Search

In Roman wall paintings, blue and green colours are less commonly encountered than red and yellow and were more expensive. Despite this, Pliny and Vitruvius describe the more common compounds used for these pigments, translated today as azurite, lazurite, chrysocolla, indigo and Egyptian blue for blues and verdigris, malachite, celadonite, glauconite and chlorite for greens. A confusion in their nomenclature is often found in the most common blue pigment that is the first manufactured compound, Egyptian blue. For greens, celadonite and glauconite were usual and called generically ‘green earths’, but they prove to be difficult to characterize analytically. In this paper, we evaluate the Raman spectroscopic identification of the characteristic Roman blue and green pigments as used in wall paintings using two different laser wavelengths (green and near infrared) and clarify their nomenclature.

—Chromceladonite in chromitites of the Southern Sarany chromium deposit (the Urals) occurs in two mineral associations: as crusts of acicular grains on uvarovite crystals and in thin-scale aggregates together with quartz and chlorite in brecciated zones developed after chromitites. The chemical composition of chromceladonite (wt %) is K2O 9.4, MgO 6.8, Cr2O3 17.1, SiO2 51.7, Al2O3 8.5, CaO 0.1, FeO 0.2, H2O+ 5.7. The sum is 99.7. Empirical formula: K0.82(Cr0.93Mg0.70 ⋅ Al0.25Ti0.05Fe0.01)Σ1.94[(Si3.56Al0.44)Σ4.00(O9.39OH0.61)Σ10(OH)2. Parameters of an elementary sell: a = 5.271(5), b = 9.015(6), c = 10.171(7) A, β = 101.82(8)°, V = 475(1) A3. The formation temperature of celadonite is as high as 300°C. A source of potassium for chromceladonite can be both country black shales and phlogopite-bearing rocks of the Southern Sarany massif.

We acknowledge the use of the LMA-INA (Universidad de Zaragoza) for access to dual beam equipment and expertise, the technical and human support provided by CICT of Universidad de Jaén (UJA, MINECO, Junta de Andalucía, FEDER), and the use of the PANalytical X'Pert Pro diffractometer of the Departamento de Mineralogía y Petrología, Universidad de Granada, Spain. María del Mar Abad is especially recognized for helping with the HRTEM work. The access to the HAADF FEI TITAN G2 microscope and the Philips CM20 (STEM) microscope was facilitated by the Centro de Instrumentación Científica of the Universidad de Granada. Thanks are extended to Javier Cuadros and an anonymous reviewer for their critical reviews and very helpful comments and suggestions., Glauconite and celadonite coexist at the nanometre scale in Early Jurassic submarine volcanic rocks of the Betic Cordillera (southern Spain) as a result of microbial activity. Samples from the limit between the two micas, recognizable in scanning electron microscopy, have been extracted using the focussed ion beam technique and studied by high-resolution analytical electron microscopy. Both micas are present as randomly oriented differentiated small crystals in the boundary area. They define clearly distinct compositional fields with gaps affecting to Fe, Mg and K. At the lattice scale, celadonite shows a high degree of order, with homogeneous orientation of the visible lattice parameters being a difference from glauconite, formed by packets no more than 10-layers thick. Smectite layers were also detected alongside glauconite packets, in accordance with X-ray diffractograms which indicate that glauconite is a mica-smectite interstratification being more than 90 % mica layers. The compositional gap indicates that celadonite is not the endmember of the glauconitic series and the two micas represent two different structural tendencies of mica, with glauconite having more distorted octahedral sheets, indicated by systematically higher b parameters than celadonite., MCIU-AEIFEDER PGC2018-094573-B-I00 ,PID2019-104624RB-I00 and RTI2018-093419-B-I00, Junta de Andalucia RNM-325, RNM-200 and RNM-179, Gobierno de Aragon E18_17R, European Fund

