Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ¹³C_gra value of −28.6 ± 4.4‰ (1σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ¹³C_gra values around −24.0 ± 0.3‰ (1σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies.Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ¹³C_gra values of −17.5 ± 2.5‰ (1σ), while δ¹³C_carb values in whole-rock powders average −4.0 ± 1.0‰ (1σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ¹³C_gra values averaging −13.8 ± 5.6‰ (1σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs.Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ¹³C_gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO₂- and CH₄-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO₂- and CH₄-bearing fluids that may have resulted in large ranges of δ¹³C_gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.     

变质岩中碳质物质的石墨化作用

碳质物质的石墨化作用随着变质程度的增强而增强,在低变质程度的岩石中。碳质物质实际上是非晶质的。在绿泥石变质带中,碳原子层开始按石墨构造有序堆砌,到十字石变质带时,它们几乎全部转变成了结晶好的石墨。除了变质程度以外,原岩的类型和碳的原始物质的种类也会影响碳的石墨化作用。碳颗粒的大小和形态也随变质程度规律地变化,到了十字石带,变化速度减慢。     

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.     

Thermal history recorded by the Apollo 17 impact melt breccia 73217

Lunar breccia 73217 is composed of plagioclase and pyroxene clasts originating from a single gabbronorite intrusion, mixed with a silica-rich glass interpreted to represent an impact melt. A study of accessory minerals in a thin section from this breccia (73217,52) identified three different types of zircon and anhedral grains of apatite which represent distinct generations of accessory phases and provide a unique opportunity to investigate the thermal history of the sample. Equant, anhedral zircon grains that probably formed in the gabbronorite, referred to as type-1, have consistent U-Pb ages of 4332 ± 7 Ma. A similar age of 4335 ± 5 Ma was obtained from acicular zircon (type-2) grains interpreted to have formed from impact melt. A polycrystalline zircon aggregate (type-3) occurs as a rim around a baddeleyite grain and has a much younger age of 3929 ± 10 Ma, similar to the 3936 ± 17 Ma age of apatite grains found in the thin section. A combined apatite-type-3 zircon age of 3934 ± 12 Ma is proposed as the age of the Serenitatis impact event and associated thermal pulse. X-ray mapping and electron probe analyses showed that Ti is inhomogeneous in the zircon grains on the sub-micrometer scale. However, model temperatures estimated from SHRIMP analyses of Ti-concentration in the 10 μm diameter spots on the polished surfaces of type-1 and type-2 zircons range between about 1300 and 900 °C respectively, whereas Ti-concentrations determined for the type-3 zircon are higher at about 1400-1500 °C. A combination of U-Pb ages, Ti-concentration data and detailed imaging and petrographic studies of the zircon grains shows that the gabbronorite parent of the zircon clasts formed shortly before the 4335 ± 5 Ma impact, which mixed the clasts and the felsic melt and projected the sample closer to the surface where fast cooling resulted in the crystallization of acicular zircon (type-2). The 3934 ± 12 Ma Serenitatis event resulted in partial remelting of the glass and formation of polycrystalline zircon (type-3). This event also reset the U-Pb system of apatite, formed merrillite coronas around some apatite grains, and probably re-equilibrated some pyroxenes in the clasts. Although there have been arguments for pre-3.9 Ga impacts based on other types of samples, the age of the acicular zircon at 4335 ± 5 Ma provides the first evidence of impact melt significantly predating the lunar cataclysm. Our data, combined with other chronological results, demonstrate the occurrence of pre-3.9 Ga impacts on the Moon and suggest that the lunar impact history consisted of a series of intense bombardment episodes interspersed with relatively calm periods of low impact flux.     

Nitrogen and argon isotopic signatures in graphite from the 3.8-Ga-old Isua Supracrustal Belt, Southern West Greenland

