A new view on gold speciation in sulfur-bearing hydrothermal fluids from in situ X-ray absorption spectroscopy and quantum-chemical modeling   总被引：2，自引：0，他引：2  

Gleb S. Pokrovski  Boris R. Tagirov  Jacques Schott  Jean-Louis Hazemann  Olivier Proux 《Geochimica et cosmochimica acta》2009,73(18):5406-5427

Despite the common belief that Au^I complexes with hydrogen sulfide ligands (H₂S/HS⁻) are the major carriers of gold in natural hydrothermal fluids, their identity, structure and stability are still subjects of debate. Here we present the first in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of the stability and structure of aqueous Au^I–S complexes at temperatures and pressures (T–P) typical of natural sulfur-rich ore-forming fluids. The solubility of native gold and the local atomic structure around the dissolved metal in S–NaOH–Na₂SO₄–H₂SO₄ aqueous solutions were characterized at temperatures 200–450 °C and pressures 300–600 bar using an X-ray cell that allows simultaneous measurement of the absolute concentration of the absorbing atom (Au) and its local atomic environment in the fluid phase. Structural and solubility data obtained from XAFS spectra, combined with quantum-chemical calculations of species geometries, show that gold bis(hydrogensulfide) Au(HS)₂⁻ is the dominant Au species in neutral-to-basic solutions (5.5  pH  8.5; H₂O–S–NaOH) over a wide range of sulfur concentrations (0.2 < ΣS < 3.6 mol/kg), in agreement with previous solubility studies. Our results provide the first direct determination of this species structure, in which two sulfur atoms are in a linear geometry around Au^I at an average distance of 2.29 ± 0.01 Å. At acidic conditions (1.5  pH  5.0; H₂O–S–Na₂SO₄–H₂SO₄), the Au atomic environment determined by XAFS is similar to that in neutral solutions. These findings, together with measured high Au solubilities, are inconsistent with the predominance of the gold hydrogensulfide Au(HS)⁰ complex suggested by recent solubility studies. Our spectroscopic data and quantum-chemical calculations imply the formation of species composed of linear S–Au–S moieties, like the neutral [H₂S–Au–SH] complex. This species may account for the elevated Au solubilities in acidic fluids and vapors with H₂S concentrations higher than 0.1–0.2 mol/kg. However, because of the complex sulfur speciation in acidic solutions that involves sulfite, thiosulfate and polysulfide species, the formation of Au^I complexes with these ligands (e.g., AuHS(SO₂)⁰, Au(HS₂O₃)₂⁻, Au(HS_n)₂⁻) cannot be ruled out. The existence of such species may significantly enhance Au transport by high T–P acidic ore-forming fluids and vapors, responsible for the formation of a major part of the gold resources on Earth.  相似文献   

A primordial origin for the atmospheric methane of Saturn’s moon Titan     

Olivier Mousis  Jonathan I. Lunine  Daniel Cordier  J. Hunter Waite Jr.  William S. Lewis 《Icarus》2009,204(2):749-751

The origin of Titan’s atmospheric methane is a key issue for understanding the origin of the saturnian satellite system. It has been proposed that serpentinization reactions in Titan’s interior could lead to the formation of the observed methane. Meanwhile, alternative scenarios suggest that methane was incorporated in Titan’s planetesimals before its formation. Here, we point out that serpentinization reactions in Titan’s interior are not able to reproduce the deuterium over hydrogen (D/H) ratio observed at present in methane in its atmosphere, and would require a maximum D/H ratio in Titan’s water ice 30% lower than the value likely acquired by the satellite during its formation, based on Cassini observations at Enceladus. Alternatively, production of methane in Titan’s interior via radiolytic reactions with water can be envisaged but the associated production rates remain uncertain. On the other hand, a mechanism that easily explains the presence of large amounts of methane trapped in Titan in a way consistent with its measured atmospheric D/H ratio is its direct capture in the satellite’s planetesimals at the time of their formation in the solar nebula. In this case, the mass of methane trapped in Titan’s interior can be up to ∼1300 times the current mass of atmospheric methane.  相似文献   

Radial thresholding to mitigate laser guide star aberrations on centre-of-gravity-based Shack–Hartmann wavefront sensors     

