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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.

This work presents a new calibration method for determining the provenance of obsidian artefacts based on the combined use of XRF and laser-induced breakdown spectroscopy (LIBS). At first, obsidian samples collected from the main Mediterranean sources were characterized using portable XRF and LIBS systems. After data treatment, elemental information was used to carry out principal component analysis (PCA) for each technique. Rb, Sr, Zr, Y and Fe elements, detected by using XRF, were found to be the key parameters enabling obsidians discrimination. Likewise, LIBS data helped differentiating the analysed patterns by the intensity of their main elemental components (Ca, Al, Mg and K). After selecting the key parameters detected by each technique, a new data matrix combining XRF and LIBS data was finally built. According to PCA results, the discrimination of Mediterranean sources based on combined XRF–LIBS data ensured a higher reliability over mono-analytical models, by increasing the Euclidean distance between sources projections over three-dimensional principal components plots. Knowing that the representativeness of elemental data could be compromised by the presence of superficial degradation products or deposition patinas, a shot-to-shot comparison of in-depth LIBS analyses is finally proposed as a method to disclose whether the spot under analysis was superficially contaminated or altered. Thus, the proposed strategy based on the combined use of portable XRF and LIBS spectrometers could be particularly useful for the in situ analysis of obsidian artefacts that underwent superficial alteration or could be covered by patina products.

Marble is one of the materials most susceptible to copper leaching, resulting in easily identifiable turquoise stains on the marble. This problem is particularly relevant when we are talking about marble structures of heritage value. For this reason, conservators look for cleaning materials that are specific to the structure to be treated without damaging the original surface. Materials such as agar have been studied for a long time. Agar creates a controlled water release system that adapts to the needs of conservators who seek the greatest possible cleanliness without damaging the material to be treated. To improve the cleaning, chelating agents such as EDTA are added to the agar composition. However, the microbiological growth and the damage it produces to the original material are disadvantages to take into account. In order to solve these problems, other natural materials with cleaning potential such as kudzu and konjac gels were studied in combination with other chelating agents such as citrate, oxalate, and gluconic acid. For the characterization and evaluation of copper cleaning, various analytical techniques were used, including Raman spectroscopy, colorimetry, X-ray fluorescence (XRF), and inductively coupled plasma mass spectrometry (ICP-MS). In this study, both konjac and kudzu emerged as promising alternatives to agar, revealing distinctive features such as simplified preparation methods and inherent antimicrobial properties. The EDTA chelator was found to be the most harmful for marble surfaces, as it extracted a greater amount of calcium from the marble during application of the gels doped with it. Citrate and gluconic acid have been identified as a promising substitute to prepare doped gels for the removal of copper stains. These compounds exhibit comparable or potentially superior cleaning capabilities than EDTA, with no negative side effects.

In this work, some micro-samples belonging to the open-air rock art site of Cueva de la Vieja (Alpera, Albacete, Spain) were analysed. These samples were collected after and before a desalination treatment was carried out, with the aim of removing a whitish layer of concretion that affected the painted panel. The diagnostic study was performed to study the conservation state of the panel, and to then confirm the effectiveness of the treatment. Micro energy dispersive X-ray fluorescence spectrometry, Raman spectroscopy, and X-ray diffraction were employed for the characterization of the degradation product as well as that of the mineral substrate and pigments. The micro-samples analysis demonstrated that the painted layer was settled on a dolomitic limestone with silicon aggregates and aluminosilicates as well as iron oxides. The whitish crust was composed by sulfate compounds such as gypsum (CaSO4·2H2O) with a minor amount of epsomite (MgSO4·7H2O). An extensive phenomenon of biological activity has been demonstrated since then in almost all of the samples that have been analysed, and the presence of calcium oxalates monohydrate (CaC2O4·H2O) and dehydrate (CaC2O4·2H2O) were found. The presence of both calcium oxalates probably favoured the conservation of the pictographs. In addition, some carotenoids pigments, scytonemin (C36H20N2O4), and astaxanthin (C40H52O4) were characterized both by Raman spectroscopy and by X-ray diffraction. Hematite was found as a pigment voluntarily used for the painting of the panels used in a mixture with hydroxyapatite and amorphous carbon. The results of the analyses of the samples taken after the cleaning treatment confirmed a substantial decrease in sulphate formation on the panel surface

The Ychsma society was one of the most important civilizations developed between 900 and 1532 CE in Lima, the present Peruvian capital, situated on the central coast of Peru. The Ychsma territory included the lower basin of the Rímac and Lurín valleys in the current city of Lima (Peru). Around 1470 CE, the Ychsma region was conquered and placed under the control of the Inca Empire, which ruled the region until the Spanish conquest in 1532 CE. Despite this, the Inca rule allowed local elites to maintain their position and control of the population. The archaeological site of Armatambo was an important administrative center of the Ychsma society. This site was actively occupied during the Middle Ychsma (1250–1350 CE) and Late Ychsma (1350–1532 CE) phases, and as the capital of the Sullco Curacazgo controlled a large part of the lower Rímac valley. During excavations at this site, many materials associated with ceramic production were found. One aspect crucial to the study of ceramic materials is the reconstruction of ceramic production and distribution networks, which allows us to obtain information linked to the social and economic interaction between communities. To determine the local or non-local origin of the materials found at Armatambo, 61 samples were analyzed using ICP-MS, Petrography, and SEM. The results were compared with archaeological and geological data from the Rímac valley to determine whether or not production there was local or non-local and to identify possible sources of raw materials.

244 p., The quality and authenticity assurance of food products has become an essential issue for the food industry. Even though it has been traditionally controlled using analytical destructive methods, food industry would benefit from a change that can overcome their drawbacks. The digital transformation of the industry, also known as Industry 4.0, has emerged recently as a change of paradigm in the current processes. Smart sensors have arisen as powerful tools in this digital transformation. They are a good option to perform the control of authenticity and quality in the food industry and to monitor processes. However, in order to make these sensors smart, there is the necessity of using chemometrics.Even though in other sectors this digitalization is assumed to be necessary and has already started, food industry transformation is slowed down due to its specific casuistry. In big companies, this digitalization is already a fact, but SMEs, which in Europe account for more than the 90% of the food companies, need the development of applications ad-hoc adapted for their needs, using sensors with a lower cost but still rigorous, since they have limited resources and/or digital capabilities. Therefore, more investigation is needed for the digitalization of this sector, especially regarding these enterprises.With that aim, this doctoral thesis has used three different non-destructive and portable sensors, based in different principles (near infrared spectroscopy or NIRS, bioelectrical impedance analysis or BIA and time domain reflectometry or TDR), coupled with the use of different chemometric methods, for developing five different new applications regarding the quality and authenticity control of four different food matrices: tuna, fish oil coming from by-products, avocado and béchamel sauce.

