Geochemical characterization of the Martian analogues Enekuri and Fruiz, located in the Basque-Cantabrian Basin, by spectroscopic techniques.

This work presents the geochemical characterization of two Martian analogues located in the Basque-Cantabrian Basin: Enekuri and Fruiz. In contrast to previous works carried out on the coastline analogues Meñakoz and Armintza (Biscay, Spain), these new outcrops are not in contact with sea-water nowadays. Hence, the weathering processes observed in Enekuri and Fruiz (inland) are different from those observed in Armintza and Meñakoz (coastline). In this way, among all the mineral phases found the only ones in common between inland and coastline outcrops are albite and chlorites, minerals that were formed in aqueous conditions. Understanding the differences presented in both types of outcrops could help to interpret the future results from the missions Mars2020 and the ExoMars2022, since coastline outcrops are affected by sea-water weathering and inland outcrops are altered by the high biological activity.

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.

Interrelationships in the Gypsum-Syngenite-Görgeyite System and Their Possible Formation on Mars.

Calcium sulfates are known to be potential reservoirs of organic compounds and have been detected on Mars. However, not all data that indicate the presence of sulfates collected by the Mars Exploration Rovers (Spirit and Opportunity) and Curiosity rover can be explained by the different calcium sulfate polymorphs, and therefore, mixtures of calcium sulfates with other single sulfates must be considered. In addition, the presence of mixed calcium sulfates supports the data and indicates that the molar ratio of sulfate/calcium is >1. To obtain adequate spectroscopic information of mixed-cation sulfates to be used in the interpretation of data from Mars in the next few years, the thermodynamically stable syngenite (K2Ca(SO4)2·H2O) and görgeyite (K2Ca5(SO4)6·H2O) mixed-cation sulfates have been studied along with the interrelationships in the gypsum-syngenite-görgeyite system to understand their possible formation on Mars. Raman spectroscopy and Visible-Near Infrared-Shortwave Infrared (VisNIR) spectroscopy have been used for their characterization to increase the databases for the two future Mars exploration missions, Mars2020 and ExoMars2022, where both techniques will be implemented. These VisNIR data can also help with the interpretation of spectral data of salt deposits on Mars acquired by the OMEGA and CRISM spectrometers onboard the Mars Express and Mars Reconnaissance orbiters. This work demonstrates that syngenite (K2Ca(SO4)2·H2O) easily precipitates without the need for hydrothermal conditions, which, depending on the ion concentrations, may precipitate in different proportions with gypsum. Furthermore, in this study, we also demonstrate that, under hydrothermal conditions, görgeyite (K2Ca5(SO4)6·H2O) would also be highly likely to form and may also be identified on Mars together with syngenite and gypsum.

Analytical methodology to evaluate the Terrestrial Weathering of Libyan Desert Glasses and Darwin Glasses after their formation.

Libyan Desert Glasses (LDGs) and Darwin Glasses (DGs) are impact glasses produced by the impact of an extraterrestrial body into the Earth million years ago. LDGs were formed in the Libyan Desert (Africa) and DGs in Tasmania (Australia). From their formation, they have suffered terrestrial weathering processes due to their interaction with the environment. This is the first work that has evaluated their weathering processes according to their composition, the surrounding environment, and the climate. An innovative methodology based on the leaching of organic and inorganic ions and chemical modeling simulations was employed. Inductively coupled plasma-mass spectrometry (ICP-MS), ionic chromatography (IC), and solid-phase microextraction (SPME), and head space (HS) injections coupled to gas chromatography and mass spectrometry (GC-MS) detection were used. As a result, soluble organic compounds such as oxalates, n-hexadecanoic acid, and 4-chlorobenzalacetone were detected. The inorganic ions suffered a similar process, going inside the body of glasses and precipitating the corresponding salts when water evaporated. As these compounds are polar, they were probably transported by infiltration waters from outside the glasses, remaining inside in the pores, cavities, or cracks of the glasses during thousands of years. In the case of the DGs, it could be observed that under the oxidizing conditions of the terrestrial atmosphere, sulfides present in some samples transformed into sulfates. Finally, this methodology could be applied in other extraterrestrial materials discovered in deserts, ice fields, or in locations with great living activity like those of Tasmania.

Non-destructive characterisation of the Elephant Moraine 83227 meteorite using confocal Raman, micro-energy-dispersive X-ray fluorescence and Raman-scanning electron microscope-energy-dispersive X-ray microscopies.