International audience; This study presents an inventory of possible chemical reactions affecting, or having affected, the Venus surface. Fluid rock reactions are simulated using experiments under conditions close to the present surface. Slabs or powder of several natural and synthetic silicate material (crystalline fresh basalt, altered basalt, obsidian, pumice and basalt glass) were reacted at 475°C in CO 2-H 2 O-H 2 S-SO 2-CO gas mixture. Most of the runs were carried out at roughly 90 bars with a duration of one week, some experiments having longer (one month) or shorter (one day) durations. The role of H 2 O content was explored through a wide range of water pressure: from dry gas for the current Venus conditions up to 590 bars (86%H 2 O) for early Venus (or other early terrestrial planets). The gas phase was sampled before the completion of the runs for chemical analysis of major gas components (CO, H 2 S, SO 2) as well as trace elements possibly released by the rocks. The altered samples were examined by a suite of mineralogical and chemical techniques (scanning and transmission electron microscopy, X-ray diffraction and spectroscopy). In dry atmosphere, the redox potential of the gas was close to the Ni/NiO buffer (−21.3 to −27.3 log fO 2), thus close to the current Venus conditions. The sample alteration is tenuous and limited to surface oxidation of glasses and coating of olivine by iron oxides, as well as the general deposition of (Ca,Na)SO 4 at the sample surface. The oxidation of glass is reflected in the formation of magnesioferrite under the surface and is accompanied by the release of Ca, Mg and Na into the gas phase or mineralized as sulfate at the surface. In wet atmosphere, obsidian recrystallizes into a mixture of plagioclase and amphibole while basaltic glass produced non-expandable clays minerals: chlorite-type (2:1:1) at the surface and likely celadonite (2:1) below the surface. Olivine is preserved. Using obsidian (the most alterable material) as a proxy of aluminosilicates, we discuss the surface reactions operating under supercritical conditions, and we used a shrinking-core equation for modeling the long-term reactions. These parametric exploration offer new insights into processes having affected the surface of Venus and contribute to the discussion of open questions such as the fate of water or the lifetime of vitreous dust or fine grain material if present in the current or past Venusian environment. Longer duration experiments will provide more kinetic parameters that can be extrapolated to the geologic history of Venus.

The data are given on the structure, chemical composition, and content of microelements in the ferromanganese and siliceous crusts of Pervenets Rise (the Sea of Japan). The crusts resulted from the cementation of small fragments of green clays (celadonite) with hydroxides of manganese (todorokite and birnessite) or silica. Initial was the formation of celadonite deposited during the eruption of ore-bearing hydrothermal solutions in the volcano caldera or on its slopes.The features of the crust structure show that they were originated through the diffusive infiltration of gas-hydrothermal solutions along the fractures or weakened zones in volcanic rocks and subsequent cementation of the celadonite already formed occurrences with manganese or siliceous oxides. The manganese and siliceous mineralization is separated in time and often in space and demonstrate more local distribution.

Terra verde, or Green Earth, a naturally-occurring mineral and green pigment consisting of celadonite or glauconite, is one of the most commonly-used pigments in works of art and their conservation. Its widespread use is owed primarily to its insensitivity to light, its neutral pH, and its high stability in air and moisture – attributes that collectively make it virtually unreactive with other components in an artefact. Notwithstanding this, the use of terra verde in the conservation of objects of cultural heritage is hindered due to its minimal tinting strength and hiding power, which makes the pigment effectively transparent when applied on the canvas with the most common binding media. This gives rise to problems in retouching during the restoration process. We report a robust and reliable method to overcome the problem of transparency through the application of crystal engineering techniques on the pigment Verona Green Earth, or Verona Terra Verde (VTV). The purchased pigment was co-crystallised with a selection of different co-formers and analysis was carried out on both starting compound and product via IR and XRF spectroscopy, hot-stage microscopy and powder X-ray diffraction. The results of the experiments conducted show an increase in the pigment's opacity without affecting its colour intensity.

This paper provides information on the structure, chemical composition, and concentrations of microelements in ferromanganese crusts and siliceous crusts sampled on the Pervenets Rise, Sea of Japan. The crusts were formed by cementation of small fragments of green clays (celadonite) by manganese hydroxides (todorokite and birnessite) or by silica. The primary process involved the generation of celadonite, which was deposited as ore-bearing hydrothermal brine that was discharged in the caldera of the volcano or on its slopes. The crusts have a structure that indicates their formation during diffuse percolation of gas-charged hydrothermal brine along fissures or weakened zones in volcanic rocks and subsequent cementation of the resulting celadonite deposits with manganese or siliceous oxides. The manganese and the siliceous mineralization are separated over time, as well as, frequently, in space, and are more local.

