Radiation-induced alteration of apatite on the surface of Mars: first in situ observations with SuperCam Raman onboard Perseverance.

Planetary exploration relies considerably on mineral characterization to advance our understanding of the solar system, the planets and their evolution. Thus, we must understand past and present processes that can alter materials exposed on the surface, affecting space mission data. Here, we analyze the first dataset monitoring the evolution of a known mineral target in situ on the Martian surface, brought there as a SuperCam calibration target onboard the Perseverance rover. We used Raman spectroscopy to monitor the crystalline state of a synthetic apatite sample over the first 950 Martian days (sols) of the Mars2020 mission. We note significant variations in the Raman spectra acquired on this target, specifically a decrease in the relative contribution of the Raman signal to the total signal. These observations are consistent with the results of a UV-irradiation test performed in the laboratory under conditions mimicking ambient Martian conditions. We conclude that the observed evolution reflects an alteration of the material, specifically the creation of electronic defects, due to its exposure to the Martian environment and, in particular, UV irradiation. This ongoing process of alteration of the Martian surface needs to be taken into account for mineralogical space mission data analysis.

Geographical distribution of metals and metalloids along the estuary of the Oka River in the biosphere reserve of Urdaibai, Spain.

Sediments sampled at the estuary of the Oka River in the biosphere reserve of Urdaibai, Spain were analyzed for trace elements. Sediments were collected at 45 points of the estuary and the concentration of 14 elements was measured. The geoaccumulation indexes (Igeo), Normalized Average Weighted Concentrations (NAWC) and mean Effect Range-Median quotients (mERMq) were calculated. The results obtained were complementary and allowed intra- and inter-estuary comparison. According to the present findings, the estuary was classified as healthy, since the anthropogenic contribution of metals and metalloids was generally small. However, shipping and fishing activities at the ports of Bermeo and Mundaka and urban and industrial wastes from Gernika were regarded as the major pollution sources. Nevertheless, only slightly contaminated and toxic sediments, especially related to Ni and Cu, were found in the towns of Gernika and Mundaka.

Multi-analytical characterization of an oncoid from a high altitude hypersaline lake using techniques employed in the Mars2020 and Rosalind Franklin missions on Mars.

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

A new methodology for kerogen maturity estimation based on Raman spectroscopy and chemometric analysis.

Diverse criteria or parameters have been cited as tools to determine the maturity of carbonaceous matter (CM) found in geologic samples using Raman spectroscopy. However, these approaches involve the mathematical decomposition of Raman bands which can vary with the specific method, the software employed, or even the individual user. Data should be treated spectrum by spectrum and a similar spectroscopic pre-treatment should be applied to the whole dataset. All these factors affect the final result and can introduce a wide uncertainty and bias. We propose an alternative chemometric method that avoids these sources of uncertainty by considering the entire spectrum, not just certain regions, while allowing specific regions of interest to be defined. Moreover, spectra pre-treatment is not required. We employ principal component analysis (PCA) across the whole range of spectra. While the method does not provide an absolute maturity value, it allows comparison of different CM in terms of maturity or H:C ratio. In the analysis of coal standards, samples were grouped by maturity.

Homogeneity assessment of the SuperCam calibration targets onboard rover perseverance.

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 µm. 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 µm. 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 µm in diameter. The statistical analysis showed which elements were homogeneously distributed in the 22 mineral targets of the SCCT, providing their uncertainty values for further calibration. Moreover, nine of the 22 targets showed a good Raman response and their mineral distributions were also studied. Those targets can be also used for calibration purposes of the Raman part of SuperCam using the wavenumbers of their main Raman bands proposed in this work.

Characterization of sedimentary and volcanic rocks in Armintza outcrop (Biscay, Spain) and its implication for Oxia Planum (Mars) exploration.

The landing site of the next planetary mission lead by ESA (ExoMars 2022) will be Oxia Planum. This location has been chosen due to different reasons, among them, the existence of sedimentary rocks that could host remains of organic matter. The fact that this type of rocks coexists with volcanic ones makes of high importance the study of the processes and the possible interactions that could happen among them. Therefore, in this research work the Armintza outcrop (Biscay, North of Spain) is proposed as an Oxia Planum analogue since it has the dichotomy of volcanic and sedimentary rock layers that is expected on the landing site of the ExoMars 2022 mission. As Raman and visible near infrared spectroscopies will be in the payload of the rover of that mission, they have been used to characterize the samples collected in the Armintza outcrop. With the help of these techniques, feldspars (albite mainly) and phyllosilicates (kaolinite and dickite, together with micas and chlorite minerals) have been identified as the major products on the samples, together with some weathering products (carbonates, sulphates, oxides) and apatite. Moreover, remains of kerogen have been detected in the sedimentary layers in contact with the interlayered lava flows, confirming the capability of similar sedimentary-volcanic layers to trap and store organic remains for millions of years. After establishing which compounds have volcanic or sedimentary origin, and which must be considered alteration phases, we can consider Armintza as a good Oxia Planum analogue.