519 p., In this Doctoral Thesis a thorough study to deepen in the archaeological knowledge about the Medievaland Post-Medieval pottery activity of the north-west of the Iberian Peninsula is carried out. In this way,the existing lack of information regarding the pottery production of these periods in Zamora and Aveirois filled and the provenance of local or regional origin of the ceramics is assessed, shedding light on theregional or supraregional trade and local consumption patterns. For that, on the one hand, an optimizationof the analytical method has been made and an aging experimental approach has been presented, whichincorporates different alteration and contamination ways in ceramics deposited in water environments.These alteration and contamination paths should be considered to avoid incorrect interpretations ondifferent aspects related to ceramics. Besides, the usage of a non-destructive analytical technique (LAMC-ICP-MS) is presented, whose performance is evaluated in a case study addressed in the course of thisresearch. On the other hand, an archaeometric approach of 124 ceramics from Aveiro and Zamora hasbeen performed. In this way, chemical and mineralogical analyses of the pastes have been carried out byICP-MS and XRD and analyses of the microstructure, glaze and pigment characterization have beencarried out by SEM-EDS, Raman, LA-MC-ICP-MS, solution MC-ICP-MS and LA-HR-ICP-MS.In this Doctoral Thesis a thorough study to deepen in the archaeological knowledge about the Medievaland Post-Medieval pottery activity of the north-west of the Iberian Peninsula is carried out. In this way,the existing lack of information regarding the pottery production of these periods in Zamora and Aveirois filled and the provenance of local or regional origin of the ceramics is assessed, shedding light on theregional or supraregional trade and local consumption patterns. For that, on the one hand, an optimizationof the analytical method has been made and an aging experimental approach, Doktorego Tesi honetan Iberiar penintsulako ipar-mendebaldeko Erdi Aroko eta Erdi Aro osteko zeramikaren jarduerari buruzko ezagutza arkeologikoan sakondu da. Horrela, Zamorako eta Aveiroko garai horietako zeramika-ekoizpenari buruzko informazio falta osatu da, eta zeramikaren tokiko edo eskualdeko jatorria eta eskualdeko edo eskualdez gaindiko merkataritza eta tokiko kontsumo-ereduak ebaluatu dira. Horretarako, batetik, metodo analitikoa optimizatu da, eta laborategiko zahartze esperimentu bat aurkeztu da, ur-inguruneetan jalkitako zeramikek jasan ditzaketen hainbat eraldaketa- eta kutsadura-prozesu azaltzen dituena. Prozesu horiek kontuan hartu behar dira zeramikarekin zerikusia duten alderdien interpretazio okerrak saihesteko. Gainera, teknika analitiko ez-suntsitzaile baten erabilera ere azaldu da (LA-MC-ICP-MS). Teknika honen errendimendua ikerketa honetan aztertutako kasu azterketa batean ebaluatu da. Bestalde, Aveiro eta Zamorako 124 zeramiketan hurbilketa arkeo metriko bat burutu da: pasten analisi kimikoak eta mineralogikoak ICP-MS eta XRD bidez egin dira eta mikroegituraren, beiraduren eta pigmentuen karakterizazioa SEM-EDS, Raman, LA-MC-ICP-MS,soluzio MC-ICP-MS eta LA-HR-ICP-MS bidez egin da.

The SuperCam instrument, onboard the Perseverance rover (Mars 2020 mission) is designed to perform remote analysis on the Martian surface employing several spectroscopic techniques such as Laser Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman (TRR), Time-Resolved Fluorescence (TRF) and Visible and Infrared (VISIR) reflectance. In addition, SuperCam also acquires high-resolution images using a color remote micro-imager (RMI) as well as sounds with its microphone. SuperCam has three main subsystems, the Mast Unit (MU) where the laser for chemical analysis and collection optics are housed, the Body Unit (BU) where the different spectrometers are located inside the rover, and the SuperCam Calibration Target (SCCT) located on the rover's deck to facilitate calibration tests at similar ambient conditions as the analyzed samples. To perform adequate calibrations on Mars, the 22 mineral samples included in the complex SCCT assembly must have a very homogeneous distribution of major and minor elements. The analysis and verification of such homogeneity for the 5-6 replicates of the samples included in the SCCT has been the aim of this work. To verify the physic-chemical homogeneity of the calibration targets, micro Energy Dispersive X-ray Fluorescence (EDXRF) imaging was first used on the whole surface of the targets, then the relative abundances of the detected elements were computed on 20 randomly distributed areas of 100*100 mum. For those targets showing a positive Raman response, micro-Raman spectroscopy imaging was performed on the whole surface of the targets at a resolution of 100*100 mum. The %RSD values (percent of relative standard deviation of mean values) for the major elements measured with EDXRF were compared with similar values obtained by two independent LIBS set-ups at spot sizes of 300 mum in diameter. The statistical analysis showed which elements were homogeneously distributed in the 22 mineral targets of the SCCT, providing their uncertainty v

[EN] Nowadays, miniaturization and portability are crucial characteristics that need to be considered for the development of water monitoring systems. In particular, the use of handheld technology, including microfluidics, is exponentially expanding due to its versatility, reduction of reagents and minimization of waste, fast analysis times and portability. Here, a hybrid handheld miniaturized polymer platform with a paper-based microfluidic device was developed for the simultaneous detection of nitrite and nitrate in real samples from both, fresh and seawaters. The platform contains an ionogel-based colorimetric sensor for nitrite detection and a paper-based microfluidic device for the in situ conversion of nitrate to nitrite. The platform was fully characterized in terms of its viability as a portable, cheap and quick pollutant detector at the point of need. The calibration was carried out by multivariate analysis of the color of the sensing areas obtained from a taken picture of the device. The limits of detection and quantification, for nitrite were 0.47 and 0.68mgL-1, while for nitrate were 2.3 and 3.4mgL-1, found to be within the limits allowed by the environmental authorities, for these two pollutants. Finally, the platform was validated with real water samples, demonstrating its potential to monitor nitrite and nitrate concentrations on-site as a first surveillance step before performing extensive analysis.