The present study aims to examine and treat the flowers canvas painting at the Egyptian Agric-ultural Museum. It is divided into three parts: a) USBDM, SEM-EDX, XRD, GC and FTIR studies, which revealed that the object is suffering from deterioration forms, e.g. ruptures, dust, cracks, missing parts, brittleness, fragility, acidified canvas, and incompatible treatments. The coloring materials are: The green is celadonite (K(Ca, Mg, Fe2) (Fe3Al) [Si4O10](OH)2), the red is hematite (Fe2O3), the blue is lazurite (Na,Ca)8(AlSiO4)6(SO4,S,Cl)2), the beige is hematite (Fe2O3) mixed with barite (BaSO4) and zincite (ZnO), and the gray is carbon black (C). Additionally the ground layer consists of hydrocerussite PbCO3.(OH)2, cerussite Pb3CO3 and zincite ZnO binded with animal glue. The oil media is the poppy seed oil. b) The experimental part showed that 7% Beva371 in toluene is more suitable than the fish glue for object consolidation. c) The applied part covered cleaning, consolidation, patching, lining, completing the missing parts in the painting and ground layers and varnishing.

Large amounts of stone wastes are accumulated alongside different exploiting mines of amethyst geodes in south Brazil, which are becoming an unsustainable environmental issue. For an adequate use of hydrothermal basalt in agriculture as soil remineralizer, it is fundamental to know the material's mineralogy and geochemical variability. This study aims to evaluate the mineralogical and geochemical variability of the basalt from five mines at two positions (near and far from the geodes) in different size fractions to discuss their potential use in agriculture. X-ray diffraction (XRD), X-ray fluorescence (XRF) and petrographic analyses of thin sections were used. Petrographic and mineralogical analyses showed similar compositions for the rocks, consisting of plagioclases, pyroxenes, and opaque minerals with apatite as an accessory mineral. The rock samples located near the amethyst geodes presented slightly higher clay mineral contents than the distant ones. The clay mineralogy was composed of smectite and celadonite. The subfractions preserved the characteristics of the original material. Small geochemical and mineralogical variations were observed in the hydrothermal basalts regardless of the positions and the fraction sizes studied. These characteristics confer this material a high potential for use in agriculture as a soil remineralizer. This approach contributes both to solving an environmental issue associated with geode exploitation and to create an alternative for soil fertilization.

Saint Demetrius of Stomion is a historical monastery placed in the geographical area of Larissa town, Greece, with a remarkable presence from its founding until nowadays. The monastery's present catholicon (main church) has been dated in the 16th century and its surviving wall paintings were constructed in 1758. In addition to the characterization of the materials applied, the purpose of this study is to determine the existence of a sole pictorial phase, that of the mid-18th century, or the occurrence of overpaintings. Additionally, the present study aims to begin the establishment of the documentation of materials and techniques of the late post-Byzantine iconographic guilds, which acted in Central and Northern Greece. The collected samples were analyzed by means of microscopic, spectroscopic and thermogravimetric methods. The use of fresco technique is implied by the major participation of calcium carbonate in all of the painting layers, its main contribution in the plaster layers and the microstratigraphic analysis of the samples' cross-sections, while the scarce and local presence of a proteinaceous material implies the limited use of egg-tempera technique for the highlights. The pigment analysis shows that mostly traditional pigments were used, including cinnabar, ferrous pigments (ochre, sienna, umber), minium, Naples yellow, massicot/litharge, green earth (celadonite), malachite, carbon and bone black, calcite, kaolinite and lead white. The absence of modern pigments, the consistency of all samples regarding microstratigraphy and applied materials, and the lack of the extensive use of an organic medium, strongly suggest the lack of overpaintings.