The application of a non-destructive analytical procedure to characterise the mineral phases in meteorites is a key issue in order to preserve this type of scarce materials. In the present work, the Elephant Moraine 83227 meteorite, found in Antarctica in 1983 and originated from 4 Vesta asteroid, was analysed by micro-Raman spectroscopy, micro-energy-dispersive X-ray fluorescence and the structural and chemical analyser (Raman spectroscopy coupled with scanning electron microscopy-energy-dispersive spectroscopy) working in both point-by-point and image modes. The combination of all these techniques allows the extraction of, at the same time, elemental, molecular and structural data of the studied microscopic area of the meteorite. The most relevant results of the Elephant Moraine 83227 were the finding of tridymite for the first time in a 4 Vesta meteorite, along with quartz, which means that the meteorite suffered high temperatures at a certain point. Moreover, both feldspar and pyroxene were found as the main mineral phases in the sample. Ilmenite, apatite, chromite and elemental sulphur were also detected as secondary minerals. Finally, calcite was found as a weathering product, which was probably formed in terrestrial weathering processes of the pyroxene present in the sample. Besides, Raman spectroscopy provided information about the conditions that the meteorite experienced; the displacements in some feldspar Raman bands were used to estimate the temperature and pressure conditions to which the Elephant Moraine 83227 was subjected, because we obtained both low and high formation temperature feldspar.

Detection of organic compounds in impact glasses formed by the collision of an extraterrestrial material with the Libyan Desert (Africa) and Tasmania (Australia).

Impact glasses are rich silica melted formed at high temperature and pressure by the impact of an extraterrestrial body on Earth. Here, Libyan Desert glasses (LDGs) and Darwin glasses (DGs) were studied. Two non-destructive analytical techniques were used to detect and characterize organic compounds present in their inclusions: Raman spectroscopy and scanning electron microscopy coupled to energy-dispersive X-ray spectroscopy (SEM-EDS). Phytoliths, humboldtine, palmitic acid, myristic acid, oleic acid, 4-methyl phthalic acid, and S-H stretching vibrations of amino acids were identified. The presence of these particular organic compounds in such materials has not been reported so far, providing information about (a) the ancient matter of the area where the impact glasses were formed, (b) organic matter belonging to the extraterrestrial body which impacted on the Earth, or (c) even to current plant or bacterial life, which could indicate an active interaction of the LDG and DG with the surrounding environment. Moreover, the identification of fullerene allowed us to know a pressure (15 GPa) and temperatures (670 K or 1800-1900 K) at which samples could be subjected.

Metallurgical residues reused as filler after 35years and their natural weathering implications in a mountain area.

The natural weathering of EAF (Electric Arc Furnace) and LF (Ladle Furnace) steel slag was evaluated through changes in the mineralogical and elemental composition. For that purpose, black steel slag and mixture of black and white steel slag were collected from two forest tracks, where they had been used as filler 19 and 35years ago respectively in a protected mountain area. Primary/original and secondary/degradation compounds were identified by spectroscopic techniques (Raman Spectroscopy, X-Ray Diffraction (XRD) and Scanning Electron Microscopy/Energy Dispersive X-Ray Spectroscopy (SEM/EDS)). Among secondary compounds, brucite (Mg(OH)2), portlandite (Ca(OH)2), thaumasite (Ca3Si(CO3)(SO4)(OH)6.12H2O) were identified. Secondary compounds indicated the reactivity of the slag with the surrounding environment (underground waters, atmosphere, lands and organisms), and volume change of the material. This effect could promote fractures in the road and thus, increase the possibility of leaching of hazardous elements (HE), present in the slags, to lands, rivers, etc. Besides, potentially toxic compounds such as hashemite (BaCrO4) and crocoite (PbCrO4) were identified as Cr(VI), which means a potential hazard to the surrounding environment and human life, since the sampling location is a mountain area with recreational activities. Cr(VI) can affect to the growth and development of plants, soil microbial communities, animals and cause allergy, asthma and respiratory tract cancer in humans. Moreover, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) allowed us to observe similar ranges of elemental concentrations in slag samples of the two forest tracks, with the exception of Ca, Mg, Sr, Pb, Ni and As concentration values. They were higher in the forest track with mixture of black and white slag than in the track with only black slag, and therefore, more likely to be leached and to be an environmental risk over time. By contrast, Na, V, Cr and W values were higher in the track with only black steel slag.