Olivier Lardière  Rodolphe Conan  Colin Bradley  Kate Jackson  Peter Hampton 《Monthly notices of the Royal Astronomical Society》2009,398(3):1461-1467

Sodium laser guide stars (LGSs) are elongated sources due to the thickness and the finite distance of the sodium layer. The fluctuations of the sodium layer altitude and atom density profile induce errors on centroid measurements of elongated spots, and generate spurious optical aberrations in closed-loop adaptive optics (AO) systems. According to an analytical model and experimental results obtained with the University of Victoria LGS bench demonstrator, one of the main origins of these aberrations, referred to as LGS aberrations, is not the centre-of-gravity (CoG) algorithm itself, but the thresholding applied on the pixels of the image prior to computing the spot centroids. A new thresholding method, termed 'radial thresholding', is presented here, cancelling out most of the LGS aberrations without altering the centroid measurement accuracy.  相似文献   

Atypical hotspot chains: evidence for a secondary melting zone below the Marquesas (French Polynesia)     

Christelle Legendre  Ren C. Maury  Sylvain Blais  Herv Guillou  Joseph Cotten 《地学学报》2006,18(3):210-216

The atypical age/distance to the hotspot relationships observed for the Marquesas linear chain, which present a considerable scatter, are best explained considering (1) a Pacific plate motion of 10.5 cm yr^?1 in the N115°E direction and (2) rejuvenation of volcanism in Ua Huka island. New K–Ar ages show that the main hotspot activity in Ua Huka emplaced successively shield olivine tholeiites and post‐shield alkali basalts between 3.11 ± 0.04 and 2.43 ± 0.04 Ma. Then, after a quiescence period of 1.28 ± 0.06 Myr, two small basanitic volcanoes were emplaced between 1.15 ± 0.02 and 0.763 ± 0.013 Ma. With respect to the main hotspot volcanics, their lavas originated from weaker partial melting rates of a deeper source. Field, petrologic and geochemical arguments are consistent with the existence of a secondary melting zone located c. 140 km downstream the Marquesas hotspot, which produced the rejuvenated volcanics.  相似文献   

Natural variations of Se isotopic composition determined by hydride generation multiple collector inductively coupled plasma mass spectrometry   总被引：1，自引：0，他引：1  

Olivier Rouxel  John LuddenJean Carignan  Luc MarinYves Fouquet 《Geochimica et cosmochimica acta》2002,66(18):3191-3199

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a “standard-sample bracketing” approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the ⁸²Se/⁷⁶Se isotope ratio is 0.25‰ (2σ), and the data are reported as delta notation (‰) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8‰ has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.  相似文献   

High-pressure,low-temperature metamorphism in Alpujarride Units of southeastern Betics (Spain)Métamorphisme de haute pression et basse température dans les unités Alpujarrides du Sud-Est de la cordillère Bétique (Espagne)     

Guillermo Booth-Rea  José Miguel Azañón  Bruno Goffé  Olivier Vidal  José Miguel Martı́nez-Martı́nez 《Comptes Rendus Geoscience》2002,334(11):857-865

We present the first occurrences of high-pressure, low-temperature ferro-magnesiocarpholite-bearing mineral assemblages associated to quartz segregations in the Alpujarride units of southeastern Betics (Sierra de Almagro, Sierra de los Pinos and Sierra Cabrera). Thermobarometric results show that the carpholite-bearing rocks underwent the same P–T conditions in the three outcrops, i.e. 8–10 kbar, 350–400 °C. Metamorphic and structural data allow us to conclude that these rocks belong to the same Alpujarride unit. In the Sierra de Almagro, tectonic units with carpholite-bearing rocks overlie low-pressure, low-temperature Alpujarride units, then forming a stack with an inverted tectono-metamorphic sequence, as observed in the central and western part of the Alpujarride complex. The preservation of carpholite-bearing assemblages in these rocks implies that no significant temperature increase occurred during the exhumation history. To cite this article: G. Booth-Rea et al., C. R. Geoscience 334 (2002) 857–865.  相似文献   

Partial melting below Tubuai (Austral Islands, French Polynesia)     

Martial Caroff  René C. Maury  Gérard Guille  Joseph Cotten 《Contributions to Mineralogy and Petrology》1997,127(4):369-382