A range of phyllosilicate compositions have been detected spectroscopically on Mars, but the largest fraction by far corresponds to clay minerals rich in Fe and Mg. Given that most of our understanding of Martian clays comes from remote sensing data, it is critically important to explore the details of how compositional variation affects spectral features of phyllosilicates. The greatest efforts have focused so far on near-infrared (NIR) spectroscopy. Recently, ambiguities have been detected in the NIR spectra of 2:1 phyllosilicates with intermediate Fe Mg content that preclude mineral and chemical discrimination. Such ambiguities highlight the relevance of exploring the visible spectral range as a complementary tool to characterize Martian phyllosilicates precisely. This article reports the investigation of laboratory reflectance spectra (330–800 nm) from 34 Earth analogues of Martian phyllosilicates with a wide range of Mg Fe composition, including nontronite, celadonite and saponite end-members, as well as interstratified glauconite-nontronite, talc-nontronite, and talc-saponite. The spectra indicated the presence of Fe(III) by absorption modulations and a decrease in total reflectance, especially in samples with tetrahedral Fe(III). Absorption bands at 370 and 420 nm were diagnostic of octahedrically and tetrahedrally coordinated Fe(III), respectively. Band amplitudes in the second derivative of the Kubelka-Munk function correlated positively with Fe(III) content (R2 > 0.8). Standard color analyses of the visible reflectance spectra under the CIE illuminant D65 indicated that the CIELAB color parameter a*10 was positively correlated with tetrahedral Fe(III), b*10 was positively correlated with octahedral Fe(III), and L*10 was negatively correlated with Fe(III) in both structural sites. Because Fe(II) was in relatively low amount, it did not provide clear spectral evidence. Multiple regression models using the amplitude of the diagnostic absorption bands predicted well absolute Fe content in the phyllosilicates (R2 = 0.89) and the ratio Fe/(Fe + Mg + Al) (R2 = 0.84). CIELAB color parameters improved the prediction of total Fe (R2 = 0.92) and the ratio Fe/(Fe + Mg + Al) (R2 = 0.93). Application of these analyses to Martian data has challenges set by Fe oxide dust coating and spatial and spectral resolution. However, these results mark an avenue to develop testable tools using visible-wavelength spectral data from both satellite and lander probes to help establishing Fe content and mineral identification of Martian phyllosilicates.

In this paper, we characterized for the first time the painting materials in rock art panels of the Patagonian archaeological locality La Angostura using a methodological approach that combined micro-Raman spectroscopy, attenuated total reflection Fourier Transform infrared spectroscopy, and X-ray fluorescence spectroscopy. In this way, we obtained detailed information on the red, green, and black pigments as well as on accessory minerals present in the paints. Hematite was the chromophore in the red paintings while celadonite and glauconite were identified in the green motifs. A manganese oxide, presumably pyrolusite, was characterized as the black pigment. The pigment compositions were also compared to those of natural sediments collected along the valley of the Chubut River, but the components of the red and green sediment samples differed from those present in the rock art paints. In the red motifs of two of the rock art panels, a relevant finding was the presence of gypsum and anhydrite as a priming layer of the corrugated rock support onto which the red paints were applied. This revealed a different painting technique in comparison to that at the other analyzed panels of La Angostura where paints were applied as thin layers on a smooth surface of the rock support. As far as we know, this is the first report on the identification of gypsum and anhydrite as components of a preparation layer in Patagonian rock art. This result contributes to the open discussion on the origin and function of calcium sulfate in rock art.

International audience; The structural and thermal relaxation overprint associated with the Neogene Alboran rifting have obscured the early Alpine tectono‐metamorphic evolution of the Alboran Domain, representing the metamorphic core of the Betic–Rif orogen of the western Mediterranean region. This study focuses on the Beni Mzala unit, forming the lower and deeper structural level of the Alpine metamorphic nappe stack (Upper Sebtides) in the Moroccan Rif. Meso‐ and micro‐scale structural investigations are carried out on high‐P aluminum silicate (Ky‐bearing)‐quartz segregations that occur as boudins within the main retrogressive syn‐greenschist foliation (S2/D2) and assumed to preserve the early M1 HP metamorphism associated with the Alpine orogenic construction in the Alboran Domain. These boudins host an early crenulated high‐P foliation (S1, D1/M1) made of quartz–kyanite–white mica–rutile. A large spread in white mica composition is documented, with the highest Si content per formula unit (up to 3.18 apfu) preserved along the S1 foliation and the lower Si content observed in the white mica marking the S2 retrogressive foliation (D2/M2) and the rim of S1 mica. Microtextural evidence documents post‐tectonic andalusite growth and static recrystallization of the quartz microlithons. Inverse (Zr‐in‐Rt thermometry) and forward modelling thermobarometry are integrated with Ar–Ar white mica geochronology to define the peak and exhumation pressure–temperature–time (P–T–t) path of the Beni Mzala unit. Minimum thermo‐baric estimates for the M1 event are ~1.4 GPa and 600°C, corresponding to a metamorphic gradient of ~11°/km, consistent with subduction zone metamorphism. Exhumation is constrained by re‐equilibration of the white mica composition (from high to low celadonite) between c. 29 and 22 Ma, during a nearly isothermal retrogressive path, with final equilibration at high‐T/low‐P conditions within the andalusite stability field (~0.2–0.3 GPa and 500°C). A minimum late Oligocene age is proposed for the Alpine D1 tectono‐metamorphic stage in the Rif, suggesting as feasible the previously proposed Eocene timing for the subduction‐zone metamorphism of the Alboran Domain. Conclusive evidence is provided to link the early Miocene tectono‐metamorphic event to a late thermal perturbation that affected the Alboran Domain at shallow crustal conditions, post‐dating the almost complete exhumation of the deep roots of the Alpine belt in the western Mediterranean.

