Graphitization in a high-pressure,low-temperature metamorphic gradient: a Raman microspectroscopy and HRTEM study

The graphitization of carbonaceous material (CM) in a high-pressure metamorphic gradient is characterized along a cross section in the Schistes Lustrés formation, Western Alps. Along this 25-km cross section, both the CM precursor and the host-rock lithology are homogeneous, and the prograde evolution of the pressure-temperature metamorphic conditions from the lower blueschist-facies (13 kbar, 330 °C) to the eclogite-facies (20 kbar, 500 °C) is tightly constrained by literature data. Raman microspectroscopy shows that at the micrometre scale, this process is progressive and continuous with increasing metamorphic grade, and that the structure of CM is very sensitive to temperature variations. At the nanometre scale (HRTEM), the CM is composed of a mixture of a microporous phase and an onion-ring like phase, both known as non-graphitizing under the effect of temperature at ambient pressure. The HP-LT graphitization produces structurally and microtexturally heterogeneous CM. With increasing metamorphic grade, the graphitization of the two types of CM proceeds up to the triperiodic graphite stage because of microtextural and structural changes that are specific to each type of CM. The microporous material is progressively transformed into graphite through a macroporous transitional stage. In this case, graphitization mainly occurs on the pore walls as a result of pore growth. In the case of concentric onion-ring like material, graphitization occurs in the regions with the largest radius of curvature, i.e. on the outer part of the ring. In comparison with 1-bar experiments, pressure seems to induce microtextural changes, which allows the subsequent structural modifications of the starting material.     

Extending the applicability of the Raman carbonaceous‐material geothermometer using data from contact metamorphic rocks

The degree of graphitization of carbonaceous material (CM) has been widely used as an indicator of metamorphic grade. Previous work has demonstrated that peak metamorphic temperature (T) of regional metamorphic rocks can be estimated by an area ratio (R2) of peaks recognized in Raman spectra of CM. The applicability of this method to low‐pressure (<3 kbar) contact metamorphism was tested using Raman spectroscopic analyses of samples from two contact‐metamorphic aureoles in Japan (Daimonji and Kasuga areas). A suitable measurement procedure allows the dependence of the geothermometer on sample type (thin section, chip) and incident angle of laser beam relative to the c‐axes of CM to be tested. Two important general results are: (i) in addition to standard thin sections, chips are also suitable for spectral analysis; and (ii) the incident angle of the laser beam does not significantly affect the temperature estimation, i.e. spectral measurements for the geothermometer can be carried out irrespective of the crystallographic orientation. A laser wavelength of 532 nm was used in this study compared with 514.5 nm in an independent previous study. A comparison shows that the use of a 532‐nm laser results in a slightly, but systematically larger R2 ratio than that of a 514.5‐nm laser. Taking this effect into account, our results show that there is a slight but distinct difference between the R2–T correlations shown by contact and regional metamorphic rocks: the former are slightly better‐crystallized (have slightly lower R2 values) than the latter at the same temperature. This difference is interpreted as due to the degree of associated deformation. Despite the slight difference, the results of this study coincide within the estimated errors of ±50 °C with those of the previously proposed Raman CM geothermometer, thus demonstrating the applicability of this method to contact metamorphism. To facilitate more precise temperature estimates in regions of contact metamorphism, a new calibration for analyses using a 532‐nm laser is derived. Another important observation is that the R2 ratio of metamorphosed CM in pelitic and psammitic rocks is highly heterogeneous with respect to a single sample. To obtain a reliable temperature estimate, the average R2 value must be determined by using a substantial number of measurements (usually N > 50) that adequately reflects the range of sample heterogeneity. Using this procedure (with 532‐nm laser) and adapting our new calibration, the errors of the Raman CM geothermometer for contact metamorphic rocks decrease to ～±30 °C.     