The problems involved with the interpretation of carbon isotopes as indicators for early life in highly metamorphosed early Archean rocks have prompted the search for additional chemical and isotopic biomarkers. Here we report an attempt to identify the origin of carbonaceous matter in the 3.8 Ga old Isua Supracrustal Belt in southern West Greenland by measuring the concentration and isotopic composition of a trapped nitrogen component. Stepped-combustion/pyrolysis-mass spectrometry of carbonaceous matter in several rock samples revealed three different reservoirs of trapped nitrogen: (1) nitrogen associated with a very small amount of reactive carbonaceous material, (2) nitrogen intercalated in graphite, correlated with intercalated radiogenic argon, (3) nitrogen strongly retained at defects or chemically bound in the graphite structure. The δ¹⁵N of nitrogen associated with reactive carbonaceous matter (ca. +6‰) overlaps with that of average Phanerozoic sedimentary organic matter, and is believed to be part of nonindigenous postmetamorphic biologic material. In situ Raman spectroscopy confirmed the high degree of crystallinity of the metamorphosed indigenous carbonaceous material, and this material is further referred to as graphite. Graphite interpreted as epigenetic (associated with Mg,Mn-siderite in metacarbonates) contains a very small strongly retained nitrogen component with a low δ¹⁵N ratio (−3 to −1‰). This range overlaps with values that are typically found in Archean kerogens, but also those of a metamorphically emplaced inorganic basaltic source. Geological constraints suggest that this graphite incorporated nitrogen from surrounding metabasaltic rocks. Graphite interpreted as syngenetic and biogenic found in a turbidite deposit is relatively similar to this Mg,Mn-siderite-derived graphite, based on degree of graphite crystallinity, amount of trapped radiogenic argon, low nitrogen concentration and δ¹⁵N signature. We conclude that nitrogen concentration and its isotope ratio in graphite cannot be used conclusively as a biomarker in these rocks from the highly metamorphosed Isua Supracrustal Belt.     

Metamorphism of carbonaceous material in the Tono contact aureole, Kitakami Mountains, Japan

Abstract Optical and X-ray studies of carbonaceous material in the Tono contact metamorphic aureole, Kitakami Mountains, northeast Japan, have revealed that metamorphic graphitization proceeded through two discontinuous changes: first, optically anisotropic domains develop within the coaly phytoclast, forming transitional material, and then, ordered graphite crystallizes by the decomposition of pre-existing carbonaceous materials. Coaly material disappears in the uppermost chlorite zone. Transitional material appears in the middle of the lower chlorite zone. Graphite appears in the upper chlorite zone and its modal abundance increases across the andalusite iso-grad to the cordierite isograd where all the carbonaceous materials have converted to graphite. The apparently continuous variation in the crystallographic parameters of the bulk carbonaceous material during graphitization is largely due to variation in the modal proportions of three types of carbonaceous materials. The temperature of graphitization in the present area is at least 100°C higher than the temperature in the Sanbagawa and New Caledonia high-pressure metamorphic terrains, probably due to the slow reaction rate of metamorphic graphitization and to the short duration of contact metamorphism.     

Metamorphic alteration,mineral paragenesis and geochemical re-equilibration of early Archean quartz–amphibole–pyroxene gneiss from Akilia,Southwest Greenland

Quartz–amphibole–pyroxene gneiss from the island of Akilia, Southwest Greenland has been claimed to contain the earliest traces of life on Earth in the form of biogenic carbonaceous matter encapsulated as inclusions in apatite crystals. Various lines of evidence, including petrography, geochronology, field relations, and geochemistry, have, however, been presented that challenge this interpretation. Textural relationships and geochemical signatures in this controversial gneiss presented here manifest a complex, spatially variable metamorphic history that includes granulite- and amphibolite-facies overprints and metasomatism. A peak metamorphic, granulite-facies, quartz–orthopyroxene–clinopyroxene–amphibole–magnetite assemblage is preserved in only a few centimeter-scale layers within the 5-m-thick, quartz–amphibole–pyroxene gneiss unit. Calcite veinlets that appear to postdate the peak metamorphism occur in pyroxene. The quartz–amphibole–pyroxene gneiss unit has subsequently experienced isochemical (except hydration) amphibolite-facies alteration during which pyroxenes were retrogressed to amphiboles and magnetite, and calcite was consumed. Parts of the quartz–amphibole–pyroxene gneiss that contain texturally late hornblende have experienced metasomatic alteration by Al-carrying fluids. These fluids controlled the alteration of pyroxenes and amphiboles to hornblende, and modified the trace-element composition by remobilizing LREE and Eu. Apatite has variable REE composition and ⁸⁷Sr/⁸⁶Sr in the quartz–amphibole–pyroxene gneiss, but on the local scale (cm) is in equilibrium with co-existing silicates. Effective recrystallization of apatite crystals as well as co-existing silicates during several stages of the metamorphic history makes the intact preservation of diagenetic apatite with encapsulated primary carbonaceous matter implausible. Hence, it is highly unlikely that Akilia apatite could serve as repository of the earliest traces of life on Earth.     