[EN] The study of space has always been a field of great interest and thus space missions are becoming more and more ambitious with time. Therefore, with the 50th anniversary of the first spacecraft to land on Mars, a review about how traditional analytical techniques have been adapted to the era of in situ space exploration is presented. From the Viking Project to the future MMX mission, the techniques used for the in situ study of the geochemistry of the Martian surface is described. These techniques have been differentiated according to the type of analysis: elemental and molecular. On the one hand, among the elemental analytical techniques the XRF, APXS, ISE and LIBS stand out. On the other hand, GCMS, TEGA, MBS, XRD, Raman and IR spectroscopy have been the molecular techniques used in the missions to Mars. Miniaturization, real-time measurements, automation, low power consumption and reliability of operation under extreme conditions are some of the major challenges that analytical chemistry has faced as a result of the technological and scientific requirements of space missions. In this way, this review gathers all the in situ analytical techniques that have reached the surface of Mars onboard landers or rovers with the aim of studying its geochemistry.

The toxicity and the health risk assessment associated to the presence of some hazardous elements (HEs) in dried (infant formula and powdered) milks due to manufacturing and packaging process, raw materials used, environmental conditions, etc. need to be determined. With this aim, a new methodology based on the combination of health risk quotients and non-supervised (as cluster analysis (CA) and principal component analysis (PCA)) chemometric techniques is proposed in this study. The methodology was exemplified using the concentration of 27 elements, some of them HEs, measured in 12 powdered milk samples produced for children and adults in Brazil and Colombia. The concentration values were obtained by inductively coupled plasma-mass spectrometry (ICP-MS) after acid microwave digestion. Elemental concentrations vary depending upon the type of milk (initiation, growing-up, follow-on milks and adult milks). However, hazard quotients (HQ) and carcinogenic risk (CR) values showed no risk associated to the presence of HEs on milks. The methodology designed made possible to conclude that adults' milks are more characteristic of elements naturally present in milk. Children milks present major presence of trace and minor elements. Between infant milks, sample H, designed for babies between 12 and 36 months, was identified as of poor quality. Moreover, it was possible to deduce that while the fortification process applied to children powdered milks is a probable metal and metalloid source, together with the manufacturing, the skimming process is not a contamination source for milks.

The Mars Sample Return (MSR) is a near future mission to return samples from the surface of Mars to the Earth. The field operations to carry out data collection, selection of the samples, and sampling procedure, mainly related to the CanMars MSR analog mission, are well-studied and published. In contrast, studies related to the methodology implemented to characterize the mineralogy of the returned samples are scarcer and focused on biosignature detection. This work presents a non-destructive analytical methodology based on Raman microscopy (single point and imaging), micro-energy dispersive X-ray fluorescence imaging analysis, and scanning electron microscopy coupled to energy dispersive spectroscopy that could be used as a first analytical characterization for the Martian samples that will be returned to the Earth in the upcoming MSR mission, before any destructive analysis. The analytical methodology has been tested on a fragment of the Northwest Africa 1950 Martian meteorite, which gives us a mineralogical characterization of the meteorite. This methodology also allowed to define several chemical reactions taking place in some of the mineral phases (olivines and ilmenite) of the meteorite. In addition to the geochemical characterization of the samples, the fact that this methodology allows to assess the chemical transformations in several minerals gives important clues for describing mineral processes and geological evolution that took place on Mars. This work also shows the advantages and disadvantages that each of the techniques employed has when performing a mineralogical characterization, the information that each one can provide and the importance of combining them.

[ES] El patrimonio cultural es un ámbito que requiere un buen cuidado de sus bienes. Tanto su conservación como restauración deben hacerse de la forma menos invasiva posible, a fin de no estropear las obras de arte. Pero esta tarea no siempre es fácil. En lo que implica la aparición de manchas de lixiviados de cobre en superficies de mármol, una de las alternativas más novedosas para su limpieza es el uso de geles semirrígidos de Agar. Estos geles, gracias a su adhesividad y poder de absorción, permiten la extracción de los metales sin provocar daños en la superficie. Por ello, es un campo de interés, en el cual se encuentran opciones similares como el Kudzu y el Konjac. Además, el añadir quelantes a estos geles, puede incrementar su capacidad de extracción. Este trabajo comprueba la efectividad en la limpieza de lixiviados de cobre con geles semirrígidos de Agar, Kudzu y Konjac, realizándose dos aplicaciones de 8-h cada una. Los aditivos que presentaron mejores extracciones fueron el citrato sódico, EDTA y ácido glucónico. Se utilizaron técnicas como colorimetría, XRF y espectroscopía Raman para la caracterización de las probetas de mármol, así como ICP-MS para analizar el contenido de los diferentes geles., [ENG] Cultural heritage is an area that requires good care of its assets. Both its conservation and restoration must be done in the least invasive possible way, so as not to damage the artworks. But this task is not always easy. In what involves the appearance of copper leachate stains on marble surfaces, one of the newest alternatives for their cleaning is the use of semi-rigid Agar gels. These gels, due to their adhesiveness and absorption power, allow the extraction of metals without causing damage to the surface. This is therefore a field of interest, in which similar options such as Kudzu and Konjac are found. Moreover, the addition of chelating agents to these gels can increase their extraction capacity. This labwork tests the effectiveness in the cleaning of copper leachates with semi--rigid Agar, Kudzu and Konjac gels, with two applications of 8 h each. The chelating agents that showed the best extractions were sodium citrate, EDTA and gluconic acid. Techniques such as colorimetry, XRF and Raman spectroscopy were used to characterize the marble mock-ups, as well as ICP-MS to analyze the content of the different gels.