Contrasting degrees of recrystallization of carbonaceous material in the Nelson aureole,British Columbia and Ballachulish aureole,Scotland, with implications for thermometry based on Raman spectroscopy of carbonaceous material

The degree of recrystallization of carbonaceous material (CM), as monitored by Raman microspectroscopy, was examined as a function of metamorphic grade in two well‐studied contact aureoles containing carbonaceous pelites: the Nelson aureole, British Columbia and the Ballachulish aureole, Scotland. Here, we use (a) the R2 ratio extracted from the Raman spectrum of CM as a proxy for the degree of graphitization (0.0 in perfect graphite then increasing with structural defects) and (b) the second‐order S1 band (~2,700 cm^?1) as a marker for the tridimensional ordering of CM. The Nelson aureole (garnet–staurolite–andalusite–sillimanite–K‐feldspar sequence, ~550–650°C, 3.5–4.0 kbar) was developed in rocks that were unmetamorphosed prior to contact metamorphism, whereas the Ballachulish aureole (cordierite–andalusite–K‐feldspar–sillimanite sequence, ~550–700°C, ~3.0 kbar) was developed in rocks that had been metamorphosed to garnet grade conditions (~7 kbar, ~500°C) c. 45 Ma before contact metamorphism. Thirty‐one samples were examined from Nelson and 29 samples from Ballachulish. At Nelson, the R2 ratio steadily decreases from ~0.25 to 0.0 as the igneous contact is approached, whereas at Ballachulish, the R2 ratio remains largely unchanged from regional values (~0.20–0.25) until less than 100 m from the igneous contact. The second‐order S1 band reveals that carbonaceous material (CM) was transformed to highly “ordered” locally tridimensional graphitic carbon at Ballachulish by regional metamorphism prior to contact metamorphism, whereas CM was still a disordered turbostratic (bidimensional) material before contact metamorphism in the case of Nelson. Pretexturation of CM likely induced sluggish recrystallization of CM and delayed graphitization in the Ballachulish aureole. Temperatures of recrystallization of the CM in the two aureoles were estimated using different published calibrations of the thermometry based on Raman Spectroscopy of Carbonaceous Material (RSCM), with differences among the calibrations being minor. In the Nelson aureole, temperatures are in reasonable agreement with those indicated by the metapelitic phase equilibria (all within 50°C, most within 25°C). In the Ballachulish aureole, the retarded crystallization noted above results in increasing underestimates of temperatures compared to the metapelitic phase equilibria (up to ~75°C too low within 200 m of the igneous contact). Our study calls for careful attention when using RSCM thermometry in complexly polymetamorphosed rocks to assess properly the meaning of the calculated temperature.     

Carbonaceous material in the Ryoke metamorphic rocks, Kinki district, Japan

Carbonaceous material in the Ryoke pelitic metamorphic rocks in the Wazuka area, Kinki district, Japan, has been studied by X-ray diffraction (XRD) analysis. Detrital graphite in the lower-grade rocks is recognized in both X-ray diffractograms and transmission electron micrographs. Progressive graphitization is considered to have proceeded continuously on the basis of the XRD data of the bulk concentrates of carbonaceous material, and a conspicuous asymmetric shape of XRD peaks in lower-grade samples is ascribed to the mixture of carbonaceous materials with different crystallinities. Fully-ordered graphite does not occur until the highest-grade part of the chlorite-biotite zone. The variation of degree of crystallinity of carbonaceous materials inferred from XRD data is consistent with the prograde mineral zones. The temperatures for the development of fully-ordered graphite are estimated to be between 410° and 440°C in regional metamorphism through comparing the XRD data from low-, medium- and high-pressure types of metamorphic terrains.     