Carbonaceous cherts of the Barberton Greenstone Belt, South Africa: Isotopic, chemical and structural characteristics of individual microstructures

Carbonaceous matter occurring in chert deposits of the 3.4-3.2 Ga old Barberton Greenstone Belt (BGB), South Africa, has experienced low grade regional metamorphism and variable degrees of local hydrothermal alteration. Here a detailed study is presented of in situ analysis of carbonaceous particles by LRS (laser Raman spectroscopy) and SIMS (secondary ion mass spectrometry), reporting degree of structural disorder, carbon isotope ratio and nitrogen-to-carbon ratio. This combination of in situ analytical tools is used to interpret the δ¹³C values of only the best preserved carbonaceous remains, enabling the rejection of non-indigenous (unmetamorphosed) material as well as the exclusion of strongly hydrothermally altered carbonaceous particles. Raman spectroscopy confirmed that all carbonaceous cherts studied here have experienced a regional sub- to lower-greenschist facies metamorphic event. Although this identifies these organics as indigenous to the cherts, it is inferred from petrographic observations that hydrothermal alteration has caused small scale migration and re-deposition of organics. This suggest that morphological interpretation of these carbonaceous particles, and in general of putative microfossils or microlaminae in hydrothermally altered early Archean cherts, should be made with caution. A chert in the Hooggenoeg Formation, which is older than and has been hydrothermally altered by a volcanic event 3445 Ma ago, contains strongly altered carbonaceous particles with a uniform N/C-ratio of 0.001 and a range of δ¹³C that is shifted from its original value. Cherts of the Kromberg Formation post-date this volcanic event, and contain carbonaceous particles with a N/C-ratio between 0.002 and 0.006. Both the Buck Reef Chert and the Footbridge Chert of the Kromberg Formation have retained fairly well-preserved δ¹³C values, with ranges from −34‰ to −24‰ and −40‰ to −32 ‰, respectively. Abiologic reactions associated with hydrothermal serpentinization of ultramafic crust (such as Fischer-Tropsch synthesis) were an unlikely source for carbonaceous material in these cherts. The carbonaceous matter in these cherts has all the characteristics of metamorphosed biologic material.     

Geo- and cosmochemistry of the twin elements yttrium and holmium

We have analyzed the Y/Ho-ratios in bulk chondrites, chondrules and four Ca- and Al-rich inclusions (CAIs) from carbonaceous and unequilibrated ordinary and enstatite chondrites (EC) by laser ablation inductively coupled mass spectrometry (LA-ICPMS). We demonstrate that bulk rock sample preparation by containerless melting is a suitable method for preparation of bulk rock samples for high-precision LA-ICPMS. Bulk chondrites have variable Y/Ho-ratios. Carbonaceous chondrites (CI1, CM2, CV3, and CK4) have a common Y/Ho-ratio (25.94 ± 0.08, 2σ) that is regarded as the solar system Y/Ho-ratio. The Y/Ho-ratio increases from carbonaceous, through ordinary (LL, L, H) to enstatite chondrites (EL6), which show the highest Y/Ho-ratio of 27.25. We discuss the result with respect to the origin of fractionation of Re and Os between chondrite groups. Within analytical error, Y and Ho show a good correlation in OC and CV3 chondrules and define an Y/Ho-ratio of 26.22 ± 0.40 (2σ). Y/Ho-fractionation in Ca- and Al-rich inclusions is related to differences in volatility. The bulk silicate Earth is suggested to have a solar Y/Ho-ratio and links the Earth with carbonaceous chondrites. Y/Ho variations in primitive and differentiated terrestrial igneous rocks are discussed in framework of incompatibility of Y and Ho during partial melting. Applicability of Y/Ho as tracer for or against a sedimentary origin of the putative host rock of the Earth’s oldest traces of life from the island of Akilia is briefly discussed.     

Structures, origin and evolution of various carbon phases in the ureilite Northwest Africa 4742 compared with laboratory-shocked graphite