[EN] In this work, micro-Raman spectroscopy and micro-energy-dispersive X-ray fluorescence spectroscopy (µ-EDXRF) were applied on microsamples taken from the Plaiko Zubixe footbridge (1927) located in Ondarroa (Basque Country, Spain) in order to investigate the original paint coating and make an evaluation of the conservation state before its restoration. Elemental and molecular images were acquired for the study of the compounds distribution. Some modern pigments such as phthalocyanine blue and green pigments, minium, calcium carbonate, Prussian blue, and hematite were identified. Barium sulfate and titanium dioxide were recognized as opacifier agents. Thanks to the study of the stratigraphies, it has been possible to determine the original paint layer, which includes lead white, ultramarine blue, carbon black, and barium sulfate. In addition, colorimetric analyses made it possible to know the CIELab values of the original layer in order to reproduce the original colour during the planned restoration work. The massive presence of chlorine detected by µ-EDXRF and the corrosion products of the rust layer, in particular akaganeite and hematite, highlighted the atmospheric impact in the conservation of the bridge because they were due to the effect of both marine aerosol and to the presence of acidic components in the environment coming from anthropogenic activity. This work demonstrated the usefulness of a scientific approach for the study of industrial archaeology heritage with the aim to contribute to its conservation and restoration

The Historical and Cultural Heritage of Punta Begoña Galleries in Getxo (Bizkaia, North of Spain) are currently in restoration after being abandoned for years. For that reason, many graffiti, which directly affect the wall paintings, appear on most of their walls. Moreover, several graffiti overlap each other, which makes their removal more difficult. For all these reasons, the chemical characterization of these pigments is a priority to optimize the cleaning and consolidation treatments of wall paintings. That being the case, an analysis based on Raman spectroscopy and X-ray fluorescence was carried out to obtain information to help conservators remove the graffiti without damaging the mural paintings and the support. Nevertheless, the first step, using X-ray fluorescence and Raman spectroscopy, involved the need for a database to compare the results and identify the compounds. Thus, different commercial inks were elementally and molecularly characterized to complete the existing databases. After this, an analysis of the inks was carried out that noted the presence of several organic pigments, such as phthalocyanines. Inorganic pigments such as titanium oxide were identified as well. After the analysis, the selection of the best removal process could be carried out to provide the most effective treatment, avoiding the “trial-and-error” classical practice.

In this work, decorative wallpapers (19th century) from an historical palace located in Oiartzun (Basque Country, Spain) were analyzed before their restoration. Micro-energy dispersive X-ray fluorescence spectroscopy, Raman spectroscopy, and attenuated total reflectance infrared spectroscopy were used to investigate the elemental and molecular composition of pigments, the presence of binders, and the state of conservation of the paper support. The aim of the investigation was trying to understand the possible degradation pathways and identify the raw materials in order to choose the best restoration protocol according to the original aspect of wallpapers. As stated from both the elemental distribution and the identification of mineral phases by Raman spectroscopy, the most used pigment was lead chromate. It was mixed with other pigments such as ultramarine blue, zinc chromate, hematite, and atacamite among others to obtain different shades and they were applied mixed with an animal glue. Brass, identified thanks to elemental micro-EDXRF maps, was employed as a shiny decorative element. In addition, a partial degradation of cellulose was detected due to its natural ageing, the acidic nature of lignin, and to a phenomenon of humidity of the walls. Probably the deposition of black particulate matter was the cause of the darkening of the painting surfaces.

Ancient ceramics recovered after a long burial period have probably undergone several alterations and contaminations, introducing a chemical variability, affecting the ceramic’s natural variability. That is, the chemical and the mineralogical compositions of the ceramic pastes after their deposition will not be the same as they originally were. Therefore, it is known that the alteration and contamination processes, and the discrimination of some elements, should be considered when studying the ceramics to avoid incorrect interpretations about their provenance, technology and the use of the artefact, as well as its proper preservation. In the present work, the authors performed an experimental approach in order to study the alterations and contaminations that occurred in 60 ceramic cylinders buried in two different underwater environments. Once the pieces were taken out from the water environments, they were characterized by a multi-analytical approach. For this purpose, inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), scanning electron microscopy–energy dispersive spectrometry (SEM–EDS) and Raman spectroscopy were used. Newly formed minerals of different forms have been identified, with different crystallization grades. Some examples are the needles, flakes, sponges and long and short prisms composed of several elements such as Ca, F, S and O.

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2-7 m, while providing data at sub-mm to mm scales. We report on SuperCam's science objectives in the context of the Mars 2020 mission goals and ways the different techniques can address these questions. The instrument is made up of three separate subsystems: the Mast Unit is designed and built in France; the Body Unit is provided by the United States; the calibration target holder is contributed by Spain, and the targets themselves by the entire science team. This publication focuses on the design, development, and tests of the Mast Unit; companion papers describe the other units. The goal of this work is to provide an understanding of the technical choices made, the constraints that were imposed, and ultimately the validated performance of the flight model as it leaves Earth, and it will serve as the foundation for Mars operations and future processing of the data.

The conservation of iron objects exposed to marine aerosol is threatened by the formation of akaganeite, a highly unstable Cl-bearing corrosion phase. As akaganeite formation is responsible of the exfoliation of the rust layer, chlorides trigger a cyclic alteration phenomenon that often ends with the total consumption of the iron core. To prevent this degradation process, movable iron elements (e.g. archaeometallurgical artefacts) are generally immersed in alkaline dechlorination baths. Aiming to transfer this successful method to the treatment of immovable iron objects, we propose the in-situ application of alkaline solutions through the use of highly absorbent wraps. As first step of this novel research line, the present work defines the best desalination solution to be used and optimizes its extraction yield. After literature review, a screening experimental design was performed to understand the single and synergic effects of common additives used for NaOH baths. Once the most effective variables were selected, an optimization design was carried out to determine the optimal conditions to be set during treatment. According to the experimental work here presented, the use of 0.7 M NaOH solutions applied at high temperatures (above 50 °C) is recommended. Indeed, these conditions enhance chloride extraction and iron leaching inhibition, while promoting corrosion stabilization.