Raman spectra of carbonaceous material in metasediments: a new geothermometer

Metasedimentary rocks generally contain carbonaceous material (CM) deriving from the evolution of organic matter originally present in the host sedimentary rock. During metamorphic processes, this organic matter is progressively transformed into graphite s.s. and the degree of organisation of CM is known as a reliable indicator of metamorphic grade. In this study, the degree of organisation of CM was systematically characterised by Raman microspectroscopy across several Mesozoic and Cenozoic reference metamorphic belts. This degree of organisation, including within‐sample heterogeneity, was quantified by the relative area of the defect band (R2 ratio). The results from the Schistes Lustrés (Western Alps) and Sanbagawa (Japan) cross‐sections show that (1) even through simple visual inspection, changes in the CM Raman spectrum appear sensitive to variations of metamorphic grade, (2) there is an excellent agreement between the R2 values calculated for the two sections when considering samples with an equivalent metamorphic grade, and (3) the evolution of the R2 ratio with metamorphic grade is controlled by temperature (T). Along the Tinos cross‐section (Greece), which is characterised by a strong gradient of greenschist facies overprint on eclogite facies rocks, the R2 ratio is nearly constant. Consequently, the degree of organisation of CM is not affected by the retrogression and records peak metamorphic conditions. More generally, analysis of 54 samples representative of high‐temperature, low‐pressure to high‐pressure, low‐temperature metamorphic gradients shows that there is a linear correlation between the R2 ratio and the peak temperature [T(°C) = ?445 R2 + 641], whatever the metamorphic gradient and, probably, the organic precursor. The Raman spectrum of CM can therefore be used as a geothermometer of the maximum temperature conditions reached during regional metamorphism. Temperature can be estimated to ± 50 °C in the range 330–650 °C. A few technical indications are given for optimal application.     

湖南新化煤系石墨结构演化及其热反应行为

为了探究煤系石墨形成过程中结构演化及不同石墨化程度无烟煤和石墨的热反应行为,选取湖南新化系列变质程度无烟煤和煤系石墨为研究对象,通过X射线衍射（XRD）和高分辨率透射电子显微镜（HRTEM）对其结构进行表征,并结合程序控制升温法（TPO）分析不同变质程度无烟煤和煤系石墨的热反应行为。结果表明,随变质程度的增加,碳结构由无烟煤中的无定形态转变成石墨的三维有序C原子点阵。系列石墨化煤是由多种有序度不同的碳结构相组成,体现了其结构非均质性,碳结构相含量及分布随变质程度而逐渐变化,石墨化程度最高的煤系石墨中主要为石墨微晶集合体,但依旧含有结构缺陷。无烟煤和煤系石墨中碳结构的多相性和不均匀分布是影响其热反应行为的重要原因。      

Conversion of carbonaceous material to graphite within the Greywacke Zone of the Eastern Alps

Morphology and reflectance of carbonaceous material (CM) in Late Carboniferous metasediments of the eastern Greywacke Zone (Eastern Alps) indicate a mixture of vitrinite, grainy textured and lamellar shaped particles. As imaged by high-resolution atomic-force microscopy, vitrinite and the grainy textured particles show mesophase structures which can be described as facetted nanocrystals within the carbon matrix. High-resolution transmission electron microscopy has revealed two types of microtextures representing different degrees of graphitization. The first type is characterized by elongated ring-shaped microtextures, whereas the second type is characterized by graphite lamellae and polygonal flakes with long-range ordered aromatic layers. In spite of the heterogeneity of the CMs, the geographical distribution of quantitative metamorphic parameter (Raman spectra parameter, X-ray diffraction pattern, microscopic reflectance) suggests a graphitization process which is promoted by advective heat transport during post-collisional processes. In a tentative pressure-time path, Late Cretaceous thrusting results in a turbostratic ordering of the aromatic layer. Ordering to long-range ordered aromatic layers was achieved during the Late Cretaceous-Paleogene exhumation of mid-crustal rocks beneath the eastern Greywacke Zone.     