The Voltri Unit and adjacent Tertiary Piedmont Basin, Western Alps, preserve complementary bedrock and sedimentary archives of Alpine subduction and exhumation. Combined PT modeling and phengite Rb–Sr geochronology of bedrock and clast samples shows that Fe–Ti metagabbros and metasediments preserve a record of protracted high-pressure metamorphism, between ~ 50 and ~ 40 Ma. Bedrock and clast Fe–Ti metagabbros yield similar eclogite-facies peak conditions, between 23 and 25 kbar, 510–530 °C; phengite, zoned in celadonite content, with cores > 3.5 Si c.p.f.u. and rims 10 Myr until subduction ceased on arrival of the European continent into the orogenic wedge. As shear tractions on the plate interface are considered to exceed available buoyancy forces for exhumation, we suggest that syn-subduction exhumation occurred along the wedge-plate interface.

International audience; Hypothesis: The objective is to elucidate the multiscale dynamics of water within natural mixtures of minerals, green earth pigments that are mainly composed of phyllosilicates containing large amount of iron. In particular, the interaction of water with the different kinds of surfaces has to be probed. One issue is to examine the influence of surface type, basal or edge, on the dispersion quality.Experiment: The study was carried out using 1H variable field NMR relaxometry on various green earth pigment dispersions and concentrations. To analyse the data, a new analytical model was developed for natural phyllosilicates containing large amount of paramagnetic centres.Finding: The proposed theoretical framework is able to fit the experimental data for various samples using few parameters. It allows to determining water diffusion and residence times in complex phyllosilicate dispersions. Furthermore, it makes it possible to differentiate the contribution of the basal and edge surfaces and their respective surface area in interaction with water. Moreover, NMR relaxation profile reveals to be highly sensitive to the structural aspect of the phyllosilicates and to the accessibility of water to iron, hence allowing to discriminate clearly between two very similar phyllosilicates (glauconite and celadonite) that are difficult to distinguish by standard structural methods.

Phengite series is a dioctahedral solid solution between two end-members of muscovite [K1[Al2]VI[Al1,Si3]IVO10(OH)2] and celadonite [K1[(Fe3+,Al)1,(Mg,Fe2+)1]VI[Si4]IVO10(OH)2], which have a hetero-valent substitution of AlVIAlIV &harr, (Mg, Fe)VISiIV. In this study, we report a hydrothermal-originated authigenic Mg-phengite-series mineral, which occurred as polycrystalline aggregates (Type 1), pore-fillings (Type 2) and well-crystallized lath form (Type 3) from the Haengmae Formation, a dolomite&ndash, pebble-bearing fine sand-sized dolostone, in South Korea. Based on micro-textural observation, three types of Mg-phengite are associated with crystalline dolomite, and are followed by calcite precipitation as pore-filling, indicating that these should be formed by the influx of a Mg-rich hydrothermal fluid after the deposition of some clastic sediments and before calcite-filling. The structural formula based on O10(OH)2 shows that the number of Mg atoms per formula unit (apfu) of Mg-phengite ranges from 0.00 to 0.70 with no Fe, which is relatively high, compared with the previously reported metamorphic phengites. In REEs mineral chemistry, the Mg-phengites are characterized by the enrichment of REEs and by the particular enrichment of LREEs in the polycrystalline aggregates of Mg-phengite. It strongly suggests that the Mg-phengite should be formed by the infiltration of the highly evolved Mg- and REEs-enriched hydrothermal fluid into the clastic sedimentary rock (Haengmae Formation) as a strata-bound form, syngenetically or during early diagenesis.