Development of innovative non-destructive analytical strategies for Mars Sample Return tested on Dar al Gani 735 Martian Meteorite.

This work proposes an innovative non-destructive analytical strategy, based on Confocal Raman micro-spectroscopy, High Resolution Raman Imaging and micro-X-Ray Fluorescence imaging, as part of the quick non-destructive techniques that could be used to characterize the Martian samples from the Mars Sample Return mission when back on Earth. Until that moment, Martian Meteorites are the only Martian samples in our hands to develop such Analytical Strategies. To demonstrate its capabilities, this analytical strategy has been applied to characterize the Dar al Gani 735 Martian Meteorite with the aim to identify the terrestrial and non-terrestrial alterations suffered by the meteorite as a very valuable complementary methodology to the more traditional petrographic analyses and single point measurements. The combination of these techniques allows extracting at the same time elemental, molecular and structural information of the studied area of the sample. The most relevant results on the analyzed DaG 735 shergottite thick samples revealed the presence of several altered mineral phases originated from the temperature and pressure conditions during the shock on Mars (anhydride, calcite and ilmenite), as well as from terrestrial weathering processes that degraded the meteorite from its landing on Earth (calcite and hematite in fractures together with gypsum, mirabilite and thenardite). As most of the conclusive results come from Raman spectroscopy, this study shows the potential of Raman spectroscopy as a key technique in the upcoming new explorations of Mars materials by the Rosalind Franklin rover (Exomars2022 mission from ESA) and the Perseverance rover (Mars2020 mission from NASA), where Raman spectrometers are mounted for the first time in an extra-terrestrial research in the field.

SuperCam Calibration Targets: Design and Development.

SuperCam is a highly integrated remote-sensing instrumental suite for NASA's Mars 2020 mission. It consists of a co-aligned combination of Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), Visible and Infrared Spectroscopy (VISIR), together with sound recording (MIC) and high-magnification imaging techniques (RMI). They provide information on the mineralogy, geochemistry and mineral context around the Perseverance Rover. The calibration of this complex suite is a major challenge. Not only does each technique require its own standards or references, their combination also introduces new requirements to obtain optimal scientific output. Elemental composition, molecular vibrational features, fluorescence, morphology and texture provide a full picture of the sample with spectral information that needs to be co-aligned, correlated, and individually calibrated. The resulting hardware includes different kinds of targets, each one covering different needs of the instrument. Standards for imaging calibration, geological samples for mineral identification and chemometric calculations or spectral references to calibrate and evaluate the health of the instrument, are all included in the SuperCam Calibration Target (SCCT). The system also includes a specifically designed assembly in which the samples are mounted. This hardware allows the targets to survive the harsh environmental conditions of the launch, cruise, landing and operation on Mars during the whole mission. Here we summarize the design, development, integration, verification and functional testing of the SCCT. This work includes some key results obtained to verify the scientific outcome of the SuperCam system.

A first evaluation of the usefulness of Kudzu starch in cultural heritage restoration.

In recent times, the use of natural and harmless products for the environment and restorer is taking place in the field of Cultural Heritage restoration. In this sense, wheat, rice and corn starches as adhesives, have suitable characteristics without toxicity risks. A new starch in this field, is the Kudzu, an almost pure compound (99.5% starch) that is processed by a natural way from a plant called Pueraria lobata. This is a preliminary study of the potential use of Kudzu starch for the restoration of Cultural Heritage, focusing, firstly, in its capacity as adhesive through a comparative evaluation with common starches. The accelerated aging process carried out proved that Kudzu ensures optimal chromatic behaviour. On the other hand, the main problem in starch paste is the biological colonization. The daidzein, a natural antimicrobial compound implicit in Kudzu starch, confirmed the resistance to microorganism in this preliminary approach. The evaluation of the adhesive capacity, and the reversibility of the starches, suggest that Kudzu starch is a valid adhesive in the field of paper restoration. Thus, the potential of this starch in the conservation of Cultural Heritage is evidenced and its use as cleaner, resistance to biological colonization and consolidant is promising.

