Boron isotopic fractionation related to boron sorption on humic acid and the structure of surface complexes formed     

Emmanuel Lemarchand  Jérôme Gaillardet 《Geochimica et cosmochimica acta》2005,69(14):3519-3533

Boron isotopic fractionation during adsorption onto Ca-flocculated Aldrich humic acid (HA) has been investigated experimentally as a function of solution pH at 25°C and I = 0.15 M. Boron aqueous concentration and isotopic composition were determined by Cs₂BO₂⁺ Positive Thermal Ionization Mass Spectrometry analysis, while the structure of B surface complexes on HA was characterized using ¹¹B Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Significant B sorption on HA was observed at 6 < pH < 12 with a maximum value of Kd, the partition coefficient between adsorbed and aqueous boron, equal to 40 at pH = 9.5-10. Combined ¹¹B MAS NMR analysis and FITEQL modeling of B sorption on HA showed that this element forms tetrahedrally coordinated five- or six-membered ring chelates, most likely 1,2-diol and 1,3-diol complexes at alkaline pH (8 < pH < 11) and dicarboxylic complexes at near neutral conditions (6 < pH < 9). Results of this study demonstrate for the first time that boron sorption on HA induces a strong pH-dependent isotope fractionation—with ¹¹B depleted at the surface of HA—that reaches a maximum at 5 < pH < 9 (α = 0.975, Δ = −25‰) and decreases sharply at pH >9. The measured isotope fractionation cannot be modeled assuming that the isotopic composition of the sorbed borate species is identical to that of B(OH)₄^- species in the parent solution. It is shown that the extent of isotopic fractionation depends not only on B aqueous speciation but also on the distribution and structure of the borate surface complexes formed. In agreement with energetic constrains, calculation of the isotope fractionation factors between aqueous boric acid and boron surface complexes suggests that the formation of the strained six-membered ring 1,3-diol complex yields a much higher fractionation (α_BLP1−III = 0.954-0.960, Δ = −41/-47‰) than that of the very stable five-membered ring 1,2-diol (α_BLP2−III = 0.983, Δ = −18‰). The results of this study open new perspectives to understand and model boron biogeochemical cycle. It is predicted that boron sorption onto organic matter can have important consequences for the boron isotopic composition of surface water reservoirs (seawater, groundwater, soil waters) in which either abundant organic surfaces or significant boron concentrations are available. In addition, the large isotope fractionation between aqueous boric acid and surface boron-organic complexes found in the present work makes boron a promising tracer of biologic activity.  相似文献   

An insight into the formation of severe ozone episodes: modeling the 21/03/01 event in the ESCOMPTE region   总被引：1，自引：0，他引：1  

Fanny Lasry  Isabelle Coll  Emmanuel Buisson 《Atmospheric Research》2005,74(1-4):191-215

High ozone concentrations are observed more and more frequently in the lower troposphere. The development of such polluted episodes is linked to a complex set of chemical, physical and dynamical parameters that interact with each other. To improve air quality, it is necessary to understand and quantify the role of all these processes on the intensity of ozone formation. The ESCOMPTE program, especially dedicated to the numerical simulation of photochemical episodes, offers an ideal frame to investigate details of the roles of many of these processes through 3D modeling. This paper presents the analysis, with a 3D eulerian model, of a severe and local episode of ozone pollution that occurred on the 21st of March 2001 in the ESCOMPTE region. This episode is particularly interesting due to the intensity of the observed ozone peaks (450 μg/m³ during 15 mn) but also because it did not occur in summer but at the beginning of spring. As part of the premodeling work of the ESCOMPTE program, this study focuses on the sensitivity of the simulated ozone peaks to various chemical and physical phenomena (long-range transport, industrial emissions, local dynamic phenomena…) to determine their influence on the rise of high local photooxidant concentrations and to better picture the photochemistry of the ESCOMPTE region. Through sensitivity tests to dynamical calculation resolution and emissions, this paper shows how the combination of sea and pond breezes with emissions of reactive VOCs can generate local intense ozone peaks.  相似文献   

Tectonostratigraphy and base-metal mineralization controls, Aravalli province (western India): New interpretations from geophysical data analysis     

Alok Porwal  Emmanuel John M. Carranza  Martin Hale   《Ore Geology Reviews》2006,29(3-4):287-306