Are children playgrounds safe play areas? Inorganic analysis and lead isotope ratios for contamination assessment in recreational (Brazilian) parks.

In city playgrounds, there is a potential risk of harming children's health by contamination coming from anthropogenic activities. With the aim to determinate the sources and the risk of hazardous elements, soil samples were collected in 19 selected playgrounds of different urban and rural areas from the Rio Grande do Sul state (Brazil). The concentration of 23 metals and metalloids and lead isotopic ratios were determined by ICP-MS. The methodology proposed here, firstly, classified the parks according to the average metal content by means of the NWACs (Normalized-and-Weighted Average Concentrations) and assess the contamination risk determining the Contamination Factors (CFs). Finally, statistical tools (correlation analysis and principal component analysis) were used to identify the most important contamination sources. The statistical tools used, together with lead isotopic composition analysis of the samples, revealed that coal combustion is the main source of contamination in the area. Vegetation was identified as a barrier for the contamination coming from the city. Nonetheless, some of the soils present a possible toxicological risk for humans. In fact, Cr, Sb, and Pb concentrations were higher than the Residential Intervention Values (VIRs) defined by the Environmental Protection Agency of the State of São Paulo, also in Brazil.

Contamination study of forest track soils located in a recreational area and filled with steel industry waste 30years ago.

The reuse of waste is increasingly widespread in order to avoid the exploitation of natural resources and to reduce costs. An example of that reuse is the employment of steel slag, a by-product from the steel making process. When the steel is produced through an electric arc furnace (EAF), two types of slag are generated: black and white slag. One application rarely used for this waste is as filler in forest tracks. In this work, two forest tracks of the Basque Country (northern Spain) filled with black and white slag 19 and 35years ago, respectively, have been studied. Leaching tests were performed using Milli-Q water and acetic acid over the slags collected in that area. Additionally, soil samples collected near the slags were subjected to acid digestion. In these soil samples, there were elements of natural origin and others that could come from the leaching of the slag. Some of the more leached elements from the black slag (Ca, Fe, K, Cr, Se, W, Mn and Mo) and white slag (Mg, Al, Na, Co, Ni and Cu) coincided with the elements of highest concentration found in the soil samples. Moreover, there were differences in some elemental concentrations of soil samples with only black slag (higher presence of Ca and Mg) and soil samples with a mixture of both types of slag. It was noticeable that the highest concentration values of the measured elements were found on a specific side of the forest tracks, possibly due to the runoff water or the higher inclination of that side. On the other hand, some areas of both forest tracks could be considered contaminated by Cr according to a standard values from the Basque regulation, posing a risk to human health since they are recreational areas.

Multispectroscopic methodology to study Libyan desert glass and its formation conditions.

Libyan desert glass (LDG) is a melt product whose origin is still a matter of controversy. With the purpose of adding new information about this enigma, the present paper analyzes the inner part of LDG specimens and compares them with the results of LDG surfaces. An integrated analytical methodology was used combining different techniques such as Raman spectroscopy, in point-by-point and imaging modes, scanning electron microscopy with X-ray microanalysis (SEM-EDS), energy-dispersive micro X-ray fluorescence spectrometry (µ-EDXRF), electron probe micro analyzer (EPMA), and optical cathodoluminescence (Optical-CL). According to our results, flow structures of the melt and the amorphous nature of the matrix could be discerned. Moreover, the observed displacement of Raman bands, such as in the cases of quartz and zircon, and the identification of certain compounds such as coesite (the most clarifying phase of high pressures), α-cristobalite, gypsum, anhydrite, corundum, rutile, amorphous calcite, aragonite, and calcite allowed us to know that LDGs could be subjected to shock pressures between 6 and more than 30 GPa, and temperatures between 300 and 1470 °C. The differences of temperature and pressure would be provoked by different cooling processes during the impact. Besides, in most cases the minerals corresponding to high pressure and temperatures were located in the inner part of the LDGs, with some exceptions that could be explained because they were trapped subsequently to the impact; there was more than one impact or heterogeneous cooling.Furthermore, nitrogen and oxygen gases were identified inside bubbles, which could have been introduced from the terrestrial atmosphere during the meteorite impact.These data helped us to clarify some clues about the origin of these enigmatic samples.