A non-invasive spectroscopic study to evaluate both technological features and conservation state of two types of ancient Roman coloured bricks.

The study of both original and decaying compounds is relevant in understanding the chemistry behind the deterioration processes, above all in open museum contexts where environmental stressors affect the artefacts. In this sense, a combination of non-invasive spectroscopy techniques (Raman spectroscopy, µ-X-ray fluorescence and X-ray diffraction) was applied on an ancient Roman building (130 CE), the "Casa di Diana" Mithraeum at Ostia Antica archaeological site. The aim is to study the raw materials, manufacturing and decaying products of the two observed types of Roman fired bricks (red and yellow) that compose the building. The present study estimates an illite raw material of carbonate-bearing marine clay likely referring to the common deposits of central/southern Italy, which contain calcite as accessory phase and a-plastic fraction constituted by quartz, feldspar and opaques. This clay material was added with volcanic temper characterised by abundant clinopyroxene and analcime (from analcimization of leucite) that are typical of the Roman Province volcanism. The firing would be probably the result of oxidizing conditions, as proved by the hematite presence. Thanks to the existence of specific neoformed mineral phases during firing it was possible to assess different temperatures ranges. In detail, the red/orange bricks, for the existence of gehlenite (formed from calcite and its reaction with silicates), were fired at 800-900 °C range; whereas, the yellow ones are characterised by the lack of gehlenite and the disappearance of illite/muscovite, which indicates firing temperature at over 900 °C. Regarding the decaying products, the gypsum covers most of the surface of most bricks, both red and the yellow ones, but these latter are more susceptible to environmental stressors (sulphates and carbonates). Therefore, this work points out how by integrated non-invasive approaches it is possible trace back to original firing temperature, technology of manufacture, interpreting ceramic data.

In-situ multianalytical approach to analyze and compare the degradation pathways jeopardizing two murals exposed to different environments (Ariadne House, Pompeii, Italy).

This study aimed at using portable analytical techniques to characterize original and decayed materials from two murals paintings of Ariadne House (archaeological site of Pompeii, Italy) and define the degradation pathways threatening their conservation. The first wall, located in an outdoor environment, has been directly exposed to degradation processes triggered by weathering and atmospheric pollution. The second wall, placed in a basement under the ground floor, has been constantly sheltered from sunlight exposure and drastic temperature fluctuations. The analytical data obtained in-situ by using Raman spectroscopy and Laser Induced Breakdown Spectroscopy (LIBS) correlates the degradation patterns affecting the two surfaces to their environmental context. The deterioration processes detected on the outdoor wall, which entailed the complete loss of the paint layer, were mostly related to leaching and thermal fluctuation phenomena. The mural painting from the basement instead, showed deep degradation issues due to soluble salt infiltration and biological colonization. The results obtained from this unique case of study highlight the indispensable role of in-situ spectroscopic analysis to understand and predict the degradation pathways jeopardizing the cultural heritage and provide to the Archaeological Park of Pompeii important inference to consider in future conservation projects.

Resonance Raman imaging as a tool to assess the atmospheric pollution level: carotenoids in Lecanoraceae lichens as bioindicators.

Raman spectroscopy differentiation of carotenoids has traditionally been based on the ν 1 position (C = C stretching vibrations in the polyene chain) in the 1500-1600 cm(-1) range, using a 785 nm excitation laser. However, when the number of conjugated double bonds is similar, as in the cases of zeaxanthin and ß-carotene, this distinction is still ambiguous due to the closeness of the Raman bands. This work shows the Raman results, obtained in resonance conditions using a 514 mm laser, on Lecanora campestris and Lecanora atra species, which can be used to differentiate and consequently characterize carotenoids. The presence of the carotenoid found in Lecanoraceae lichens has been demonstrated to depend on the atmospheric pollution level of the environment they inhabit. Astaxanthin, a superb antioxidant, appears as the principal xanthophyll in highly polluted sites, usually together with the UV screening pigment scytonemin; zeaxanthin is the major carotenoid in medium polluted environments, while ß-carotene is the major carotenoid in cleaner environments. Based on these observations, an indirect classification of the stress suffered in a given environment can be assessed by simply analysing the carotenoid content in the Lecanoraceae lichens by using resonance Raman imaging.

A chemical status predictor. A methodology based on World-Wide sediment samples.