Mineralogical structures of carbon phases within the ureilite North West Africa 4742, a recent find, are investigated at various scales by high-resolution transmission electron microscopy (HRTEM), Raman microspectrometry and X-ray diffraction. Ureilites are the most carbon-rich of all meteorites, containing up to 6 wt.% carbon. Diamond, graphite and so-called “amorphous carbon” are typically described, but their crystallographic relationships and respective thermal histories remain poorly constrained. We especially focus on the origin of “amorphous carbon” and graphite, as well as their relationship with diamond.Two aliquots of carbon-bearing material were extracted: the insoluble organic matter (IOM) and the diamond fraction. We also compare the observed structures with those of laboratory-shocked graphite.Polycrystalline diamond aggregates with mean coherent domains of about 40 nm are reported for the first time in a ureilite and TEM demonstrates that all carbon phases are crystallographically related at the nanometre scale.Shock features show that diamond is produced from graphite through a martensitic transition. This observation demonstrates that graphite was present when the shock occurred and is consequently a precursor of diamond. The structure of what is commonly described as the “amorphous carbon” has been identified. It is not completely amorphous but only disordered and consists of nanometre-sized polyaromatic units surrounding the diamond. Comparison with laboratory-shocked graphite, partially transformed into diamond, indicates that the disordered carbon could be the product of diamond post-shock annealing.As diamond is the carrier of noble gases, whereas graphite is noble gas free, graphite cannot be the sole diamond precursor. This implies a multiple-stage history. A first generation of diamond could have been synthesized from a noble gas rich precursor or environment by either a shock or a condensation process. Thermally-induced graphitization of chondritic-like organic matter could have produced the graphite, which was then transformed by shock processes into polycrystalline nanodiamond aggregates. The formation of the disordered carbon occurred by diamond post-shock back-transformation during post-shock heating. The noble gases in the first generation diamond could then be incorporated directly into the disordered carbon during the transformation.     

Graphite of the Turgenevskoe and Tamginskoe deposits of the Lesozavodsk area in the Primor’e region

The regional carbonization of the Riphean metamorphic complexes is discussed using as an example the Tamginskoe and Turgenevskoe graphite deposits located in the northern part of the Khanka terrane. It is shown that the noble metal mineralization associates closely with the graphitization. Isotopic, X-ray, and thermal analyses and Raman spectroscopy were first used for investigating the structural state of the graphite with defining its two varieties. The first of them is represented by nanocrystalline fluidogenic graphite that was formed during gas condensate crystallization from deep-seated reduced ore-bearing fluid. The second variety (large-flake graphite) represents a product of metamorphic recrystallization of carbonaceous terrigenous protoliths. The recrystallization was accompanied by the granitization of the sedimentary protolith, mobilization, and the transfer of the carbonaceous and ore matter of the host rocks. It is inferred that the graphitization associated with noble metal mineralization is a polygenic process. The graphite of the first generation associates closely with amorphous diamond-like carbon. This unexpected find may bear genetic information useful for geological and geochemical reconstructions.     

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.     

Meteorite ablation products and their contribution to the atmospheres of terrestrial planets: An experimental study using pyrolysis-FTIR

We have used a recently developed quantitative pyrolysis-Fourier transform infrared spectroscopy method to measure the production of water and carbon dioxide during 250 °C desorption and 1000 °C gasification steps for a range of carbonaceous chondrites. Greater yields of water and carbon dioxide during gasification are associated with meteorites believed to have experienced more aqueous alteration on their asteroid parent body (i.e. gas yields for petrographic type 1 > type 2 > type 3). Volatile yields most likely reflect quantities of hydrated mineral phases and partially oxidised organic matter. Methane was not detected in the gasification products of the meteorites, allowing an upper limit on its production of around 100 ppm to be calculated based on the sensitivity of the pyrolysis-Fourier transform infrared spectroscopy technique employed. When considered alongside rates of infall of cosmic dust throughout Earth history, the data can be used to evaluate the production of volatiles during the thermal ablation of dust upon atmospheric entry, and to estimate their contribution to a terrestrial planet’s atmosphere and hydrosphere. Over the long term, it appears that contributions of this nature to the Earth’s volatile inventory are small, although production rates are calculated to have been substantially higher before and during the Late Heavy Bombardment of 3.8-4.0 Ga. Moreover, ablation of carbonaceous chondritic material does not appear to be a plausible source of the atmospheric methane budget of Mars.     

