Formation and preservation of pedogenic carbonates in South India, links with paleo-monsoon and pedological conditions: Clues from Sr isotopes, U-Th series and REEs

The influence of the pedogenic and climatic contexts on the formation and preservation of pedogenic carbonates in a climosequence in the Western Ghats (Karnataka Plateau, South West India) has been studied. Along the climosequence, the current mean annual rainfall (MAR) varies within a 80 km transect from 6000 mm at the edge of the Plateau to 500 mm inland. Pedogenic carbonates occur in the MAR range of 500-1200 mm. In the semi-arid zone (MAR: 500-900 mm), carbonates occur (i) as thick hardpan calcretes on pediment slopes and (ii) as nodular horizons in polygenic black soils (i.e. vertisols). In the sub-humid zone (MAR: 900-1500 mm), pedogenic carbonates are disseminated in the black soil matrices either as loose, irregular and friable nodules of millimetric size or as indurated botryoidal nodules of centimetric to pluricentimetric size. They also occur at the top layers of the saprolite either as disseminated pluricentimetric indurated nodules or carbonate-cemented lumps of centimetric to decimetric size.Chemical and isotopic (⁸⁷Sr/⁸⁶Sr) compositions of the carbonate fraction were determined after leaching with 0.25 N HCl. The corresponding residual fractions containing both primary minerals and authigenic clays were digested separately and analyzed. The trend defined by the ⁸⁷Sr/⁸⁶Sr signatures of both labile carbonate fractions and corresponding residual fractions indicates that a part of the labile carbonate fraction is genetically linked to the local soil composition. Considering the residual fraction of each sample as the most likely lithogenic source of Ca in carbonates, it is estimated that from 24% to 82% (55% on average) of Ca is derived from local bedrock weathering, leading to a consumption of an equivalent proportion of atmospheric CO₂. These values indicate that climatic conditions were humid enough to allow silicate weathering: MAR at the time of carbonate formation likely ranged from 400 to 700 mm, which is 2- to 3-fold less than the current MAR at these locations.The Sr, U and Mg contents and the (²³⁴U/²³⁸U) activity ratio in the labile carbonate fraction help to understand the conditions of carbonate formation. The relatively high concentrations of Sr, U and Mg in black soil carbonates may indicate fast growth and accumulation compared to carbonates in saprolite, possibly due to a better confinement of the pore waters which is supported by their high (²³⁴U/²³⁸U) signatures, and/or to higher content of dissolved carbonates in the pore waters. The occurrence of Ce, Mn and Fe oxides in the cracks of carbonate reflects the existence of relatively humid periods after carbonate formation. The carbonate ages determined by the U-Th method range from 1.33 ± 0.84 kyr to 7.5 ± 2.7 kyr and to a cluster of five ages around 20 kyr, i.e. the Last Glacial Maximum period. The young occurrences are only located in the black soils, which therefore constitute sensitive environments for trapping and retaining atmospheric CO₂ even on short time scales. The maximum age of carbonates depends on their location in the climatic gradient: from about 20 kyr for centimetric nodules at Mule Hole (MAR = 1100 mm/yr) to 200 kyr for the calcrete at Gundlupet (MAR = 700 mm/yr, Durand et al., 2007). The intensity of rainfall during wet periods would indeed control the lifetime of pedogenic carbonates and thus the duration of inorganic carbon storage in soils.     

Cenozoic geodynamic evolution of the Aegean

The Aegean region is a concentrate of the main geodynamic processes that shaped the Mediterranean region: oceanic and continental subduction, mountain building, high-pressure and low-temperature metamorphism, backarc extension, post-orogenic collapse, metamorphic core complexes, gneiss domes are the ingredients of a complex evolution that started at the end of the Cretaceous with the closure of the Tethyan ocean along the Vardar suture zone. Using available plate kinematic, geophysical, petrological and structural data, we present a synthetic tectonic map of the whole region encompassing the Balkans, Western Turkey, the Aegean Sea, the Hellenic Arc, the Mediterranean Ridge and continental Greece and we build a lithospheric-scale N-S cross-section from Crete to the Rhodope massif. We then describe the tectonic evolution of this cross-section with a series of reconstructions from ~70 Ma to the Present. We follow on the hypothesis that a single subduction has been active throughout most of the Mesozoic and the entire Cenozoic, and we show that the geological record is compatible with this hypothesis. The reconstructions show that continental subduction (Apulian and Pelagonian continental blocks) did not induce slab break-off in this case. Using this evolution, we discuss the mechanisms leading to the exhumation of metamorphic rocks and the subsequent formation of extensional metamorphic domes in the backarc region during slab retreat. The tectonic histories of the two regions showing large-scale extension, the Rhodope and the Cyclades are then compared. The respective contributions to slab retreat, post-orogenic extension and lower crust partial melting of changes in kinematic boundary conditions and in nature of subducting material, from continental to oceanic, are discussed.     

Coastal Phytoplankton Do Not Rest in Winter

The climatology and interannual variability of winter phytoplankton was analyzed at the Long Term Ecological Research Station MareChiara (LTER-MC, Gulf of Naples, Mediterranean Sea) using data collected from 1985 to 2006. Background winter chlorophyll values (0.2–0.5 μg chl a dm⁻³) were associated with the dominance of flagellates, dinoflagellates, and coccolithophores. Winter biomass increases (<5.47 μg chl a dm⁻³) were often recorded until 2000, generally in association with low-salinity surface waters (37.3–37.9). These blooms were most often caused by colonial diatoms such as Chaetoceros spp., Thalassiosira spp., and Leptocylindrus danicus. In recent years, we observed more modest and sporadic winter biomass increases, mainly caused by small flagellates and small non-colonial diatoms. The resulting negative chl a trend over the time series was associated with positive surface salinity and negative nutrient trends. Physical and meteorological conditions apparently exert a strict control on winter blooms, hence significant changes in winter productivity can be foreseen under different climatic scenarios.     