Graphitization of dispersed carbonaceous material in metamorphic rocks

Dispersed carbonaceous material concentrated from some New Zealand and Japanese metamorphic rocks has been analysed by X-ray and electron diffraction methods. A classification to describe sub-graphitic material (graphite-d) is proposed. Progressive graphitization is related to metamorphic grade as conventionally defined by mineral assemblages. Thus carbonaceous material in zeolite facies rocks as well as some lawsonite-albite-chlorite facies rocks is nearly amorphous (graphite-d ₃); material from slightly higher grade rocks of the lawsonite-albite-chlorite, pumpellyite-actinolite, greenschist, and blueschist facies show a more advanced degree of crystallinity (graphite-d ₂,-d ₁). Fully-ordered graphite is first recognized in albite-epidote amphibolite and amphibolite facies rocks.X-ray diffraction data are also presented for New Zealand coals of known rank. Lignite and high volatile bituminous coal samples yield graphite -d ₃ patterns. A low volatile bituminous sample is transitional between graphite-d ₂ and -d ₃, while a semi-anthracite sample is graphite-d ₂.Analysis of X-ray and electron diffraction data permits some understanding of the structure of sub-graphitic materials. It is shown that peak broadening may be produced by structural variations within a given sample, and for this reason the estimation of crystallite size solely on the basis of diffractograms should be regarded with caution.The controls of graphitization are discussed and it is tentatively concluded that graphitization is primarily dependent upon metamorphic temperature; pressure and variation in starting material presumably constitute secondary controls. Under metamorphic conditions, true graphite probably forms above 400° C.     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

Evidence for the influence of fCH 4 on the crystallinity of disseminated carbon in greenschist facies rocks,Rhode Island,USA

Disseminated carbon has been extracted from 19 samples of arkosic rocks from the chlorite, biotite and garnet zones in the Narragansett basin, and analysed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD of these samples yields only the (002) peak which may be as much as four times wider than the silicon internal standard peak and is always skewed to low angles 2θ. All (002) peaks were digitized and the four moments calculated. The results suggest that width at half-height (W_1/2) provides a poorer estimate of peak shape than coefficients of skewness and kurtosis. The positive correlation of these coefficients with grain size determined by SEM in the range of 0.1–100 μm suggest a direct relationship between peak shape and grain size. No variable measured in this study correlates with metamorphic grade. However, W_1/2, skewness and kurtosis of the (002) diffraction peak of the carbonaceous material in the biotite and garnet zones correlates inversely with modal carbon. This suggests that the volatilization reaction: C+2H₂=CH₄ may be an important step in the mechanism of graphitization. Variable fugacities of H₂ and CH₄ and/or variable permeabilities may be responsible for the non-uniform development of graphite crystallinity in the greenschist facies rocks in Rhode Island.     

不同变质程度煤系石墨结构特征

煤系石墨形成于煤层的接触变质带,通常被当作煤开采利用而造成严重的资源浪费.为了了解煤系石墨在成矿过程中分子结构的变化,利用X射线衍射（XRD）、透射电子显微镜（TEM）、拉曼光谱（Raman）等技术,对我国陕西凤县、湖南新化和湖南郴州鲁塘地区处于不同变质程度煤系石墨进行测试分析.结果表明:凤县样品石墨化度最低,仍处于超无烟煤阶段;新化石墨处于半石墨阶段,鲁塘样品石墨化程度最高,其结构比较完美,接近于三维有序理想石墨结构,但仍存在少量的无序化畴.XRD分析显示随着样品石墨化程度的升高,堆砌层数与堆砌延展度均增大;拉曼光谱中D峰减弱,G峰逐渐增强并尖锐,D峰与G峰的强度比和面积比均减小,显示碳原子sp2平面域增大.透射电子显微镜晶格像显示,由无烟煤向石墨结构转变过程中,煤的芳香片层首先形成类石墨结构的微柱体,然后这些微柱体之间相互联结,最后形成横向无限延展的石墨晶层.      

Evaluating the thermal metamorphism of CM chondrites by using the pyrolytic behavior of carbonaceous macromolecular matter