Complex history of a zircon aggregate from lunar breccia 73235

Results are reported of an investigation of the age and origin of the exceptional zircon aggregate in an anorthositic clast from lunar breccia 73235. Cathodoluminescence and birefringence images show that the aggregate consists of numerous angular fragments of sector zoned primary zircon in a matrix of secondary zircon with an overall texture that resembles a pseudotachylite. SIMS U-Pb analyses of the primary fragments and the matrix yielded two clearly defined ages, an age of 4.315 ± 0.015 Ga and initial Th/U ratio of 0.21-0.35 for the primary zircon and an age of 4.187 ± 0.011 Ga and Th/U of 0.04-0.17, for the secondary zircon matrix. A Raman spectroscopic study the secondary matrix zircon was undertaken to investigate its structure. Results showed that the matrix has a zircon structure but there is also evidence for the presence of an amorphous component. Implications of the structural and U-Pb age data are discussed in terms of the origin and evolution of the aggregate and the history of lunar events. It is proposed that an original single, millimetre-sized, sector zoned zircon, formed at 4.31 Ga, was subjected to a severe shock event at 4.18 Ga. This event resulted in the fracturing of the zircon, the displacement and rotation of fragments, the compression of the aggregate to a lensoid shape, and the shock reduction of zircon to sub-micron-sized and amorphous granules in crush zones in the mosaic of fractures. Volatilisation loss of Pb and the addition of U to the secondary zircon is attributed to processes activated by the extreme thermal pulse which accompanied the 4.18 Ga shock event. Shock effects are seen in some of the primary fragments but Raman spectra of the primary and secondary zircon show no evidence for pressure-induced transformation of zircon to a scheelite structure. The zircon U-Pb system has not been affected by the ca. 3.95 Ga thermal pulse that accompanied formation of the host breccia although this event has largely reset the K-Ar systems.     

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.     

Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ²⁵Mg = −0.14 ± 0.06; δ²⁶Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ⁷Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ⁷Li = 3.5 ± 0.5‰, δ²⁵Mg = −0.10 ± 0.03‰ and δ²⁶Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ⁷Li and δ²⁶Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ⁷Li and δ²⁶Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ⁷Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ⁷Li seen in some oceanic basalts.     

Mineralogical Characterization of Graphite Deposits from Thodupuzha-Kanjirappally Belt, Madurai Granulite Block, Southern India

Graphite from deposits occurring in the high-grade metamorphic rocks and their larteritized equivalents of the Thodupuzha-Kanjirappally Belt in Madurai Granulite Block, southern India is structurally fully ordered (crystallite size, Lc₍₀₀₂₎ ranging from 469 to 749 Å), possess high degree of graphitization (DG value ranging from 105 to 267 Å) and reflect crystallization at high temperature (700±100°C). Raman spectra of graphite display profiles corresponding to high crystallinity and high structural ordering. The high temperature crystallinity characteristics of graphite were not obliterated during retrogression of granulites to amphibolite facies gneisses. Preliminary carbon stable isotope results show a spread in isotope values from —11.8 to —26.8 %, which suggest more than one sources for carbon. The lighter carbon isotope values are suggestive of biogenic origin, whereas the heavier ones are probably fluid precipitated graphite.     

Monazite, iron oxide and barite exsolutions in apatite aggregates from CCSD drillhole eclogites and their geological implications

We have identified abundant exsolutions in apatite aggregates from eclogitic drillhole samples of the Chinese Continental Scientific Drilling (CCSD) project. Electron microscope and laser Raman spectroscopy analyses show that the apatite is fluorapatite, whereas exsolutions that can be classified into four types: (A) platy to rhombic monazite exsolutions; (B) needle-like hematite exsolutions; (C) irregular magnetite and hematite intergrowths; and (D) needle-like strontian barite exsolutions. The widths and lengths of type A monazite exsolutions range from about 6-10 μm (mostly 6 μm) and about 50-75 μm, respectively. Type B exsolutions are parallel with the C axis of apatite, with widths ranging from 0.5 to 2 μm, with most around 1.5 μm, and lengths that vary dramatically from 6 to 50 μm. Type C exsolutions are also parallel with the C axis of apatite, with lengths of ∼30-150 μm and widths of ∼10 to 50 μm. Type D strontian barite exsolutions coexist mostly with type B hematite exsolutions, with widths of about 9 μm and lengths of about 60-70 μm. Exsolutions of types B, C and D have never been reported in apatites before. Most of the exsolutions are parallel with the C axis of apatite, implying that they were probably exsolved at roughly the same time. Dating by the chemical Th-U-total Pb isochron method (CHIME) yields an U-Pb isochron age of 202 ± 28 Ma for monazite exsolutions, suggesting that these exsolutions were formed during recrystallization and retrograde metamorphism of the exhumed ultrahigh pressure (UHP) rocks. Quartz veins hosting apatite aggregates were probably formed slightly earlier than 202 Ma. Abundant hematite exsolutions, as well as coexistence of magnetite/hematite and barite/hematite in the apatite, suggest that the oxygen fugacity of apatite aggregates is well above the sulfide-sulfur oxide buffer (SSO). Given that quartz veins host these apatite aggregates, they were probably deposited from SiO₂-rich hydrous fluids formed during retrogression of the subducted slab. Such SiO₂-rich hydrous fluids may act as an oxidizing agent, a feasible explanation for the high oxygen fugacity in convergent margin systems.     

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.     

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.