Hydraulic conductivity distribution in crystalline rocks, derived from inflows to tunnels and galleries in the Central Alps, Switzerland   总被引：4，自引：3，他引：1  

Olivier Masset  Simon Loew 《Hydrogeology Journal》2010,18(4):863-891

Inflow data from 23 tunnels and galleries, 136 km in length and located in the Aar and Gotthard massifs of the Swiss Alps, have been analyzed with the objective (1) to understand the 3-dimensional spatial distribution of groundwater flow in crystalline basement rocks, (2) to assess the dependency of tunnel inflow rate on depth, tectonic overprint, and lithology, and (3) to derive the distribution of fracture transmissivity and effective hydraulic conductivity at the 100-m scale. Brittle tectonic overprint is shown to be the principal parameter regulating inflow rate and dominates over depth and lithology. The highest early time inflow rate is 1,300 l/s and has been reported from a shallow hydropower gallery intersecting a 200-m wide cataclastic fault zone. The derived lognormal transmissivity distribution is based on 1,361 tunnel intervals with a length of 100 m. Such interval transmissivities range between 10^?9 and 10^?1 m²/s within the first 200–400 m of depth and between 10^?9 and 10^?4 m²/s in the depth interval of 400–1,500 m below ground surface. Outside brittle fault zones, a trend of decreasing transmissivity/hydraulic conductivity with increasing depth is observed for some schistous and gneissic geological units, whereas no trend is identified for the granitic units.  相似文献   

Measuring Hg Isotopes in Bio-Geo-Environmental Reference Materials   总被引：1，自引：0，他引：1  

Nicolas Estrade  Jean Carignan  Jeroen E. Sonke  Olivier F.X. Donard 《Geostandards and Geoanalytical Research》2010,34(1):79-93

With the emergence of new analytical techniques and the expansion of scientific fields explored by using mercury isotopes, the community needs reference materials (RM) to validate and assure the accuracy of the results. The present work investigates (1) the characterisation of secondary RM in order to validate analytical systems, (2) the effects of two complex matrices on isotopic determination using stannous chloride cold vapour generation coupled to MC-ICP-MS (CV-MC-ICP-MS), (3) the effects of multiple digestion techniques for total Hg extraction and (4) the characterisation of nine geo-bio-environmental RM. Two secondary mono-elemental RMs analysed using two different analytical setups yielded isotopic compositions on δ²⁰²Hg of −3.54 ± 0.27‰ (CRPG-F65A, 2SD, n = 38) and +2.59 ± 0.19‰ (CRPG-RL24H, 2SD, n = 30) relative to the CRM NIST SRM 3133. These two RMs cover the whole range of Hg isotopic fractionation in natural samples and are made available to the scientific community. Complex fly ash and hydroxysulfate green rust matrices were synthesised, spiked with NIST SRM 3133, then digested and finally analysed versus the mono-elemental NIST SRM 3133 to show potential effect of these complex matrices during CV-MC-ICP-MS. Three digestions techniques, including traditional acid digestion, microwave digestion and high pressure-high temperature digestion, were applied to the lichen RM BCR-482 in order to compare advantages and drawbacks of these methods. Finally, the isotopic compositions of nine RMs including soils (NIST SRM 2711; GXR-2; GSS-4), sediment (GSD-10), jasperoid (GXR-1), ore deposit (GXR-3), fly ashes (BCR-176; BCR-176R) and lichen (BCR-482) are reported. These selected materials have δ²⁰²Hg values ranging from −1.75‰ to +0.11‰. Some RMs also presented mass-independent fractionation with Δ¹⁹⁹Hg and Δ²⁰¹Hg of up to −0.6‰.  相似文献   

Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS     

Olivier J. Rouxel  Maureen Auro 《Geostandards and Geoanalytical Research》2010,34(2):135-144

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.  相似文献   

Dehydration of dioctahedral aluminous phyllosilicates: thermodynamic modelling and implications for thermobarometric estimates   总被引：1，自引：1，他引：0  

Benoît Dubacq  Olivier Vidal  Vincent De Andrade 《Contributions to Mineralogy and Petrology》2010,159(2):159-174

We propose a solid-solution model for dioctahedral aluminous phyllosilicates accounting for the main compositional variations, including hydration, observed in natural smectites, interlayered illite/smectite, illites, and phengites from diagenetic to high-grade metamorphic conditions. The suggested formalism involves dehydrated micas and hydrated pyrophyllite-like thermodynamic end-members. With these end-members, the equilibrium conditions of quartz + water + K-bearing mica-like phyllosilicates of fixed 2:1 composition are represented by a line in P–T space along which the interlayer water content varies. The relevant thermodynamic properties required for the calculation of equilibrium conditions were derived using a set of 250 natural data of known maximal temperature and pressure conditions, which covers a range between 25°C and few MPa to 800°C and 5 GPa. The temperatures calculated at fixed pressure with our model are in fair agreement with those reported in the literature for the 250 natural data. At low temperature and pressure, the amount of interlayer water in K-deficient phengite and illite is predicted to reach 100% of the apparent vacancies, which is consistent with previous values reported in the literature. Although the amount of interlayer water is predicted to decrease with pressure and temperature, it is calculated to be significant in K-deficient phengite from LT–HP pelites metamorphosed at about 350°C, 10 kbar. The presence of molecular water in the interlayer site of such phengites has been confirmed by FTIR mapping. Its implications for P–T estimates are discussed.  相似文献   