The SuperCam instrument suite provides theMars 2020 rover, Perseverance, with a number of versatile remote-sensing techniques that can be used at long distance as well as within the robotic-arm workspace. These include laser-induced breakdown spectroscopy (LIBS), remote time-resolved Raman and luminescence spectroscopies, and visible and infrared (VISIR; separately referred to as VIS and IR) reflectance spectroscopy. A remote micro-imager (RMI) provides high-resolution color context imaging, and a microphone can be used as a stand-alone tool for environmental studies or to determine physical properties of rocks and soils from shock waves of laser-produced plasmas. SuperCam is built in three parts: The mast unit (MU), consisting of the laser, telescope, RMI, IR spectrometer, and associated electronics, is described in a companion paper. The on-board calibration targets are described in another companion paper. Here we describe SuperCam's body unit (BU) and testing of the integrated instrument. The BU, mounted inside the rover body, receives light from the MU via a 5.8 m optical fiber. The light is split into three wavelength bands by a demultiplexer, and is routed via fiber bundles to three optical spectrometers, two of which (UV and violet; 245-340 and 385-465 nm) are crossed Czerny-Turner reflection spectrometers, nearly identical to their counterparts on ChemCam. The third is a high-efficiency transmission spectrometer containing an optical intensifier capable of gating exposures to 100 ns or longer, with variable delay times relative to the laser pulse. This spectrometer covers 535-853 nm (105-7070 cm-1 Raman shift relative to the 532 nm green laser beam) with 12 cm-1 full-width at half-maximum peak resolution in the Raman fingerprint region. The BU electronics boards interface with the rover and control the instrument, returning data to the rover. Thermal systems maintain a warm temperature during cruise to Mars to avoid contamination on the optics, and cool the

Although Raman spectroscopy is a common technique for the analysis of cement-based materials in the research studies or in the field of Cultural Heritage to carried out multianalytical studies, it is not generally used as unique technique of a research or to carry out analysis during ordinary restoration works of modern urban buildings affected by environmental stressors. The disadvantages associated with Raman spectroscopy as fluorescence limits its implementation beyond research studies, more in the case of in situ equipment. However, the technological development allows high-quality results with in situ equipment, so its use could be useful during restoration works. Thus, this work demonstrates how the implementation of the correct methodology could lead to useful and fast results during restoration works. The proposed methodology is based on the use of in situ analysis (screening) on the scaffolding, followed by the sampling of layers based on the previous screening and a posterior exhaustive laboratory analysis. The research has been conducted during the restoration works of a reinforced concrete building in which the attack of atmospheric acid gases (CO2, SO2, and NOx) was identified as the main affection suffered, and the fixed sulfates were the most important intermediary compounds of decaying processes. Many of the pollutants and decaying compounds were even identified during the in situ analysis, improving the anticipation and responsiveness. Therefore, this methodology allows the understanding of the chemistry of the materials to evaluate its health state in a fast and reliable way.

This paper deals with the findings of Hospital Viejo site of Logroño (La Rioja, Spain), which yielded the largest evidence of local pottery production, comprising three kilns and a potters’ dump (13th–15th centuries). The study of pottery production in inland Iberia provides valuable information on the material conditions in which the Iberian medieval and post-medieval society occurred. Yet, the territory of La Rioja has been largely eclipsed by studies at coastal and southern areas of Iberia, due to their role in maritime exchange.With the aim of understanding the specific incidence and evolution of medieval pottery at regional scale, 77 sherds (MNI 637) including glazed and unglazed ware and kiln utensils were archaeometrically examined by combining the use of ICP-MS, XRD and SEM-EDS. Likewise, NAA was applied for provenance analysis, including the collation with a large majolica NAA database. The results provided the first chemical fingerprint of the production from Logroño consisting on three compositional groups within the same workshop (LOG-A, LOG-B and LOG-C). Moreover, pottery trading from Teruel and Valencia was detected, sustaining the historical records of these trade-networks. The imports showed tin lead glazes obtained by known recipes, contrasting with simpler manufactures (mostly unglazed or only lead glazed) of contemporary Logroño.

The present study aims to present new archaeometric data from a wide typological rank of ceramics collected in Ksar Seghir (Morocco) and Ceuta (Spain), two different archaeological sites in the south bank of the Strait of Gibraltar occupied by the Portuguese from the 15th to the middle of the 16th centuries. We characterise and illustrate the most common ceramic fabrics and shapes found in these settlements, only possible by the intensive excavation of these two sites. Its mineralogical and chemical analyses confirm the idea that Seville and Lisbon were the most significant production centres in the Iberian Peninsula to supply the two Portuguese North African strongholds. These results reinforce the idea that Seville and Lisbon, besides being two great pottery workshops, played a complementary role as key cities in the logistics of the Iberian overseas expansion since its early beginning. The combination of the typological and archaeometrical studies will allow to better identify the centres of production of these ceramics, which were widely disseminated in the Mediterranean Sea and the Atlantic Ocean during this period.

211 p., NASA and ESA will carry out their own planetary missions (Mars 2020 and ExoMars 2022 respectively) whose main objective is the demonstration of the potential habitability of the neighbouring planet. In this sense, all the findings that evidence the possibility of any life signature in the Martian history could be very interesting to fulfil this objective. With this purpose, the present PhD thesis is based in the geochemical characterization of different emplacements from the Basque-Cantabrian Basin, which are proposed as Martian analogues. All the studied locations are antique submarine volcano scenarios which have been subjected to different weathering processes since their eruption till nowadays. This characterization was done with spectroscopic techniques, among others Raman and visible near infrared spectroscopies, since they are on-board the mentioned missions. Therefore the use of these techniques in analogue emplacements could serve as a background for the Martian exploration. An example of one of the most common compounds found in these emplacements, are phyllosilicates. They play a very important role for the existence of life due to the necessity of water for their formation as well as sulfates and carbonates. Some of the found minerals in these emplacements have been already found on Mars but others, are not reported to be present in its surface yet and therefore their spectroscopic characterization will help in the interpretation of the upcoming results from the future missions. Moreover, some signals of organic molecules could also be identified in the analogue samples. Thanks to that, and due to the difficulty of the detection and interpretation of organic molecules, we have a spectroscopic background, and as in the case of the unknown minerals the understanding of the future data, would be easier.

