Metals and metalloids in high-altitude Pyrenean lakes: sources and distribution in pre-industrial and modern sediments.

High-altitude Pyrenean lakes are ecosystems far from local pollution sources, and thus they are particularly sensitive to the atmospheric deposition of metals and metalloids. This study aims to quantify the effect of human activity in 18 lakes located in both side of the France-Spain frontier. Sediment cores were collected in summer 2013, sampled at a 1cm resolution and the concentration of 24 elements was measured by ICP-MS. Statistic and chemometric analysis of the results highlights the influence of the geographical position and lithogenic features of each lake basin on trapping pollutants. More than the 80% of the lakes showed values of enrichment factor (EF) above 2 for at least one of the elements investigated in at least one core interval, which corroborates the existence of historical anthropogenic inputs of elements in the studied area. The results demonstrate the natural origin of As and Ti in Pyrenees, together with the significant anthropogenic inputs of Cd, Pb, Sb and Sn from ancient times. The data set points mining activities as the main historical source of pollution and illustrate the large impact of the industrial revolution. The regional variability could reflect also differential long-range transport, followed by dry or wet deposition.

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.

Long-term in situ non-invasive spectroscopic monitoring of weathering processes in open-air prehistoric rock art sites.

In this work, an innovative non-destructive monitoring methodology based on the analysis over time of open-air rock art sites is presented. This approach is based on the combination of in situ spectroscopic and chemometric studies to diagnose and monitor the state of conservation of rock art sites. Data acquired over a period of time by non-invasive analytical techniques such as portable Raman spectrometry (RS) and handheld energy-dispersive X-ray fluorescence (HH-EDXRF) spectrometry are compared to detect physicochemical changes that could affect the rock painting integrity. To demonstrate the applicability of the proposed procedure, three analysis campaigns (between 2013 and 2016) were carried out, analyzing Levantine rock pictographs preserved in the rock shelter of Solana de las Covachas VI (Albacete, Spain; see Electronic Supplementary Material (ESM) Fig. S1). The analyzed areas showed different types of active weathering processes such as gypsum and calcium oxalate formation, giving rise to conservation issues such as painting fading, surface loss, microbial colonizations, and formation of crusts. Results evidence that the proposed methodology can be very useful to monitor chemical changes in the surface of the walls where the rock art is located, thus obtaining crucial information for its preservation and management.

Biodeterioration of Pompeian mural paintings: fungal colonization favoured by the presence of volcanic material residues.

This work was focused on the study of the biodegradation processes jeopardizing a mural painting conserved in the basement of Ariadne House (archaeological site of Pompeii, Italy). The fresco stood out for its peculiar state of preservation: the upper part, recovered in 1988, was just barely colonized by microorganisms. On the contrary, the lower part (excavated in 2005) was almost completely covered by extensive biological patinas. The genomic characterization carried out by polymerase chain reaction (PCR) highlighted the presence of seven different fungi strains on the mural surface. Beside, in situ and laboratory analyses were performed with the purpose of identifying the causes of the heterogeneous spatial distribution of the biopatinas. The in situ Raman spectroscopy and energy dispersive X-ray fluorescence (ED-XRF) spectroscopy measurements excluded any link between the heterogeneous colonization and the original materials present in the wall. On the other side, X-ray diffraction (XRD) and scanning electron microscopy (SEM) on microsamples proved the presence of a thin volcanic material layer overlying the lower part of the fresco. Considering that most of the biofilms of the studied mural painting only growth over these residues, it was confirmed the role of volcanic material as a suitable support for biological colonization. Thanks to the obtained results, this research helped to understand more in depth an important degradation pathway threatening the artworks from one of the most important archaeological sites in the world.

Study of corrosion in archaeological gilded irons by Raman imaging and a coupled scanning electron microscope-Raman system.

In this work, analytical and chemical imaging tools have been applied to the study of a gilded spur found in the medieval necropolis of Erenozar (Bizkaia, Spain). As a first step, a lot of portable equipment has been used to study the object in a non-invasive way. The hand-held energy-dispersive X-ray fluorescence equipment allowed us to characterize the artefact as a rare example of an iron matrix item decorated by means of a fire gilding technique. On the other hand, the use of a portable Raman system helped us to detect the main degradation compounds affecting the spur. Afterwards, further information was acquired in the laboratory by analysing detached fragments. The molecular images obtained using confocal Raman microscopy permitted us to characterize the stratigraphic succession of iron corrosions. Furthermore, the combined use of this technique with a scanning electron microscope (SEM) was achieved owing to the use of a structural and chemical analyser interface. In this way, the molecular characterization, enhanced by the magnification feature of the SEM, allowed us to identify several micrometric degradation compounds. Finally, the effectiveness of one of the most used desalination baths (NaOH) was evaluated by comparing its effects with those provided by a reference bath (MilliQ). The comparison proved that basic treatment avoided any side effects on the spur decorated by fire gilding, compensating for the lack of bibliographic documentation in this field.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

The mobilization of hazardous elements after a tropical storm event in a polluted estuary.

