Multi-stage mixing in subduction zones: Application to Merapi volcano (Java island, Sunda arc)

Many studies have argued for the contribution of at least three components, namely the mantle wedge, the subducted oceanic crust, and its sediment cover, to describe the geochemistry of island arc volcanics. However, isotope correlations reflecting a simple binary mixing can be observed at the scale of a single arc island or volcano. Here we investigate the possibility that these trends reflect pseudo-binary mixing relationships in a three-component system. We present a simplified, two-stage model for the systematic isotope modelling of a cogenetic suite of arc lavas. This includes metasomatism of portions of the mantle wedge by hydrous phases released from the down-going oceanic crust, and sediments, followed by progressive mixing and melting. A consequence of this model is that it leads to a two end-member mixing process from the mantle wedge, oceanic crust, and sediment components. To solve the model we reduce it to a step-by-step procedure combined with a Monte-Carlo simulation. The procedure consists of: (i) producing a large number of random values on each variable of the model; (ii) using the computed values to calculate the isotopic compositions of lavas; and (iii) comparing the obtained isotopic compositions with measured data. Applied to a new set of Sr, Nd, and Pb isotope data for volcanics (basalts, basaltic andesites, trachybasalts, and basaltic trachyandesites) from Merapi volcano (Java island, Sunda arc), the model successfully reproduces the binary mixing relationships previously documented for the medium-K and high-K lava series from this volcano, thus giving further support to the hypothesis that this distinction is inherited from the primary magmas and primarily reflects a property of the mantle source. The results allow identification of a set of numerical values for bulk partition coefficients (solid/hydrous fluid, and solid/H₂O-rich melt) and variables (e.g., the mass ratio between the metasomatizing phase and the mantle wedge), which can be used for quantitative arc-lava petrogenetic calculations. They also require a direct relationship between dehydration of the slab and melting of the metasomatized mantle wedge. Finally, our evaluation shows that for isotope modelling of the Merapi lavas, the two-stage procedure is controlled more by the considered source components (mantle wedge, oceanic crust, sediments, and their derivatives) than by the various processes involved (dehydration, melting, and mixing).     

Characterization and migration of atmospheric REE in soils and surface waters

Rainwater and snow collected from three different sites in France (Vosges Mountains, French Alps and Strasbourg) show more or less similar shapes of their REE distribution patterns. Rainwater from Strasbourg is the most REE enriched sample, whereas precipitations from the two mountainous, less polluted catchments are less REE enriched and have concentrations close to seawater. They are all strongly LREE depleted.Different water samples from an Alpine watershed comprising snow, interstitial, puddle and streamwater show similar REE distributions with LREE enrichment (rainwater normalized) but MREE and HREE depletion. In this environment, where water transfer from the soil to the river is very quick due to the low thickness of the soils, it appears that REE in streamwater mainly originate from atmospheric inputs. Different is the behaviour of the REE in the spring- and streamwaters from the Vosges Mountains. These waters of long residence time in the deep soil horizons react with soil and bedrock REE carrying minerals and show especially significant negative Eu anomalies compared to atmospheric inputs. Their Sr and Nd isotopic data suggest that most of the Sr and Nd originate from apatite leaching or dissolution. Soil solutions and soil leachates from the upper soil horizons due to alteration processes strongly depleted in REE carrying minerals, have REE distribution patterns close to those of lichens and throughfall. Throughfall is slightly more enriched especially in light REE than filtered rainwater probably due to leaching of atmospheric particles deposited on the foliage and also to leaf excretion.Data suggest that Sr and Nd isotopes of the soil solutions in the upper soil horizons originate from two different sources: 1) An atmospheric source with fertilizer, dust and seawater components and 2) A source mainly determined by mineral dissolution in the soil. These two different sources are also recognizable in the Sr and Nd isotopic composition of the tree’s throughfall solution. The atmospheric contributions of Sr and Nd to throughfall and soil solution are of 20 to 70 and 20%, respectively. In springwater, however, the atmospheric Sr and REE contribution is not detectable.     

Seismic endoscopy: multi-offset multi-azimuth imaging around boreholes – data processing and experimental results

An acoustic method, called seismic endoscopy, able to perform 3D imaging around shallow-depth boreholes is presented. A probe, composed of an isotropic source and a directional receiver working in the 20–100 kHz frequency range, provides images of cylindrical volumes having radii of a few metres, with an accuracy of centimetres and 25° azimuthal directivity. In order to obtain clear images of the medium discontinuities, multi-offset and multi-azimuth data acquisition allows specific algorithms to be used to determine vertical directivity correction, azimuthal focusing and reflected wave enhancement by cancellation of the tube waves. The method is tested with data acquired in an acoustic tank and with synthetic data. Initial experimental results at a test site demonstrate the performance of the seismic endoscopy probe.     