The degrees of thermal metamorphism of 10 CM chondrites and of the Allende CV3 chondrite were evaluated from the viewpoint of “graphitization” of the carbonaceous macromolecular matter by means of flash pyrolysis-gas chromatography (GC). The unheated chondrites, Yamato- (Y-) 791198, Murray and Cold Bokkeveld, yielded larger amounts and wider varieties of pyrolyzates than the chondrites strongly heated in the parent asteroids, Y-82054, Y-86695, and Belgica- (B-) 7904, and Asuka- (A-) 881334 (more strongly heated than Y-793321, which has been weakly heated, but lesser than the other strongly heated meteorites). The weakly heated chondrites, Y-793321 and A-881458, showed intermediate features. The data indicate that graphitization of the carbonaceous matter is most extreme in the strongly heated chondrites and that during graphitization, the matter has lost its labile portion, which can generate pyrolyzates such as naphthalene. In order to establish a new method for the evaluation of the degree of graphitization of chondritic carbonaceous matter, a diagram was developed to show the relationship between the total amounts of pyrolyzates with retention times later than 5 min (=S_RT>5) and the ratio of the amount of naphthalene, a pyrolysis product, to S_RT>5 (=S_N/S_RT>5). The diagram indicates a possible evolutionary pathway of graphitization of the carbonaceous matter in carbonaceous chondrites.     

The association of poorly ordered graphite, coke and bitumens in greenschist facies rocks of the Poniklá Group, Lugicum, Czech Republic: the result of graphitization of various types of carbonaceous matter

Greenschist facies rocks of the Poniklá Group (Ordovician-Silurian), Czech Republic, contain several types of carbonaceous matter that differ in their morphology, texture, reflectance and Raman characteristics. The first type consists of large (up to 3 mm) irregularly bound particles of low reflectance (R_omin = 0.9%; R_omax = 5.6%). The area ratio of the 1585 cm^-1 to 1350 cm^-1 Raman peaks (1.08–1.17) indicates an intermediate degree of graphitization. The formation of this type of highly porous particle, displaying a texture reminiscent of regular or needle coke, is attributed to the thermal alteration of the amorphous (structureless) kerogen of the precursor sediments. The second type consists of lamellar particles up to 30 μm thick, which can be associated with the latter or can occur independently in white mica-rich laminae. This type is characterized by high bireflectance (R_omin = 0.6%; R_omax = 11.9%) and by lower ratios (0.70–0.82) of the Raman peak areas. These particles are interpreted as the product of solid-state, diffusion-controlled graphitization of a chemically homogeneous organic material, e.g. of graptolite periderms. The third type consists of isometric, up to 2 mm large, commonly fractured grains and fragments which mainly occur in quartz-rich laminae. In reflected light, the texture is either homogeneous or consists of various types of anisotropic mozaics. The Raman peak area ratios (0.75–1.14) indicate a highly variable degree of structural ordering. These particles are considered as the remains of metamorphosed bitumens, accumulated in the sandy laminae of the original sediments. The fourth type consists of small particles of carbonaceous matter (maximum length 25 μm, thickness 1-2 μm), which occur adjacent to crystal faces of white micas. This type is probably the product of epitaxial growth of graphite from the gaseous phase. The results of this work indicate that the differences in the degree of graphitization of the carbonaceous matter in low-grade metamorphosed rocks can be mainly related to the initial nature of the sedimentary organic matter and to its premetamorphic history.     

Graphite and Graphite-like Materials from Black Shale and Magmatic Ores: Raman Spectroscopy Data

Graphite and graphite-like materials widely are present at black shale and magmatic ores. The nature of these carbon materials (CM) is multifarious. In what cause connects a mineralization with carbon. The great numbers of parameters, namely, the temperature, the pressure, the shear stress, the catalytic species, the host-rock lithology, the time and etc., have an influence on the graphitization process. Accumulations of gold and platinum group elements in black graphite shale and extraction of these metals from rocks depend in considerable degree from structural properties of CM. Raman spectroscopy has wide applied for various carbon modifications, including nano-structuring materials. The first and second-order Raman spectrum have been correlated with changes in the structure of graphite. There is a linear relationship between temperature and Raman R2 and R1 parameters (derived from the area and intensity of the defect band (D) relative to the ordered graphite band (G), respectively). The purpose of the present study is to characterize the rocks and CM from carbon-rich rocks of gold-ore deposits of the black-shale formation and magmatic ores using micro-Raman spectroscopy technique (Horiba Jobin Ivon LabRam spectrometer). Exciting was performed with 325 nm line of He-Cd laser. The graphite and graphite-like samples from many ore deposits of Russia and Kazahstan are investigations. R1 and R2 ratio indicate variable degree of organisation CM in the samples. The results show different spectral variations of CM with metamorphic grade: the well-ordered graphite from magmatic rocks, more - ordered and the disordered less graphitized CM from black-shale ores. For the first time in the world practice the Raman spectroscopy technique has been applied to determine the temperature of graphitizing for CM at gold-ore deposits of the black-shale formation. The temperatures obtained on carboniferous substance for the gold deposits range from 405°С to 280°С. Temperature of CM formation from Pt-low sulphide ores of the Talnakh deposit ranges from 4700C to 6500C. It has been shown that the carbon-rich phases from black-shale and magmatic rocks have various degrees of graphitization and different carbon forms.     