Evidence of geomorphology traces of past liquid water on the surface of Mars suggests that this planet once had habitable conditions and leads to question about life. To investigate that, ESA and NASA space explorations organizations will send two rovers. For this reason, the necessity for the proper understanding and interpretation of the results obtained implies the study of terrestrial Martian analogues. In this work, Armintza, the Cretaceous alkaline submarine volcano outcrop has been studied and proposed as a Martian analogue. The samples were geochemically characterizes by Raman and Vis-NIR spectroscopies, considering that they are the two techniques that will go on-board the rovers of the next planetary missions. As was expected, silicates (phyllosilicates) were the major minerals but also compounds such as carbonates, sulphates and oxides could be detected. Phyllosilicates have special importance because they are indicators of aqueous weathering processes of primary magmatic rocks and they need liquid water for their formation. In addition, these compounds have been reported to be present in the Mars surface, specifically in Oxia Planum, the landing site for the Exomars2020 rover of the ESA mission as well as in Jezero crater, the landing site for the Mars 2020 rover of the NASA mission.; Marteko iraganeko lurzoruan agerian utzitako ur-likidoaren aztarna geomorfologikoak noizbait izandako bizigarritasun-baldintzetara aditzera ematen du eta honek, bizitzari buruzko galderak egitera. Horretarako 2020. urtean ESA-k eta NASA-k Martera ibilgailu robotiko bana bidaliko dute. Beraz, lortutako emaitzak ulertzeko eta interpretatzeko lurreko analogoen ikerketak egitea garrantzitsua da. Ikerketa lan honetan, Armintza, Kretazeo garaian gertatutako izaera alkalinodun itsaspeko sumendiaren ondoriozko azaleratzea Marteko analogo gisa proposatu da. Laginen ikerketa geokimikoa egiteko hurrengo Marteko misioetan erabiliko diren Raman eta Vis-NIR espektroskopia teknikak erabil

A set of 34 archaeological ceramics, including olive jars, transparent green lead glazed, tin-lead glazed and unglazed ceramics, from seventeenth century Angra D shipwreck found at Terceira Island (Azores Archipelago, Portugal) was archaeometrically characterized by inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Ceramic provenance has been established by statistical exploration of the ICP-MS chemical data, suggesting as being mainly from Seville origin (southern Spain) and, at a lesser extent, from the north of Portugal, piling up evidences to suggest a Spanish ship. Alteration and contamination effects of underwater environment in calcareous ceramics are assessed by XRD and SEM-EDS analyses, like the crystallization of zeolites, as well as pyrite.

Supplementary data to this article can be found online at https://doi.org/10.1016/j.jasrep.2020.102648., Aveiro, a city located in northern Portugal that lies next to the Atlantic Ocean, has a long potting tradition. Indeed, during the 15th–17th centuries, this region played an important role in the maritime trade between the north of Europe, the Iberian Peninsula and the Atlantic. Historical records reflect regular trade contacts between ship-owners and masters of Aveiro with English, Irish, Flemish, Galician and Basque entrepreneurs, in Europe and overseas. The archaeological research carried out on the Ria de Aveiro A (RAVA) shipwreck collection (16th – beginning 17th centuries), revealed a large amount of ceramics as cargo, tentatively produced in Aveiro Region. That was compared to a collection from Santo Ant´onio church, in Aveiro, which includes ceramics used to fill the upper choir dome, with an exact chronology (1524), also manufactured in Aveiro. Such set of pottery enabled the establishment of a typology divided in three groups, used in everyday life at that time in Aveiro (tableware, longdistance storage and transportation and sugar moulds) and combining red and black pastes and shiny and matteblack finished surfaces. With a view to characterize and to assess the provenance of local or regional origin of this Post-Medieval pottery assemblage from the two sites, an archaeometric approach of 25 unglazed ceramics showing red and black pastes has been performed. In this way, chemical and mineralogical analyses have been carried out by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and X-Ray Diffraction (XRD), and microstructural analysis by Scanning Electron Microscopy-Energy Dispersive Spectrometry (SEM-EDS) analytical techniques. The results show that ceramics from RAVA have a compatible chemical fingerprint with those from the church, forming the A-1 local production reference group. Moreover, the A-1 reference group has been further assessed by comparing against the main reference groups from the Iberian Peninsula.

361 p., El eje central de la presente Tesis Doctoral es el análisis composicional de cerámicas arqueológicas, el cual es ampliamente utilizado en Arqueología para obtener profundizar en el conocimiento de las sociedades humanas pasadas. Así, se presenta un aporte metodológico transdisciplinar en forma de método abierto basado en software R, que incorpora al análisis arqueométrico tecnologías de la información para desarrollo de investigación reproducible. Además, se ha desarrollado una metodología de screening químico no destructiva mediante ED-XRF para la clasificación de cerámicas arqueológicas de época medieval y post-medieval. Para llevar a cabo estos aportes metodológicos se han evaluado cinco casos de estudio correspondientes a centros productores cerámicos de La Rioja (Logroño y Nájera) y del País Vasco (Orduña, Durango y Elosu), cuyos resultados representan el primer estudio arqueométrico abordado desde una perspectiva de producción que se ha llevado a cabo sobre esta región y cronologías. En este estudio se han evaluado 347 fragmentos cerámicos, permitiendo establecer 21 grupos composicionales, de los cuales 13 se han podido asociar a una producción local, mientras que 6 se han atribuido a diferentes proveniencias exógenas peninsulares. Asimismo, se han determinado los aspectos tecnológicos que caracterizan las producciones estudiadas, tales como el tipo de vidriado, pigmentos utilizados y las temperaturas de cocción, permitiendo identificar diversas fábricas en cada producción, Doktorego-tesi honen ardatz nagusia zeramika arkeologikoen konposizio-analisia da, Arkeologian asko erabiltzen den baliabidea, iraganeko gizarteei buruzko ezagutzan sakontzeko. Horrela, R softwarean oinarritutako metodo ireki baten bidez diziplinarteko ekarpen metodologiko bat aurkezten da, informazioaren teknologiak analisi arkeometrikoan txertatzen dituena. Gainera, bahetze-metodologia ez-suntsitzaile bat garatu da, Erdi Aroko eta ondorengoko zeramika arkeologikoak sailkatzeko. Ekarpen metodologiko horiek gauzatzeko, Errioxako (Logroño eta Najera) eta Euskal Herriko (Urduña, Durango eta Elosu) ekoizle-zentroei dagozkien bost azterketa-kasu ebaluatu dira. Lan horren ondorioz, ekoizpen-ikuspegi batetik landutako lehen azterlan-arkeometrikoa aurkezten da, eskualde eta kronologia horiei dagokienez. Ikerketa honetan 347 zeramika-zati ebaluatu dira, eta 21 konposizio-talde ezarri dira; horietako 13 tokiko ekoizpenarekin lotu direnak, eta 6, berriz, penintsulako beste jatorriekin. Era berean, aztertutako ekoizpenen ezaugarri teknologikoak zehaztu dira, hala nola, beira-mota, erabilitako pigmentuak eta erreketa-tenperatura; horrela, ekoizpen bakoitzean hainbat fabrika desberdinak identifikatuz.