Spatiotemporal changes in cadmium contamination in the Seine estuary (France)

Cadmium (Cd) is among the major contaminants in the Seine estuary. In the biota, the RNO (Réseau National d’Observation, the French Mussel-Watch) has shown that Cd concentrations in mussels living at the mouth of the estuary are related to changes in inputs to this area of phosphogypsum, a calcium sulphate that is a by-product of the phosphoric acid naturally enriched with Cd. In the water column, Cd concentrations at several key estuary sites show a very marked trend toward decreased contamination in the particles as well as in the dissolved phase. The behavior of Cd in the estuary has been studied between 1991 and 1998 in the framework of the scientific program Seine-Aval. This program has highlighted punctual Cd inputs in the estuarine water column. The partition of Cd between the dissolved and the particulate phase, previously described in various estuaries, is characterized by an intense phenomenon of solubilization in the mixing zone freshwater-seawater, but the colloidal Cd fraction remains low along the whole salinity gradient, about 5% to 10% of the apparent dissolved fraction. Although the decrease of inputs induced a fall of Cd concentrations in the water column, laboratory experiments show that the estuarine particles are far from being exhausted in Cd. Despite continuous efforts to reduce the urban and industrial inputs into the estuarine and coastal waters, the Seine estuary still remains very contaminated by Cd.     

Role of the Kazerun fault system in active deformation of the Zagros fold-and-thrust belt (Iran)

Field structural and SPOT image analyses document the kinematic framework enhancing transfer of strike-slip partitioned motion from along the backstop to the interior of the Zagros fold-and-thrust belt in a context of plate convergence slight obliquity. Transfer occurs by slip on the north-trending right-lateral Kazerun Fault System (KFS) that connects to the Main Recent Fault, a major northwest-trending dextral fault partitioning oblique convergence at the rear of the belt. The KFS formed by three fault zones ended by bent orogen-parallel thrusts allows slip from along the Main Recent Fault to become distributed by transfer to longitudinal thrusts and folds. To cite this article: C. Authemayou et al., C. R. Geoscience 337 (2005).     

Coeval potassic and sodic calc-alkaline series in the post-collisional Hercynian Tanncherfi intrusive complex, northeastern Morocco: geochemical, isotopic and geochronological evidence

The post-collisional late Hercynian Tanncherfi intrusive complex (TIC) is part of a widespread intrusive episode in the Moroccan Meseta. The complex contains a wide range of rock types, from monzogabbros to monzogranites. Two distinct magmatic series are recognized: (1) a potassic (shoshonitic) series consisting of monzogabbros, quartz monzonites and monzogranites; and (2) a sodic (granodioritic) series represented by quartz monzodiorites and granodiorites. All the Tanncherfi plutonic rocks display similar spider-diagram profiles, with LILE and LREE enrichment and Nb, Ta, Ti depletion, which are typical of subduction-related magmas. Combined major, trace element compositions and Sr, Nd isotopic results indicate that the two series have been derived from a LILE- and LREE-enriched continental lithospheric mantle source, under different partial melting and/or depth conditions. Intrusion of the Tanncherfi rocks was not temporally related to subduction and the enrichment of their source is likely to be linked to preceding subduction events. The two series evolved by fractional crystallization, of clinopyroxene, plagioclase, hornblende, biotite, K-feldspar and accessories (Fe–Ti oxide minerals, titanite, apatite and zircon) for the potassic series while the sodic series combined fractional crystallization with assimilation of felsic magmas with lower Sr isotopic ratio than the more mafic term of the series, the quartz monzodiorite. The intrusion of the potassic magmas (344±6 Ma) marks a major change in the tectonic regime of eastern Meseta. These magmas intruded during post-thickening uplift and extension, both probably favored by convective thinning of the lithosphere. This model provides a reasonable mechanism for the genesis of other Hercynian intrusive complexes in Morocco.     

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.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Heliocentric evolution of the degradation of polyoxymethylene: Application to the origin of the formaldehyde (H2CO) extended source in Comet C/1995 O1 (Hale-Bopp)

The H₂CO production rates measured in Comet C/1995 O1 (Hale-Bopp) from radio wavelength observations [Biver, N., and 22 colleagues, 2002a. Earth Moon Planets 90, 5-14] showed a steep increase with decreasing heliocentric distance. We studied the heliocentric evolution of the degradation of polyoxymethylene (formaldehyde polymers: (CH₂O)_n, also called POM) into gaseous H₂CO. POM decomposition can indeed explain the H₂CO density profile measured in situ by Giotto spacecraft in the coma of Comet 1P/Halley, which is not compatible with direct release from the nucleus [Cottin, H., Bénilan, Y., Gazeau, M.-C., Raulin, F., 2004. Icarus 167, 397-416]. We show that the H₂CO production curve measured in Comet C/1995 O1 (Hale-Bopp) can be accurately reproduced by this mechanism with a few percents by mass of solid POM in grains. The steep heliocentric evolution is explained by the thermal degradation of POM at distances less than 3.5 AU. This study demonstrates that refractory organics present in cometary dust can significantly contribute to the composition of the gaseous coma. POM, or POM-like polymers, might be present in cometary grains. Other molecules, like CO and HNC, might also be produced by a similar process.