Carbonaceous material in pelitic schists of the Sanbagawa metamorphic belt in central Shikoku,Japan

Carbonaceous material in pelitic schists of the Sanbagawa metamorphic belt in central Shikoku, Japan, was separated from the host rocks and its X-ray diffraction and chemical composition were studied. Its crystal structure and chemistry change continously with increasing metamorphic grade and approach those of well-ordered graphite near the biotite isograd. As graphitization is a rate process, the temperature of complete graphitization differs from one metamorphic terrain to another as a function of the duration of metamorphism. In an individual metamorphic terraan, however, the degree of graphitization is a useful indicator of relative metamorphic temperature in lower-grade rocks.     

油气化探样品酸解气中甲烷与氢气的相关性研究

酸解烃是油气化探方法中准确度相对较高的一项指标,已得到广泛的应用,深入研究酸解气有助于对其机理的进一步解释,并且有利于开发新的分析指标。本文利用气相色谱法测定了油气化探样品经盐酸分解后所得气体中烃类组分与非烃气体组分的含量,发现了酸解气中甲烷与氢气的含量具有正相关性。进而通过X射线荧光光谱和X射线衍射分析样品的元素和矿物组成、样品再粉碎分析以及激光拉曼光谱分析包裹体成分等实验,获得以下结论:(1)酸解气中的甲烷和氢气含量与样品元素组成无关,与碳酸盐矿物正相关,其含量可以反映深部油气的情况;(2)两种气体并不是以物理吸附形式存在于样品中,而是存在于更小的空间内,证明了酸解烃分析方法具有相当高的稳定性;(3)获得了甲烷和氢气同时存在于包裹体的直接证据,由此推测这两种气体可能具有同源性。由于甲烷和氢气含量相关性的存在,酸解脱气中氢气的含量测定有望成为油气化探的新指标,应用于油气资源调查。     

New method for in situ characterization of loose material for landslide mapping purpose

The assessment of grain size distribution and plasticity of loose geological material, during in situ geological investigations, is not obvious. Visual appreciation allows an approximative quantification of the coarse granulometric fractions, but not of the fine ones. Field soils determination methods suggested until now, are visual and tactile tests leading to a very rough estimate, which is only qualitative and not very reproducible. The new proposed field test (GEOLEP method) allows a quick quantification of the fine fraction of loose material. It allows the determination of the sand fraction (fine and medium grained sands) as well as the methylene blue value of the samples. The necessary equipment to perform this test is light and compact and the time needed to analyze one sample is approximately 15 min. Thus it is also possible to carry out numerous measurements in one day. The calibrations were carried out on a selection of 13 natural samples, chosen for their representativeness of the typical alpine quaternary deposits. The results obtained with GEOLEP method are relevant compared with standardized laboratory tests; the obtained correlation indexes are of 73% for the comparison with laboratory stain test results and of 89% with a laboratory method using a similar procedure than the field test. The correlation we performed with Atterberg's limits tests shows that a rough approximation of plasticity index can also be obtained (R² = 75%). This method thus brings a new tool which should allow taking into account the lithological factor (by some quantitative and representative variables) in a reliable way for the evaluation of landslide hazards.     