Origin of the giant Allard Lake ilmenite ore deposit (Canada) by fractional crystallization,multiple magma pulses and mixing     

Bernard Charlier  Olivier Namur  Simon Malpas  Cédric de Marneffe  Jean-Clair Duchesne  Jacqueline Vander Auwera  Olivier Bolle 《Lithos》2010,117(1-4):119-134

The late-Proterozoic Allard Lake ilmenite deposit is located in the Havre-Saint-Pierre anorthosite complex, part of the allochtonous polycyclic belt of the Grenville Province. Presently the world's largest Fe–Ti oxide deposit, it had a pre-mining amount in excess of 200 Mt at grades over 60 wt.% hemo-ilmenite. The main ore body is a funnel-shaped intrusion, measuring 1.03 × 1.10 km and 100–300 m-thick. Two smaller bodies are separated by faults and anorthosite. The ore is an ilmenite-rich norite (or ilmenitite) made up of hemo-ilmenite (Hem_22.6–29.4, 66.2 wt.% on average), andesine plagioclase (An_45–50), aluminous spinel and locally orthopyroxene. Whole-rock chemical compositions are controlled by the proportions of ilmenite and plagioclase ± orthopyroxene which supports the cumulate origin of the deposit. Ore-forming processes are further constrained by normal and reverse fractionation trends of Cr concentration in cumulus ilmenite that reveal multiple magma emplacements and alternating periods of fractional crystallization and magma mixing. Mixing of magmas produced hybrids located in the stability field of ilmenite resulted in periodic crystallization of ilmenite alone. The unsystematic differentiation trends in the Allard Lake deposit, arising from a succession of magma pulses, hybridisation, and the fractionation of hemo-ilmenite alone or together with plagioclase suggest that the deposit formed within a magma conduit. This dynamic emplacement mechanism associated with continuous gravity driven accumulation of Fe–Ti oxides and possibly plagioclase buoyancy in a fractionating ferrobasalt explains the huge concentration of hemo-ilmenite. The occurrence of sapphirine associated with aluminous spinel and high-alumina orthopyroxene (7.6–9.1 wt.% Al₂O₃) lacking exsolved plagioclase supports the involvement of a metamorphic overprint during the synchronous Ottawan orogeny, which is also responsible for strong textural equilibration and external granule of exsolved aluminous spinel due to slow cooling.  相似文献   

Climate response to the physiological impact of carbon dioxide on plants in the Met Office Unified Model HadCM3   总被引：1，自引：1，他引：0  

Olivier Boucher  Andy Jones  Richard A. Betts 《Climate Dynamics》2009,32(2-3):237-249

The concentration of carbon dioxide in the atmosphere acts to control the stomatal conductance of plants. There is observational and modelling evidence that an increase in the atmospheric concentration of CO₂ would suppress the evapotranspiration (ET) rate over land. This process is known as CO₂ physiological forcing and has been shown to induce changes in surface temperature and continental runoff. We analyse two transient climate simulations for the twenty-first century to isolate the climate response to the CO₂ physiological forcing. The land surface warming associated with the decreased ET rate is accompanied by an increase in the atmospheric lapse rate, an increase in specific humidity, but a decrease in relative humidity and stratiform cloud over land. We find that the water vapour feedback more than compensates for the decrease in latent heat flux over land as far as the budget of atmospheric water vapour is concerned. There is evidence that surface snow, water vapour and cloudiness respond to the CO₂ physiological forcing and all contribute to further warm the climate system. The climate response to the CO₂ physiological forcing has a quite different signature to that from the CO₂ radiative forcing, especially in terms of the changes in the temperature vertical profile and surface energy budget over land.  相似文献   

Local coordination of Zn in hydroxy-interlayered minerals and implications for Zn retention in soils     

Olivier Jacquat  Ruben Kretzschmar 《Geochimica et cosmochimica acta》2009,73(2):348-7172

The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615-8600 mg/kg Zn) were evaluated by shell fitting. In Zn-HIS, Zn was octahedrally coordinated to oxygen at 2.06-2.08 Å and surrounded by Al atoms at 3.03-3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251-1039 mg/kg Zn) with acidic to neutral pH (pH 4.1-6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29-84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn-HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn-HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.  相似文献   

Soil properties controlling Zn speciation and fractionation in contaminated soils   总被引：2，自引：1，他引：1  

Olivier Jacquat  Andreas Voegelin  Ruben Kretzschmar 《Geochimica et cosmochimica acta》2009,73(18):5256-5272

We determined the speciation of Zn in 49 field soils differing widely in pH (4.1–7.7) and total Zn content (251–30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.  相似文献   

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