The morphology, chemical, and mineralogical composition of subsurface filamentous fabrics (SFF) from the Deccan Volcanic Province (DVP) were investigated to determine the origin of these spectacular aggregates. SFF occur in a wide variety of morphologies ranging from pseudo-stalactites to irregular fabrics and are classified as SFFIr (irregular) or SFFMa (matted). The SFF samples exhibit a thread-like (or filament-like) center from which mineral precipitation starts to form the final macroscopic morphologies. Detailed investigations revealed organic material (fungal chitin) in the innermost filamentous core, which may have acted as an initial nucleus for the mineralization processes. The morphometric characteristics of certain filamentous fabrics are very similar to those of microbial filaments and the fabrics formed from them but are clearly distinct from similar types of non-biological precipitates (fibrous minerals, speleothems, and &ldquo, chemical gardens&rdquo, ). These features indicate that the filamentous cores might be products of microbial communities that were active in the basaltic cavities. The SFF cross-sections display similar concentric layers of the mineral succession and reach thicknesses of several centimeters with spectacular lengths up to 100 cm and constant diameters. The typical mineralization sequence points to temporal variation in the chemical composition of the mineralizing fluids from Fe(Mg)-rich (Fe-oxides/-hydroxides, Fe-rich sheet silicates such as celadonite and di-/tri-smectite) to Ca-dominated (Ca-rich zeolites) and finally pure SiO2 (opal-CT, chalcedony, and macro-crystalline quartz). Assuming biological activity at least during the early mineralization processes, circumneutral pH conditions and maximum temperatures of 100&ndash, 120 &deg, C were supposed. The formation of filamentous cores including Fe-bearing phyllosilicates probably occurred near the surface after cooling of the lava, where the elements necessary for mineral formation (i.e., Si, Mg, Al, Fe) were released during alteration of the volcanic host rocks by percolating fluids.

In 2012, the ruins of a temple of the old Russian period were found during archaeological research in the medieval historical territory of Smolensk. The archaeological complex consists of the ruins of an ancient temple, built in the middle of the XIIth century AD, and adjacent to it from the South-West of the territory, which housed the remains of the market XI-turn XIII-XIV centuries AD and necropolis XIII–XVI centuries AD. Chronologically diverse use of the investigated territory up to the XVIth century AD was determined by the nearby Church. Approximately 1000 fragments of wall paintings, 5 fragments window glass and 4 glazed floor tiles were found near the ruins of the Church building. For the first time fragments of wall paintings medieval of Old Russian temple were dated by the AMS radiocarbon dating and went through chemical-technological research (analysis of the plaster foundation, the definition of used pigments) by X-RAY diffractometry (XRD) and scanning electron microscopy (SEM/EDS). Optical microscopy also was used for visual observations of the samples of the wall painting. According to the results of the radiocarbon analysis, the fragments of the wall paintings were divided into two chronological groups. The earlier belongs to the last quarter of the XIIth–the first quarter of the XIIIth century AD. Samples of the wall paintings from the second group are dated back to the third quarter of the XIIIth century AD. A narrow range of Accelerator Mass Spectrometry (AMS) radiocarbon dating of fragments of the murals, obtained from carbonates due to the presence of high content of C14 isotope in carbon of the plaster, is simultaneous in age to the moment of creation of the plaster base. As a result of chemical and technological researches of the fragments of the wall paintings it was established that the plaster basis of the fragments of the wall painting consists of two layers. The plaster base contains organic binders. Chemical and technological analysis of pigments presents the following results: (1) the basis of the blue paint layer is ultramarine (mineral) and anatase (mineral); (2) the basis of the green paint layer is celadonite (mineral); (3) the basis of the brown paint layer is ochre (clay); (4) black particles in the colorful mixture of brown is an organic wood coal pigment.