Process identification diagrams based on trace element data show that mafic lavas from Tubuai, including alkali basalts, basanites, analcitites and nephelinites, result from different degrees of partial melting of an isotopically homogeneous mantle source. Our fractionation-corrected data are consistent with a batch melting model or a dynamic melting model involving a threshold value for melt separation close to 1% and degrees of melting ranging from 5–8% (alkali basalts) to 1.5–3% (nephelinites). The relative source concentration pattern, calculated using an inverse numerical method, shows an enrichment in highly incompatible elements. We propose that the Tubuai lava suite was derived from a two-stage partial melting process. Melting first affected the plume material located within the transition zone between garnet and spinel domains, producing alkali basalts and basanites. Then, the melting zone migrated upwards to the base of the overlying spinel-bearing lithospheric mantle, producing highly silica-undersaturated lavas. The lower lithosphere had previously been enriched by intrusion of pyroxenite veins representing plume-derived melts which percolated away from the main magma conduits. Received: 11 June 1996 / Accepted: 8 January 1997  相似文献   

Les « Porphyroı̈des » de Bretagne méridionale : une unité de HP–BT dans la chaı̂ne hercynienneEvidence for HP–LT Hercynian metamorphism within the ‘Porphyroı̈des’ of South Brittany (France)     

Florence Le Hébel  Olivier Vidal  Jean-Robert Kienast  Denis Gapais 《Comptes Rendus Geoscience》2002,334(3):205-211

The so-called ‘Porphyro??des’ Unit of South Brittany is located below units marked by an early HP–LT event (blueschists from the Île de Groix) and above units marked by Upper Carboniferous HT metamorphism. P–T estimates in the Porphyro??des (at Belle-Île-en-Mer), using the phengite–chlorite thermobarometer, indicate pressures around 8 kbar and temperatures of 350–400 °C. These new estimates suggest that the early tectonic history of the ‘Porphyro??des’ should be linked to that of the overlying Blueschists, and imply a much larger areal extension of the HP–LT domain in this part of the Hercynian Belt. To cite this article: F. Le Hébel et al., C. R. Geoscience 334 (2002) 205–211.  相似文献   

Coastal Precipitation Regimes in Kenya     

Pierre Camberlin  & Olivier Planchon 《Geografiska Annaler: Series A, Physical Geography》1997,79(1-2):109-119

Kenya is under the influence of the seasonal reversal of the Indian ocean monsoons. However, its coastal belt, up to about 50 km inland, exhibits original climatic features. Hierarchical clustering of mean monthly rainfall for a large number of stations, particularly in the south-eastern region, strongly differentiate a maritime climate characterised by enhanced and delayed "long rains" and no dry season in the northern summer. Most of these rains fall at night or in the morning. Using daily rainfall data and twice-daily surface and upper-air wind observations, monsoon-breeze interactions and their role on April–August coastal precipitation are assessed. Rain spells common to the whole Kenya coast are associated to a slight weakening of the sea breeze, a strong easterly or south-easterly wind anomaly over most of Kenya at around 850–700 hPa, and sea surface temperatures greater than air temperatures.  相似文献   

Evidence of a major environmental change recorded in a macrotidal bay (Marennes-Oléron Bay, France) by correlation between VHR seismic profiles and cores     

Isabelle Billeaud  Eric Chaumillon  Olivier Weber 《Geo-Marine Letters》2005,25(1):1-10

New, very high-resolution (25 cm) seismic profiles have revealed the internal architecture of the infilling of a macrotidal bay, the Marennes-Oléron Bay, France. Within this geometry, a major seismic unconformity has been correlated with core data. This correlation provides evidence that the seismic unconformity corresponds to a sharp grain-size decrease. Both seismic and core data indicate that this change of grain size can be interpreted as a record of a recent (around 1,000 years b.p.) decrease in hydrodynamical energy with time and/or a larger supply of fine-grained material. This recent environmental change can be related to natural infilling of the Marennes Oléron Bay, and to tidal prism decrease, increasing human activities (e.g. land reclamation, deforestation, agricultural land use) and climate fluctuations during the late Holocene, such as the transition between the cold period of the Dark Ages (1,550–1,050 years b.p.) and the Medieval warm period (1,050–550 years b.p.).  相似文献