Analysis and synthesis of multi-disciplinary geoscience information from geological literature/maps and from digitally-processed aeromagnetic and gravity data pertinent to the Aravalli province were carried out to address some hitherto unresolved questions about the tectonostratigraphy of this Archaean–Proterozoic metallogenic province. Based on the magnetic anomalies, several tectonic domains were identified. These domains, bounded by regional-scale geophysical lineaments, have distinct crustal, lithological, metamorphic, and metallogenic characteristics and correlate broadly with lithostratigraphic belts identified by several earlier workers. New interpretations on the tectonostratigraphy and the base-metal mineralization controls in the Aravalli province are as follows. The Hindoli sequences, in the eastern parts of the province, constitute an independent Palaeo–Proterozoic tectonic domain and do not form part of the Archaean basement complex. The base-metal-bearing metasedimentary enclaves in the central parts of the province also constitute an independent Palaeo–Proterozoic tectonic domain, which is quite distinct from the surrounding (basement complex?) rocks. The base-metal-bearing metavolcano-sedimentary sequences in the western parts of the province constitute an independent Neo–Proterozoic tectonic domain. The base-metal deposits in the province are spatially associated with the regional-scale lineaments and with the mafic metavolcanic rocks deduced from the aeromagnetic data. The regional-scale lineaments, which possibly represent Proterozoic crustal-scale faults, are plausible structural controls on the base-metal mineralization in the province. The mafic metavolcanic rocks are plausible heat-source controls on the SEDEX- and/or VMS-type base-metal mineralizations and are possible metal-source controls on the VMS-type base-metal mineralization in the province.  相似文献   

Erosion balance in the watersheds of the western Paris Basin by high-frequency monitoring of discharge and suspended sediment in surface water     

Benoît Laignel  Emmanuel Dupuis  Alain Durand  Jean-Paul Dupont  Emmanuel Hauchard  Nicolas Massei 《Comptes Rendus Geoscience》2006,338(8):556-564

An accurate quantification of erosion, based on high-frequency monitoring of river discharge and suspended sediment fluxes is proposed for two watersheds in the western Paris Basin, a sensitive area with respect to erosion phenomena. This continuous monitoring makes it possible to include flood events of short duration, but significant erosion potential. The obtained erosion rate (16 and 21 t?km^?2?yr^?1) is among the weakest of the planet (3.5 to 18?000 t?km^?2?yr^?1). However, this annual balance does not reflect the behaviour of these rivers which can be torrential in certain cases. To cite this article: B. Laignel et al., C. R. Geoscience 338 (2006).  相似文献   

The mobilization of debris flows from shallow landslides   总被引：8，自引：3，他引：8  

Emmanuel J. Gabet  Simon M. Mudd 《Geomorphology》2006,74(1-4):207-218

According to critical state theory, a soil will approach a critical void ratio during shear such that loose soils contract and dense soils dilate. Theory indicates that failing soils must be loose to generate the pore pressures needed for the mobilization of debris flows. Previously published results from large-scale experiments have also suggested that soils must be initially loose to fail as debris flows. In this contribution, this mechanism for soil liquefaction is tested in the field through observations and geotechnical analysis of soils that failed during a large storm in central California. Surprisingly, we find that the debris flows mobilized from soils that were initially dense. In addition, we find that the potential for debris flow mobilization was strongly linked to the fines/sand ratio. We present results from a numerical model that indicate that, as dilational soils approach the critical void ratio, the arresting effect of negative pore pressures generated by dilation is greatly reduced, leading to a rapid increase in basal pore pressure and rapid downslope acceleration. In addition, the model results suggest that the downslope displacement required to reach the critical state porosity in a dilative soil will be on the order of 0.1 to 1 m. Because the rate of the approach to critical state is fundamentally a function of the hydraulic conductivity of the soil, sandy soils will approach critical state much more rapidly than clay-rich soils.  相似文献   

Chironomid (Insecta: Diptera) Assemblages from a Gradient of Lotic and Lentic Waterbodies in River Floodplains of France: A Methodological Tool for Paleoecological Applications     

Emmanuel Gandouin  Alain Maasri  Brigitte Van Vliet-Lanoë  Evelyne Franquet 《Journal of Paleolimnology》2006,35(1):149-166

  相似文献   

Petrology and CHIME geochronology of Pan-African high K and Sr/Y granitoids in the Nkambe area, Cameroon   总被引：1，自引：1，他引：0  

Samuel Tetsopgang  Kazuhiro Suzuki  Emmanuel Njonfang 《Gondwana Research》2008,14(4):686

The Central African Belt in the Nkambe area, northwestern Cameroon represents a collisional zone between the Saharan metacraton and the Congo craton during the Pan-African orogeny, and exposes a variety of granitoids including foliated and massive biotite monzogranites in syn- and post-kinematic settings. Foliated and massive biotite monzogranites have almost identical high-K calc-alkaline compositions, with 73–67 wt.% SiO₂, 17–13 wt.% Al₂O₃, 2.1–0.9 wt.% CaO, 4.4–2.7 wt.% Na₂O and 6.3–4.4 wt.% K₂O. High concentrations of Rb (264–96 ppm), Sr (976–117 ppm), Ba (3680–490 ppm) and Zr (494–99 ppm), with low concentrations of Y (mostly< 20 ppm with a range 54–6) and Nb (up to 24 ppm) suggest that the monzogranites intruded in collisional and post-collisional settings. The Sr/Y ratio ranges from 25 to 89. K, Rb and Ba resided in a single major phase such as K-feldspar in the source. Garnet was present in the source and remained as restite at the site of magma generation. This high K₂O and Sr/Y granitic magma was generated by partial melting of a granitic protolith under high-pressure and H₂O undersaturated conditions where garnet coexists with K-feldspar, albitic plagioclase. CHIME (chemical Th–U-total Pb isochron method) dating of zircon yields ages of 569 ± 12–558 ± 24 Ma for the foliated biotite monzogranite and 533 ± 12–524 ± 28 Ma for the massive biotite monzogranite indicating that the collision forming the Central African Belt continued in to Ediacaran (ca 560 Ma).  相似文献   

