Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

Inclusions of silicate and sulfate melts in chrome diposide from the Inagli deposit,Yakutia, Russia

Melt inclusions were studied in chrome diopside from the Inagli deposit of gemstones in the Inagli massif of alkaline ultrabasic rocks of potassic affinity in the northwestern Aldan shield, Yakutia, Russia. The chrome diopside is highly transparent and has an intense green color. Its Cr₂O₃ content varies from 0.13 to 0.75 wt %. Primary and primary-secondary polyphase inclusions in chrome diopside are dominated by crystal phases (80–90 vol %) and contain aqueous solution and a gas phase. Using electron microprobe analysis and Raman spectroscopy, the following crystalline phases were identified. Silicate minerals are represented by potassium feldspar, pectolite [NaCa₂Si₃O₈(OH)], and phlogopite. The most abundant minerals in the majority of inclusions are sulfates: glaserite (aphthitalite) [K₃Na(SO₄)₂], glauberite [Na₂Ca(SO₄)₂], aluminum sulfate, anhydrite (CaSO₄), gypsum (CaSO₄ × 2H₂O), barite (BaSO₄), bloedite [Na₂Mg(SO₄)₂ × 4H₂O], thenardite (NaSO₄), polyhalite [K₂Ca₂Mg(SO₄)₄ × 2H₂O], arcanite (K₂SO₄), and celestite (SrSO₄). In addition, apatite was detected in some inclusions. Chlorides are probably present among small crystalline phases, because some analyses of aggregates of silicate and sulfate minerals showed up to 0.19–10.3 wt % Cl. Hydrogen was identified in the gas phase of polyphase inclusions by Raman spectroscopy. The composition of melt from which the chrome diopside crystallized was calculated on the basis of the investigation of silicate melt inclusions. This melt contains 53.5 wt % SiO₂, considerable amounts of CaO (16.3 wt %), K₂O (7.9 wt %), Na₂O (3.5 wt %), and SO₃ (1.4 wt %) and moderate amounts of Al₂O₃ (7.5 wt %), MgO (5.8 wt %), FeO (1.1 wt %), and H₂O (0.75 wt %). The content of Cr₂O₃ in the melt was 0.13 wt %. Many inclusions were homogenized at 770–850°C, when all of the crystals and the gas phase were dissolved. The material of inclusions heated up to the homogenization temperature became heterogeneous even during very fast quenching (two seconds) producing numerous small crystals. This fact implies that most of the inclusions contained a salt (rather than silicate) melt of sulfate-dominated composition. Such inclusions were formed from salt globules (with a density of about 2.5 g/cm³) occurring as an emulsion in the denser (2.6 g/cm³) silicate melt from which the chrome diopside crystallized.     

Late Palaeozoic hydrocarbon migration through the Clair field, West of Shetland, UK Atlantic margin

Geochemical analysis of bitumen- and hydrocarbon-bearing fluid inclusions from the Devonian-Carboniferous Clair field indicates that the reservoirs contain a mixture of oils from different marine and lacustrine sources. Reconstruction of the Clair field oil-charge history using fluid inclusion petrography show that oil-charging occurred at times of K-feldspar, quartz and calcite cementation. Temperature–composition–time data yielded from the integration of fluid inclusion microthermometry with high-resolution Ar–Ar dating, date hydrocarbon-bearing K-feldspar overgrowths at 247 ± 3.3 Ma. These data show that in order for oil to be trapped within primary fluid inclusions in K-feldspar overgrowths, hydrocarbon migration throughout the UK Atlantic margin must have been taking place during the Late Palaeozoic and as such, current industry oil-play models based solely on oil charging from Jurassic-Cretaceous marine sources are clearly incomplete and need revision. Apatite fission track analysis and vitrinite reflectance data were used to reconstruct thermal burial histories and assess potential oil generation from Middle Devonian lacustrine source rocks. Thermal history data from wells along The Rona Ridge adjacent to the Clair field show that the Palaeozoic section was heated to greater than 100 °C at some time between 270 and 230 Ma, confirming that Devonian source rocks were mature and expelling oil during the Late Palaeozoic at the time that authigenic K-feldspar overgrowths were growing in the Clair field.     

Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Enhancing understanding of breakdown and collapse in the Yorkshire Dales using ground penetrating radar on cave sediments

Historical evidence shows block breakdown and collapse are actively occurring in large fault aligned caverns in the Yorkshire Dales karst. Deployment of ground penetrating radar at two such sites has provided detailed images of the sedimentary sequences below the present day cavern floor but no large blocks are imaged within the sediments. Solutional processes must be removing limestone from the sediment to allow continued cavern growth. Possible mechanisms to account for the lack of large blocks within the sediment fill are discussed.     

Assessing soil erosion in Mediterranean karst landscapes of Lebanon using remote sensing and GIS

Maps showing the potential for soil erosion at 1:100,000 scale are produced in a study area within Lebanon that can be used for evaluating erosion of Mediterranean karstic terrain with two different sets of impact factors built into an erosion model. The first set of factors is: soil erodibility, morphology, land cover/use and rainfall erosivity. The second is obtained by the first adding a fifth factor, rock infiltration. High infiltration can reflect high recharge, therefore decreasing the potential of surface runoff and hence the quantity of transported materials. Infiltration is derived as a function of lithology, lineament density, karstification and drainage density, all of which can be easily extracted from satellite imagery. The influence of these factors is assessed by a weight/rate approach sharing similarities between quantitative and qualitative methods and depending on pair-wise comparison matrix.The main outcome was the production of factorial maps and erosion susceptibility maps (scale 1:100,000). Spatial and attribute comparison of erosion maps indicates that the model that includes a measure of rock infiltration better represents erosion potential. Field investigation of rills and gullies shows 87.5% precision of the model with rock infiltration. This is 17.5% greater than the precision of the model without rock infiltration. These results indicate the necessity and importance of integrating information on infiltration of rock outcrops to assess soil erosion in Mediterranean karst landscapes.