The Tubarão River (Santa Catarina, Brazil) is affected by hazardous elements (HEs) pollution from abandoned coal mines, agricultural activities, urban discharges, industrial and leisure zones, etc. In order to study the distribution and sources of HEs contamination in a polluted estuary after a tropical storm, waters and surface sediments were collected from 15 sampling sites along the Tubarão River. The concentration of 24 elements (Ag, Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, Tl, V, W, and Zn) were measured by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the mineralogical composition of the sediments by Raman spectroscopy and X-ray diffraction (XRD). The metal concentrations in water and sediment showed wide spatial variation due to the variability in water discharges and anthropogenic inputs after a storm. In general, higher metal concentration in water and lower in sediments were found upstream (closer to coal mining). Downstream sampling sites and the Oratorio River sampling site (one of the eight tributaries of the estuary) showed the highest values in sediment samples. Normalized and Weighed Average Concentrations (NWAC) were calculated, which allow us to identify, in a very simple way, the sampling sites of higher concern (hotspots of contamination) in the studied area. NWAC suggested that the strong rainfall events could affect to the metal distribution in sediments. The results of this study were compared with a previous study in the same area during dry season by Principal Component Analysis (PCA), showing changes in environmental pollution of the sediment after a strong storm event.

The properties of the nano-minerals and hazardous elements: Potential environmental impacts of Brazilian coal waste fire.

Brazilian coal area (South Brazil) impacted the environment by means of a large number of coal waste piles emplaced over the old mine sites and the adjacent areas of the Criciúma, Urussanga, and Siderópolis cities. The area studied here was abandoned and after almost 30 years (smokeless visual) some companies use the actual minerals derived from burning coal cleaning rejects (BCCRs) complied in the mentioned area for industry tiles or refractory bricks. Mineralogical and geochemical similarities between the BCCRs and non-anthropogenic geological environments are outlined here. Although no visible flames were observed, this study revealed that auto-combustion existed in the studied area for many years. The presence of amorphous phases, mullite, hematite and other Fe-minerals formed by high temperature was found. There is also pyrite, Fe-sulphates (eg. jarosite) and unburnt coal present, which are useful for comparison purposes. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present study using advanced analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and mineral formation. It is reporting huge numbers of rare minerals with alunite, montmorillonite, szomolnokite, halotrichite, coquimbite and copiapite at the BCCRs. The data showed the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing hazardous elements, such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. By Principal Component Analysis (PCA), the mineralogical composition was related with the range of elemental concentration of each sample. Most of the nano-minerals and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important role to environment and human health.

Finnish wallpaper pigments in the 18th-19th century: presence of KFe3(CrO4)2(OH)6 and odd pigment mixtures.

Several Finish wallpapers from the 18th and 19th century were analysed by using Raman spectroscopy assisted with EDXRF instrumentation, in an attempt of determine the pigments used in their manufacture process as well as of trying to date some of the samples through pigment composition. All pigments present in samples were determined and surprisingly the unusual and strange iron (III) chromate yellow pigment was found. Besides, unusual mixtures were found to obtain fashionable colours, especially in blue and green areas, where more than one blue pigments were mixed with green and yellow pigments. Blue verditer, ultramarine blue, Prussian blue, chrome yellow, calcite, lead white, red and yellow iron oxide, gypsum and carbon black were identified. The presence of the risky and poisonous emerald green must be highlighted. The results were compared with those found in other wallpapers from Spain and France.

Ultrasound energy focused in a glass probe: an approach to the simultaneous and fast extraction of trace elements from sediments.

The 3051 USEPA method (or alternatively, the 3051A) can be considered nowadays as a reference method to extract metals from sediments. However, after microwave heating, the sample must be allowed to cool down, which results in a considerable lengthening of the whole analytical process. Microwave ovens and their maintenance are, in addition, expensive, and its use is relatively dangerous. The use of ultrasound focused energy to assist the extraction of chemicals from solid samples is a safe and relatively cheap technique. In this work we propose a new method to extract simultaneously several elements from sediments using ultrasound energy focused in a glass probe to accelerate the process, and check its possibilities to become an alternative to the EPA3051(A) approach. The optimised procedure allows extracting 13 elements in only 6 min, with similar recoveries and, in general, better repetitivities than the EPA3051. In addition, the suspension is only slightly heated during the leaching process.