SiO2 and CaCO3. The addition of these matrices had a pronounced analytical effect on those compounds prepared as pressed pellets. However, results indicated the absence of matrix effects when the samples were presented to the laser as loose powders on tape and results were compared to certified values, indicating the reliability of this approach for accurate analysis, provided the sample particle diameters are greater than approximately 100 microm. Finally, the simultaneous analysis of two different elements was demonstrated using powders on tape.