Compositional analysis of ceramics plays a crucial role in Archaeology because following the proper methodology, it enables to obtain knowledge about past human behavior. In this regard, X-Ray Fluorescence Spectrometry (XRF) involves promising possibilities on the non-destructive analysis of pottery. Nonetheless, in comparison to traditionally employed techniques such as ICP-MS or NAA, there are several limitations to overcome (e.g. limits of detection, precision, accuracy, etc.). The goal of this work was to develop a non-destructive multi-point strategy based on ED-XRF and, subsequently, assess to what extent a destructively obtained classification by ICP-MS can be reproduced by the one obtained non-destructively. The experiment was applied to a set of 47 representative Medieval and post-Medieval ceramics from the Iberian Peninsula corresponding to 4 archaeological sites. The results from both methods were explored statistically (HCA and PCA) and showed that the classification obtained non-destructively achieved a high-level of correspondence with the one obtained by ICP-MS. Thus, the screening potential of the methodology was demonstrated. Likewise, factors involved in the geochemical characterization such as instrumental parameters, concentration ranges of these ceramics typologies, their heterogeneity and the role of the ubiquitous lead glazes were addressed.

additional files, The city of Nájera, located in the north of the Iberian Peninsula, hosts an alcazar of Arab origin, which became the residence of the king of Pamplona-Nájera and later of the duke and duchess of Nájera. From this last period (1500–1600) date the ceramics that were unearthed during the recent excavations of the Alcázar of Nájera. These findings constitute the largest post-Medieval assemblage of ceramic pieces unearthed in the city. They include a large set of plain tin–lead glazed pieces of tableware, as well as some mono or polychrome decorated sherds. In this work, an archaeometric characterization was carried out on a subsample of these ceramics (n = 94) by means of a multi-analytical strategy. The pastes were analyzed chemically and mineralogically by ICP-MS and XRD, respectively. Further evaluations on a subsample of ceramic glazes was carried out by SEM–EDS and Raman microscopy. The preliminary results enabled establishing a main large compositional group (NAJ-A) and a smaller one (NAJ-B) which could tentatively be linked to a local production origin. Moreover, exogenous provenances such as Muel and Talavera were identified after the comparison with data from other Spanish contemporary majolica pottery productions.

Mercury (Hg) in agricultural soils could have negative effects on the environment and the human health. The exposure to high level of Hg through different absorption pathways, such as ingestion and diet through soil-plant system could permanently damage developing foetus of animals and humans. With the aim to assess the potential environmental and health risk and to study the behaviour and fate of Hg from agricultural soils to the environment, 47 soil samples were collected around a thermoelectric power plant in the Santa Catarina (Brazil). The Hg concentration measured by inductively coupled plasma mass spectrometry (ICP-MS) ranged from 0.16 to 0.56 mg kg−1. The distribution obtained by kriging interpolation allowed the identification of the main pollution sources. To see the morphology and composition of soil samples, field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM) were used combined with energy dispersive X-ray spectroscopy (EDS), showing that the carbon nanotubes and magnetite as nanomineral contributed to Hg retention. The mentioned molecular characterization, and the low Contamination Factors (CF) values obtained, suggested that there is low risk to the food security of the agro-ecosystems area near to the CFPP in the terms of Hg inputs and contamination.

Collection of the raw Raman and NIR spectral data

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.

Marine aerosol is a complex inorganic and organic chemistry system which contains several salts, mainly forming different type of salt clusters. Different meteorological parameters have a key role in the formation of these aggregates. The relative humidity (%RH), temperature, CO, SO2 and NOx levels and even the O3 levels can promote different chemical reactions giving rise to salt clusters with different morphology and sizes. Sulfates, nitrates and chlorides and even mixed chlorosulfates or nitrosulfates are the final compounds which can be found in environments with a direct influence of marine aerosol. In order to collect and analyze these types of compounds, the use of adequate samplers is crucial. In this work, salt clusters were collected thanks to the use of a self-made passive sampler (SMPS) installed in a 20th century historic building (Punta Begoña Galleries, Getxo, Basque Country, Spain) which is surrounded by a beach and a sportive port. These salt clusters were finally analyzed directly by micro-Raman spectroscopy and Scanning Electron microscopy coupled to Energy Dispersive X-ray spectrometry (SEM-EDS).

Part of special issue: Proceedings of the 30th anniversary Eurosensors Conference – Eurosensors 2016, 4-7. Sepember 2016, Budapest, Hungary, The increment of uncontrolled nutrients concentration in water is the subject of increasing environmental concern. In particular, the increment of nitrate causes the eutrophication of algae, leading to fauna and flora demise. In order to favour an easy and adequate monitoring of this environmental problem, we have developed an ionogel-based sensor for the colorimetric determination and image analysis detection of nitrite and nitrate in water. The sensor consists on a small poly(methyl)methacrilate (PMMA) device cut by a CO2 laser where both the detection and the calibration zones are integrated. A simple photograph of the whole device, followed by colour processing of the different sections of the chip was used for the determination of nitrite concentrations.

Punta Begoña Galleries were built in 1918 in Getxo (Basque Country, North of Spain) but were abandoned in 1960. Nowadays, their conservation state is very poor. In this work, portable Raman spectroscopy was applied to evaluate the original composition and possible deterioration products of the mortars used in the inner walls and those covering the concrete of the ceilings allowing us to select the most appropriate sampling points. In the laboratory, Raman microscopy and Raman imaging, assisted with scanning electron microscopy equipped with an energy dispersive spectrometer (SEM‐EDS), X‐ray diffraction and energy dispersive X‐ray fluorescence (ED‐XRF) imaging, allowed to identify the key compounds to understand the deterioration processes taking place in the mortars of the galleries. The main components of the mortars from the walls were calcite and gypsum. In some cases, alite (Ca3SiO5) and belite (Ca2SiO4) were identified; these components are characteristic of Portland cement clinker. The main components of the mortar covering the concrete were calcite, quartz, aragonite and gypsum. The aragonite identification confirmed the use of beach sand as the aggregate in the mortar. The concrete from the ceiling of the lower gallery is covered with three different mortar layers; the outermost layer is covered with a black crust. In the three mortars, the main components are similar to those used in the mortar covering the concrete from the upper gallery. Thanks to Raman, ED‐XRF and SEM‐EDS imaging, it was possible to map the distribution of the main components through the three mortar layers and also to identify the presence of dolomite {[CaMg(CO3)2]}, which was not possible to detect following single‐point micro‐Raman analyses.