The Pulo do Lobo domain is one of the units exposed within the orogenic suture zone between the Ossa-Morena and the South Portuguese zones in the SW Iberian Variscides. This metasedimentary unit has been classically interpreted as a Rheic subduction-related accretionary prism formed during pre-Carboniferous convergence and eventual collision between the South Portuguese Zone (part of Avalonia) and the Ossa-Morena Zone (peri-Gondwanan terrane). Discrete mafic intrusions also occur within the dominant Pulo do Lobo metapelites, related to an intra-orogenic Mississippian transtensional and magmatic event that had a significant thermal input. Three different approaches have been applied to the Devonian-Carboniferous phyllites and slates of the Pulo do Lobo domain in order to study their poorly known low-grade metamorphic evolution. X-ray diffraction (XRD) was used to identify the mineralogy and measure crystallographic parameters (illite "crystallinity" and K-white mica b-cell dimension). Compositional maps of selected samples were obtained from electron probe micro-analysis, which allowed for processing with XMapTools software, and chlorite semiempirical and thermodynamic geothermometry was performed. Thermometry based on Raman spectroscopy of carbonaceous material (RSCM) was used to obtain peak temperatures. The microstructural study shows the existence of two phyllosilicate growth events in the chlorite zone, the main one (M-1) related to the development of a Devonian foliation S-1 and a minor one (M-2) associated with a crenulation cleavage (S-2) developed in middle-upper Carboniferous times. M-1 entered well into epizone (greenschist facies) conditions. M-2 conditions were at lower temperature, reaching the anchizone-epizone boundary. These data accord well with the angular unconformity that separates the Devonian and Carboniferous formations of the Pulo do Lobo domain. The varied results obtained by the different approaches followed, combined with microstructural analysis, provide different snapshots of the metamorphic history. Thus, RSCM temperatures are higher in comparison with the other methods applied, which is interpreted to reflect a faster re-equilibration during the short-lived thermal Mississippian event. Regarding the metamorphic pressure, the data are very homogeneous: very low celadonite content (0 %-10 %) in muscovite (and low values of K-white mica b-cell dimension; 8.995 angstrom mean value), indicating a low pressure-temperature gradient, which is unexpected in a subduction-related accretionary prism., This research has been supported by the Spanish Ministry of Science and Innovation (grant no. CGL2011-24101), the Spanish Ministry of Economy and Competitiveness (grant nos. CGL2015-71692-P, CGL2016-75679-P), the Andalusian Government (grant nos. RNM-148, RNM-179), and the doctoral scholarship to Irene Perez-Caceres from the Spanish Ministry of Science and Innovation (grant no. BES-2012-055754). The Raman facility in Paris has been funded by the city of Paris (Emergence program).

The present work studies the tuffs associated with the volcanic area of the Paleogene Sheinovets caldera, located on the southeastern part of the Rhodope massif, in Bulgaria. Its purpose is to describe the mineralogical and geochemical composition of the zeolitized volcaniclastic deposits in the broader area of Petrota village, in the northwesternmost part of the Greek regional unit of Evros, in northeast Greece. The samples studied in this work were collected from seven (7) different locations, covering an area of almost 4 km in length and 2 km in width. Macroscopically, the samples display a greyish-green hue and they are widespread in the area of study. They often contain fragments of the crystalline metamorphic basement (mica-schists, phyllites, amphibolites, quartzites) and/or rhyolitic clasts. A rhyolitic outcrop of greyish-pink hue is observed in the Mavri Petra region, probably related to the Rupelian acid volcanism that occurred in the Sheinovets caldera. The mineralogy of the tuffs was studied under light polarizing microscope and using Scanning Electron Microscopy (SEM), and it was further confirmed by X-ray powder diffraction (XRPD) method. The initial matrix of the tuffs consisted predominantly of glass shards that are now partly or fully altered into zeolites and clay minerals, such as celadonite, displaying characteristic pseudomorphic structures. The dominant zeolite is clinoptilolite, while in some areas the presence of mordenite is also noticed. Feldspar phenocrysts are abundant, and they are represented by plagioclase and sanidine. Although quartz crystals can be observed under light-polarizing microscope solely in metamorphic fragments, the presence of silica polymorphs was also confirmed through SEM and XRPD analysis, with quartz and cristobalite prevailing. The mineralogical assemblage includes phenocrysts of biotite and in some cases amphiboles, while pyroxene, epidote, garnet, titanite, apatite, zircon, ilmenite, magnetite and rutile are additional minerals which have been identified locally in accessory quantities. Chemical analysis was carried out for major and trace elements, using the X-ray fluorescence (XRF) method and 4 Acid digestion ICP-MS analysis, respectively. The samples of Mavri Petra region, exhibit high concentrations in Cu, Pb, Mn, V, P and W. The analyzed concentrations of U in the area of Palaeokklisi are relatively high in comparison to the rest due to its proximity to a fault. Towards the northwestern study area, close to the Greek-Bulgarian border, the concentrations of Sr appear to be particularly high, probably because the area is closer to the volcanic centre.