Raman spectrum of carbonaceous material: a possible metamorphic grade indicator for low-grade metamorphic rocks

Raman spectral analyses of carbonaceous material (CM) extracted from pelitic samples along two sections traversing the metamorphic belt of Taiwan were carried out in the present study. The results show similar spectral variations of CM with metamorphic grade as those documented in the literature. However, continuous sampling from zeolite facies through prehnite–pumpellyite facies to greenschist facies metamorphic rocks in the present study does reveal some interesting features on the Raman spectra of CM that were not noted before. Both the Raman D (disordered-)/O (ordered-) peak area (i.e. integrated intensity) ratio and the D/O peak width (i.e. full width at half maximum, FWHM) ratio of the CM decrease with progressive metamorphism, but the most prominent change in the D/O peak area ratio occurs in samples of lower greenschist facies metamorphic grade, while the most significant decrease in the D/O peak width ratio occurs in samples near the boundary of prehnite–pumpellyite facies and greenschist facies. This phenomenon is interpreted as a result of the decoupling of the changing rates of in-plane crystallite size and degree of defects of CM with progressive metamorphism. It is postulated that the Raman spectrum of CM can serve as a metamorphic grade indicator to distinguish samples of prehnite–pumpellyite facies metamorphic grade from those of greenschist facies metamorphic grade.     

Mineralogy and spectroscopy (visible near infrared and Fourier Transform Infrared) of Mukundpura CM2: Implications for asteroidal aqueous alteration

We report the textures, mineralogy and mineral chemistry of the Mukundpura matrix component, a clast-bearing, brecciated, new CM2 carbonaceous chondrite. Like other CMs, Mukundpura is matrix-enriched and has experienced different degrees of aqueous alteration with evidences of fracturing and compaction of clasts due to the impact. A few relict chondrule clasts and CAIs (diopside and spinel) survived despite of the alteration amidst accessory phases of olivine, magnetite, sulphides and calcite. X-Ray Diffraction (XRD), Visible Near Infrared (VNIR) and Fourier Transform Infrared (FTIR) spectroscopic studies reveal higher phyllosilicate content (∼90 %) comprising of both Mg and Fe-serpentine and abundant serpentine-sulphide intergrowths. Even then, the presence of accessory olivine as relict clasts can be interpreted from the presence of certain typical olivine absorptions in the FTIR spectra. The non-stoichiometric, Tochilinite-Cronstedtite occurrences probably relate to broadening of XRD and FTIR spectra and can be explained by coupled Al–Si and Mg–Al substitutions in talc and serpentine. The FTIR spectra suggest widespread transformation of olivine to serpentine, unlike the largely unaltered chondrules. The correlations of mineralogical alteration index with FeO/SiO₂ and S/SiO₂ in different domains of matrix suggest different extent of alterations. Thus, the aqueous alteration is extensive but not pervasive. The majority of alteration seems to have occurred within the asteroidal parent body. The Mukundpura CM2 thus preserves a unique combination of relict chondrules and highly aqueous altered variegated matrix clasts, although the surface mineralogy resembles the C-type asteroids recently probed by OSIRIS-REx and Hayabusa-2 missions.     

Mineralogy of poorly crystalline aluminium phases in the B horizon of Podzols in southern Sweden

Poorly crystalline Al components of the clay fraction are often neglected in soil mineralogical studies. In this study 7 B horizons from podzolised soils in Sweden were analysed using a combination of infrared (IR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and selective extractions. It was found that most Bhs and Bs horizons contained allophane, imogolite and more or less hydroxy-interlayered vermiculite. Some Bhs and Bs horizons also contained small amounts of kaolinite and/or gibbsite. In one acid Bh horizon organically complexed Al was the only reactive Al fraction of importance. The vertical patterns of vermiculite and allophane/imogolite suggested that both had formed during the podzolisation process, but due to different mechanisms. The pattern of kaolinite and gibbsite occurrences indicated that these minerals were mostly inherited from the parent material. Oxalate and pyrophosphate extractions suggested that allophane and imogolite constituted the most important reactive inorganic Al fraction in the soils. This shows that allophane and imogolite seem to be the typical, rather than the occasional, reactive inorganic Al phases that form in the B horizon as a result of podzolisation.