226 p., Se desarrollan metodologías analíticas no destructivas para el diagnostico in situ del Patrimonio Construido afectado por factores ambientales. A lo largo del trabajo, la caracterización y severidad de daño sufrido por los materiales es evaluada en casos reales, prestando especial atención a establecer el origen y el proceso químico involucrado en las patologías, contribuyendo a la preservación. Además, para comprobar la efectividad de un innovativo método de conservación, se realiza su monitoreo a través de un enfoque multianalítico, evaluando su capacidad para reducir el deterioro así como, para determinar los requerimientos para su implementación.Las metas propuestas han sido logradas gracias al desarrollo de diferentes metodologías, destacando la utilidad de la espectroscopia Raman. Los hándicaps resultantes del análisis de campo han sido reducidos gracias a la implementación de DRIFT. Paralelamente, técnicas como SEM y XRF han sido propuestas para detectar la capacidad de penetración de los agentes de deterioro así como, IC para cuantificar la severidad del daño salino, de acuerdo a la legislación existente. A sí mismo, los datos cuantitativos son sometidos a estudios quimiométricos y termodinámicos con objeto de corroborar el análisis espectroscopico. Finalmente, dadas las diferencias observadas en los análisis por cambios estacionales, se llevo a cabo un estudio para describir el comportamiento del contenido salino bajo condiciones climáticas variables con objeto de seleccionar las acciones preventivas, evitando la necesidad de tomar decisiones solamente basadas en la experiencia del conservador.

193 p., Tesi lan honetan, ondare kulturalaren ikerketarako infragorri islapen espektroskopioaren erabilera aztertu da. Alda batetik, laborategian genuen infragorri espektrofotometroak ahalbidetzen zituen neurketa moduak (trasmitantzia, ATR eta DR), infragorri eremu desberdinetan aztertu ditugu. Lehenengo kasu praktikoan, T-FIR eta DR-MIR tekniken konbinazioa erabiliz, Santa Isabel paper margotu baten karakterizazioa egin genuen. Behin laborategiko analisiak menperatu genituenean, in situ infragorri analisiak egiteko eskuragarri genuen DRIFT ekipo baten erabilgarritasuna aztertu genuen. e

The road traffic has become one of the most serious environmental problems in many cities and the main source of pollution of urban soils. To diagnose properly the magnitude of such impacts on roadside soils, eight urban and metropolitan soils were selected as a function of traffic density, distance to the road and years of operation, for which the concentration of 60 elements (major, minor and trace elements) were measured by semi-quantitative ICP-MS after acid digestion, as a first step in assessing the traffic impact. With this information, a comprehensive study was carried out focusing on the quantitative analysis of the concentration of 46 elements from the 8 sampling areas, analyzing the vertical and horizontal distributions of the metals in the roadside soils. The chemometric analysis showed that only the traffic-related elements accumulate in topsoil and present a high decreasing profile with depth and the distance to the road; however, this clear behavior takes places only in old roads that have undergone the traffic impact for a long time, but not in new roads or roads with low traffic density. Finally, the geoaccumulation indexes are suggested to be used instead of the local guidelines to assess the pollution state of the roadside soils, especially for the emerging trace elements like Antimony.

Urban soils are potential reservoirs of toxic metals as a consequence of traffic emissions. Sources like brake linings, tyres, road pavement, exhaust fumes, guardrail, traffic signals and other galvanised steel structures are used in a large variety of external constructions in the modern urban areas. Their beneficial properties from a corrosion and oxidation perspective are well-known but less is known about their contribution to the environmental fate of corrosion-induced released zinc. In this work, the impact of guardrails and other traffic pollutants on urban soils has been studied by means of Raman spectroscopy (molecular speciation) and thermodynamic speciation to understand the mechanisms of metal release and uptake by the soils. Hydrozincite, Zn 5(CO 3) 2(OH) 6, was identified by means of Raman spectroscopy as the degradation compound of the galvanised zinc layer from guardrails which leads to the formation of soluble zinc, by acidic attack of the urban atmosphere, that drops and accumulate (zinc nitrate was identified) in soils. This fact shows the environmental risk of zinc release from the guardrails because zinc nitrate can be easily mobilised by water runoff, affecting the surrounding areas or groundwater. Other traffic pollutant that reaches guardrail and soil by atmospheric deposition, such as barium, was also identified in soil as well as in the guardrail in its carbonate form, BaCO 3. Because of its low solubility, barium will accumulate in urban soils.

The aim of this work was to demonstrate that an archaeological ceramic piece has remained buried underground in the same stratum for centuries without being removed. For this purpose, a chemometric model based on Principal Component Analysis, Soft Independent Modelling of Class Analogy and Linear Discriminant Analysis classification techniques was created with the concentration of some selected elements of both soil of the stratum and soil adhered to the ceramic piece. Some ceramic pieces from four different stratigraphic units, coming from a roman archaeological site in Alava (North of Spain), and its respective stratum soils were collected. The soil adhered to the ceramic pieces was removed and treated in the same way as the soil from its respective stratum. The digestion was carried out following the US Environmental Pollution Agency EPA 3051A method. A total of 54 elements were determined in the extracts by a rapid screening inductively coupled plasma mass spectrometry method. After rejecting the major elements and those which could have changed from the original composition of the soils (migration or retention from/to the buried objects), the following elements (25) were finally taken into account to construct the model: Li, V, Co, As, Y, Nb, Sn, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Au, Th and U. A total of 33 subsamples were treated from 10 soils belonging to 4 different stratigraphic units. The final model groups and discriminate them in four groups, according to the stratigraphic unit, having both the stratum and soils adhered to the pieces falling down in the same group.