Agate samples collected from the vicinity of Asni and Agouim (Western Atlas, Morocco) were investigated using microscopic observations supported by Raman micro-spectroscopy. The agates are marked by the presence of various microtextures typical of epithermal vein deposits, including jigsaw-puzzle, feathery, and lattice-bladed. The first two indicate that the formation of agates was likely marked by recrystallization of metastable silica phases (i.e., opaline silica or massive chalcedony). The presence of lattice-bladed (after barite and calcite) quartz may be, in turn, ascribed to the boiling-related conditions that could have triggered the formation of abundant copper and iron sulfides found within silica matrix. Additionally, the local occurrence of growth lines (so-called Bambauer quartz) and intergrowth of length-slow and length-fast chalcedony are linked to the variations of physico-chemical conditions during rock formation (alkaline-acidic). According to Raman spectroscopy, silica matrix of the agates is made of &alpha, quartz with a local admixture of moganite (from 0.0 up to 78 wt.%), but also contains numerous solid inclusions of hematite, celadonite, as well as poorly-organized carbonaceous material and rutile. These phases were likely emplaced during low-temperature hydrothermal activity of SiO2-bearing fluids that originated from post-magmatic hydrothermal activity developed within host rocks and/or meteoric waters.

In porous media, effects of internal gradient caused by magnetic susceptibility contrast between the matrix and infilling fluid shifts transverse relaxation time (T2) to shorter time, resulting in imprecise classification of pore sizes. In shale, details of the effects of paramagnetic and clay minerals that induce the internal gradients are poorly understood. We measured a brine mixture with a granular form of minerals, including kaolinite, montmorillonite, glauconite, illite, pyrite, celadonite, and chamosite, to infer contributions of each to T2 relaxation in shale. Nuclear magnetic resonance (NMR) response of these samples was used to calculate the total mean logarithm of T2 (T2ML) and volume of water in the samples. Additionally, physical properties such as magnetic susceptibility, specific surface area, and elemental composition were acquired. Pore geometry, magnitude of internal gradients, pore-size distributions, and secular regimes in which the media relaxed (based on their shortest characteristic time scales) were characterized from these properties. These time scales measure the behavior of the relaxation regimes such as longitudinal relaxation time-to-T2 ratio and dependence of relaxation rate on echo spacing (tE). Glauconite illite, pyrite, chamosite, and kaolinite grouped into a small-pore system, whereas montmorillonite and celadonite grouped into large-pore systems. A free diffusion regime governed secular relaxation for kaolinite; a motional-averaging regime governed montmorillonite, celadonite, and large tE chamosite; whereas a localization regime dominated the rest of the minerals. We conclude that understanding the effects of internal gradients in shale is important to quantify the shortening of T2ML, which leads to overestimation of bulk fluid volume and, thus, underestimating NMR permeability when used as an input into permeability estimator equations.

Boles are markers of hiatus in successive eruptions of the Deccan flood volcanism (DFV) emplaced at the Cretaceous-Paleogene boundary that are interpreted to retain paleoenvironmental information from their subaerial exposure. To evaluate paleoenvironment during these hiatuses, mineralogy and geochemistry of three different colors of boles, i.e., red (dark = 10R-3/6 and light = 10R-4/8), brown (5YR-4/4) and green (5G-6/2) were examined. The plagioclase index of alteration (PIA) (loss of Ca and Na relative to Al) was between 76 and 81 for all the boles, indicating moderate chemical weathering that is probably due to their short subaerial exposures. Mass balance calculations show significant enrichments of K, Si, Mg and Rb in green and brown boles suggesting an allochthonous input that is interpreted as volcanic ash fallout. Mineralogically, the red bole is dominated by montmorillonite and hematite, the brown bole of ferruginous smectite and montmorillonite, and the green bole of celadonite and nontronite. Montmorillonite and hematite genesis in red boles indicates leaching in an oxidative environment at near neutral pH (~5.5 to 8) conditions. Further, heating of the altered basalt from emplacement of upper lava flows under subaerial-dry conditions could have also promoted the formation of hematite in red boles. The hydrothermal alteration of K and Mg enriched volcanic ash admixed with the altered lower flow basalt under slightly reducing oxidation potential led to the genesis of nontronite and celadonite in the green bole. The aluminous Fe-smectite in brown bole occurred from hydrothermal alteration of aluminous clays (e.g., montmorillonite). The different colored boles, therefore, suggest a range of weathering processes including chemical leaching to hydrothermal alteration in oxidative to reducing environmental conditions throughout DFV emplacement that could reflect changing surficial conditions associated with volcanically forced changes to the environment.