Absolute calibration of a photoelectric condensation nucleus counter at low values of nucleus concentration     

Marion B. Emmanuel  Patrick Squires 《Pure and Applied Geophysics》1969,72(1):268-283

Summary A new absolute condensation nucleus counter was constructed to investigate the accuracy of the calibration widely used with the Pollak-Nolan photoelectric condensation nucleus counter. An attempt was made to standardize the conditions affecting calibration and, using the new counter, to recalibrate the photoelectric counter at values of extinction less than 16%.Over this extinction range, the present work indicates nucleus concentrations which are higher by about 30% than those given by the calibration ofPollak andMetnieks [8]³). In view of the great natural variability of Aitken nucleus concentrations, this discrepancy, if real, is of little meteorological importance.  相似文献   

New alternatives for reference evapotranspiration estimation in West Africa using limited weather data and ancillary data supply strategies.     

Gorka?Landeras  Emmanuel?Bekoe  Joseph?Ampofo  Frederick?Logah  Mbaye?Diop  Madiama?Cisse  Jalal?ShiriEmail authorView author&#;s OrcID profile 《Theoretical and Applied Climatology》2018,132(3-4):701-716

Accurate estimation of reference evapotranspiration (ET ₀ ) is essential for the computation of crop water requirements, irrigation scheduling, and water resources management. In this context, having a battery of alternative local calibrated ET ₀ estimation methods is of great interest for any irrigation advisory service. The development of irrigation advisory services will be a major breakthrough for West African agriculture. In the case of many West African countries, the high number of meteorological inputs required by the Penman-Monteith equation has been indicated as constraining. The present paper investigates for the first time in Ghana, the estimation ability of artificial intelligence-based models (Artificial Neural Networks (ANNs) and Gene Expression Programing (GEPs)), and ancillary/external approaches for modeling reference evapotranspiration (ET ₀ ) using limited weather data. According to the results of this study, GEPs have emerged as a very interesting alternative for ET ₀ estimation at all the locations of Ghana which have been evaluated in this study under different scenarios of meteorological data availability. The adoption of ancillary/external approaches has been also successful, moreover in the southern locations. The interesting results obtained in this study using GEPs and some ancillary approaches could be a reference for future studies about ET ₀ estimation in West Africa.  相似文献   

Crustal‐scale fluid flow during the tectonic evolution of the Bighorn Basin (Wyoming,USA)     

Nicolas Beaudoin  Nicolas Bellahsen  Olivier Lacombe  Laurent Emmanuel  Jacques Pironon 《Basin Research》2014,26(3):403-435

Stable isotope measurements (O, C, Sr), microthermometry and salinity measurements of fluid inclusions from different fracture populations in several anticlines of the Sevier‐Laramide Bighorn basin (Wyoming, USA) were used to unravel the palaeohydrological evolution. New data on the microstructural setting were used to complement previous studies and refine the fracture sequence at basin scale. The latter provides the framework and timing of fluid migration events across the basin during the Sevier and Laramide orogenic phases. Since the Sevier tectonic loading of the foreland basin until its later involvement into the Laramide thick‐skinned orogeny, three main fracture sets (out of seven) were found to have efficiently enhanced the hydraulic permeability of the sedimentary cover rocks. These pulses of fluid are attested by calcite crystals precipitated in veins from hydrothermal (T > 120 °C) radiogenic fluids derived from Cretaceous meteoric fluids that interacted with the Precambrian basement rocks. Between these events, vein calcite precipitated from formational fluids at chemical and thermal equilibrium with surrounding environment. At basin scale, the earliest hydrothermal pulse is documented in the western part of the basin during forebulge flexuring and the second one is documented in basement‐cored folds during folding. In addition to this East/West diachronic opening of the cover rocks to hydrothermal pulses probably controlled by the tectonic style, a decrease in ^87/86Sr values from West to East suggests a crustal‐scale partially squeegee‐type eastward fluid migration in both basement and cover rocks since the early phase of the Sevier contraction. The interpretation of palaeofluid system at basin scale also implies that joints developed under an extensional stress regime are better vertical drains than joints developed under strike‐slip regime and enabled migration of basement‐derived hydrothermal fluids.  相似文献