As a consequence of the limited resources of underdeveloped countries and the limited interest of the developed ones, the assessment of the chemical quality of entire water bodies around the world is a utopia in the near future. The methodology described here may serve as a first approach for the fast identification of water bodies that do not meet the good chemical status demanded by the European Water Framework Directive (WFD). It also allows estimating the natural background (or reference values of concentration) of the areas under study using a simple criterion. The starting point is the calculation the World-Wide Natural Background Levels (WWNBLs) and World-Wide Threshold Values (WWTVs), two indexes that depend on the concentration of seven elements present in sediments. These elements, As, Cd, Cr, Cu, Ni, Pb and Zn, have been selected taking into account the recommendations of the UNEP (United Nations Environment Programme) and USEPA (United States Environmental Protection Agency), that describe them as elements of concern with respect to environmental toxicity. The methodology has been exemplified in a case study that includes 134 sediment samples collected in 11 transitional water bodies from 7 different countries and 4 different continents. Six of the water bodies considered met the good chemical status demanded by the WFD. The rest of them exceeded the reference WWTVs, at least for one of the elements. The estuaries of the Nerbioi-Ibaizabal (Basque Country) and Cavado (Portugal), the sea inlet of Río San Pedro (Spain), the Sepetiba Bay (Brazil) and the Yucateco lagoon (Mexico) belong to that group.

Focused ultrasound solid-liquid extraction for the determination of organic biomarkers in beachrocks.

Beachrocks are consolidated coastal sedimentary formations resulting mainly from the relative rapid cementation of beach sediments by different calcium carbonate polymorphs. Although previous works have already studied the elemental composition and the mineral phases composing these cements, few of them have focused their attention on the organic matter present therein. This work describes an extraction methodology based on focused ultrasound solid-liquid extraction (FUSLE), followed by analysis using large volume injection (LVI) in a programmable temperature vaporizer (PTV) combined with gas chromatography-mass spectrometry (GC-MS) in order to determine organics such as polycyclic aromatic hydrocarbons (PAHs) and biomarkers (hopanes), which can increase and confirm the information obtained so far. This goal has been achieved after the optimization of the main parameters affecting the extraction procedure, such as, extraction solvent, FUSLE variables (amplitude, extraction time and pulse time) and also variables affecting the LVI-PTV (vent time, injection speed and cryo-focusing temperature). The developed method rendered results comparable to traditional extraction methods in terms of accuracy (77-109%) and repeatability (RSD<23%). Finally, the analyses performed over real beachrock samples from the Bay of Biscay (Northern Spain) revealed the presence of the 16 EPA priority PAHs, as well as some organic biomarkers which could increase the knowledge about such beachrock formation.

Recrystallization and stability of Zn and Pb minerals on their migration to groundwater in soils affected by Acid Mine Drainage under CO2 rich atmospheric waters.

The extent of vertical contamination is intimately related to the soil solution and surface chemistry of the soil matrix with reference to the metal and waste matrix in question. The present research demonstrated the impact that the dissolved CO2 of the meteoric waters, which acidify the environment with pH values below 4, has in the increase of the metal mobility. Although under the given conditions the Zn remains mainly dissolved, the initial PbS and ZnS have evolved into newly formed secondary carbonates and sulphates (i.e., hydrozincite, gunningite, hydrocerussite) that can be found in the efflorescences. The chemical simulation done on the weathering of the original sulphide ores for the formation of these secondary minerals has proved the transient storage mainly of Pb. Nonetheless, many of the minerals formed inside the galleries will be easily dissolved in the next rains and release in an ionic form to the groundwater. The analytical procedure exposed has been proved to be useful not only for the characterization of AMD but also for the prediction of the mobility of metals.

The problem of sampling on built heritage: a preliminary study of a new non-invasive method.

The relevance of a risk assessment of the built heritage was clearly justified due to the fact that it acts as a pollutant repository and hazardous pollutants have the capacity to penetrate into materials. However, the limitation of the sampling processes due to the high value of the built heritage makes a correct evaluation difficult. For that reason, in the present work, the potential of agar gels as non-invasive samplers of built heritage deterioration products, like crusts and patinas, was evaluated. Different gels of agar and Carbopol® (as control gel) were applied on these built surfaces considering several factors: the treatment time, the effectiveness of the addition of EDTA (ethylenediaminetetraacetic acid, C10H16N2O8) and its concentration and the use of a buffer at pH 7.5. All these factors were evaluated in order to determine the capacity of these gels as sampling systems under non-controlled atmospheric conditions. The results obtained in the assays were evaluated by visual examination, by evolution of pH and by the most important techniques used in the risk assessment analysis of the built heritage (Raman spectroscopy, scanning electron microscope (SEM)/energy dispersive X-ray (EDX) and inductively coupled plasma mass spectrometry (ICP-MS)). In this evaluation, the agar gels showed an intrinsic capacity as sampler with respect to the gel Carbopol® and thus, the best option between the studied gels consisted on agar gels with 2 % of EDTA and the longest application time. On the whole, the agar gels showed an interesting potential as non-invasive samplers of built heritage deterioration materials which should be studied more in depth.

Buildings as repositories of hazardous pollutants of anthropogenic origin.

In the present work the pollutant content of diverse building materials was evaluated by the combination of spectrometric and chromatographic techniques. A first non-destructive analysis carried out by µ-XRF and Raman spectroscopy revealed a high impact of pollutants, which reached depths higher than 6mm. The quantitative analyses pointed out that black crust as accumulation nucleus where concentration values up to 3408 mg/kg of lead, 752 mg/kg of chromium or 220 mg/kg of arsenic, high amounts of diverse sulphates and nitrates as well as substantial amounts of polycyclic aromatic hydrocarbons (PAHs) of a clear pyrolytic source were determined. On the other hand, samples without black crust showed also a surprising soluble salt content up to 5%. Polychlorinated biphenyls (PCB) were found to be absent in all material types. The chemometric analysis of the quantitative results revealed that the accumulation capacity and the subsequent pollutant content depends on the type of construction materials, being mortars the most susceptible.

Optimization of two methods based on ultrasound energy as alternative to European standards for soluble salts extraction from building materials.

The Italian recommendation NORMAL 13/83, later replaced by the UNI 11087/2003 norm, were used as standard for soluble salts extraction from construction materials. These standards are based on long-time stirring (72 and 2h, respectively) of the sample in deionized water. In this work two ultrasound based methods were optimized in order to reduce the extraction time while efficiency is improved. The instrumental variables involved in the extraction assisted by ultrasound bath and focused ultrasounds were optimized by experimental design. As long as it was possible, the same non-instrumental parameters values as those of standard methods were used in order to compare the results obtained on a mortar sample showing a black crust by the standards and the optimized methods. The optimal extraction time for the ultrasounds bath was found to be of two hours. Although the extraction time was equal to the standard UNI 11087/2003, the obtained extraction recovery was improved up to 119%. The focused ultrasound system achieved also better recoveries (up to 106%) depending on the analyte in 1h treatment time. The repeatabilities of the proposed ultrasound based methods were comparables to those of the standards. Therefore, the selection of one or the other of the ultrasound based methods will depend on topics such as laboratory facilities or number of samples, and not in aspects related with their quality parameters.

Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

Beachrock formation in temperate coastlines: examples in sand-gravel beaches adjacent to the Nerbioi-Ibaizabal Estuary (Bilbao, Bay of Biscay, North of Spain).

Beachrocks are coastal sedimentary formations resulting from a relative rapid cementation of beach sediments by the precipitation of carbonate cements. These lithified structures are not usually observed at temperate settings. The present work is focused on the occurrence of a significant intertidal cementation in sand-gravel beaches formed among 43°N latitude coastline, close to the Nerbioi-Ibaizabal estuary (Bilbao, Bay of Biscay, North of Spain). Raman micro-spectroscopy combined with SEM-EDX analyses and petrographic descriptions have been applied for the determination of the cement generations and the cemented materials compositions of the beachrock outcrops. In general terms, the cements described were: Cement Generation 1 (CG 1, aragonite, high-magnesium calcite and silicate mixtures), Cement Generation 2 (CG 2, aragonite) and Cement Generation 3 (CG 3, mixtures of CaCO(3) polymorphs and iron oxides). The rest of the interstitial porosity of the rocks appeared either empty or filled with heterogeneous cemented mixtures of previously reworked compounds. The mineralogy, the regular distribution and the isopachous character of the carbonate cements together with the accurate cementation at advanced seaward bands propose a possible marine-phreatic context for the beachrock formation. However, the impure cements and the materials covering the interstitial porosity seem to be the result of both, the weathering actions consequences and the surface alterations of specific grains. Moreover, the presence of modern cemented materials (e.g. slag, bricks and pebbles) suggest a recent formation of the phenomenon.