Towards an operational aqueous phase chemistry mechanism for regional chemistry-transport models: CAPRAM-RED and its application to the COSMO-MUSCAT model

Mechanism reductions of the detailed aqueous phase chemistry mechanism CAPRAM 3.0i are performed. Manual methods and automatic techniques are both applied in order to provide a less computationally intensive mechanism which is operational in regional chemistry transport models (CTMs). The finally reduced mechanism contains less than 200 reactions (4 times smaller than the detailed CAPRAM 3.0i) and describes the main characteristics of inorganic and organic aqueous phase processes occurring in tropospheric warm clouds. Most of the chemical reduction potential is realized in the CAPRAM 3.0i organic chemistry. The number of aqueous phase species decreases from 380 in the full mechanism to 130 in the final reduced version. The calculated percentage deviations between the full and reduced mechanism are on average below 5% for the most important organic and inorganic target compounds such as oxidants, inorganic and organic acids, carbonyls and alcohols. Comparisons of the required CPU times between the full and reduced mechanisms show reductions of approximately 40%. 2-D test simulations with the CTM MUSCAT were performed using prescribed meteorological conditions in order to examine the applicability of the reduced mechanism at regional scale. Simulations with the reduced CAPRAM 3.0i mechanism and a much less complex mechanism with only limited inorganic chemistry (INORG) were compared to evaluate the effects of more detailed chemistry. The model results show large differences in the level of oxidants and the inorganic and organic mass processing. Prospectively, the reduced mechanism represents the basis for studying aerosol cloud processing effects at regional scale with future CTMs and will allow more adequate interpretation of field data.     

A two‐step process for the reflooding of the Mediterranean after the Messinian Salinity Crisis

The Messinian Salinity Crisis is well known to have resulted from a significant drop of the Mediterranean sea level. Considering both onshore and offshore observations, the subsequent reflooding is generally thought to have been very sudden. We present here offshore seismic evidence from the Gulf of Lions and re‐visited onshore data from Italy and Turkey that lead to a new concept of a two‐step reflooding of the Mediterranean Basin after the Messinian Salinity Crisis. The refilling was first moderate and relatively slow accompanied by transgressive ravinement, and later on very rapid, preserving the subaerial Messinian Erosional Surface. The amplitude of these two successive rises of sea level has been estimated at ≤500 m for the first rise and 600–900 m for the second rise. Evaporites from the central Mediterranean basins appear to have been deposited principally at the beginning of the first step of reflooding. After the second step, which preceeded the Zanclean Global Stratotype Section and Point, successive connections with the Paratethyan Dacic Basin, then the Adriatic foredeep, and finally the Euxinian Basin occurred, as a consequence of the continued global rise in sea level. A complex morphology with sills and sub‐basins led to diachronous events such as the so‐called ‘Lago Mare’.This study helps to distinguish events that were synchronous over the entire Mediterranean realm, such as the two‐step reflooding, from those that were more local and diachronous. In addition, the shoreline that marks the transition between these two steps of reflooding in the Provence Basin provides a remarkable palaeogeographical marker for subsidence studies.     

Mobility of metamorphic fluids inferred from infrared microspectroscopy on natural fluid inclusions: the example of Tinos Island,Greece

OH structure of metamorphic fluids has been studied by high temperature infrared (IR) microspectroscopy on natural fluid inclusions contained in quartz veins, over the temperature range 25–370 °C. Blueschist-facies veins from Tinos island core complex (Cyclades, Greece) display H₂O–NaCl–CaCl₂–CO₂ inclusions whereas greenschist-facies veins contain H₂O–NaCl ± CO₂ inclusions. From 25 to 370 °C, peak positions of OH stretching IR absorption bands increase quasi-linearly with slopes of 0.25 and 0.50 cm^–1 °C^–1 for inclusions trapped under blueschist and greenschist conditions, respectively. Extrapolation to 400 °C yield peak positions of 3,475 cm^–1 for blueschist inclusions and 3,585 cm^–1 for greenschist inclusions. Because the smaller wave number indicates the shorter hydrogen-bond distance between water molecules, fluids involved in the greenschist event have a loose structure compared with blueschist fluids. We suggest that these properties might correspond to a low wetting angle of fluids. This would explain the high mobility of aqueous fluids suggested by structural observation and stable isotope analysis.Editorial responsibility: J. Hoefs     

Stibnite microstructures as imprints of fault movement

The natural deformation of stibnite in relation to the kinematic history of a regional fault is resolved using microstructural analysis of massive stibnite along the Biards Fault in the Massif Central (France). Stibnite underwent intra-crystalline deformation associated with a strong linear and planar anisotropy. Lepidoblastic textures, undulatory extinction of oriented grains, growth of antimony between these grains, and a colour change of stibnite from white to black, result from dynamic recrystallisation. A range of asymmetric microstructures indicate non-coaxial deformation and a left-lateral sense of shear, related to the movement of the fault zone. The computed displacement corresponds to the geological offsets measured along the fault. We conclude that stibnite has microstructurally recorded the bulk kinematics of its host fault zone.Editorial Handling: F. Tornos     

Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: When clay minerals lead to identical molecular signature

Different studies have already pointed out the influence of clays during the analysis of pure organic compounds (especially alkanols, alkanoic acids) as well as macromolecules (humic acids) by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS). Especially, the occurrence of clay minerals favors the generation of aromatic units such as alkylbenzenes and polycyclic aromatic hydrocarbons. So as to better identify the nature of the organic compounds which are sensitive to the presence of clays during flash pyrolysis, a humic acid mixed in variable proportions of a Na-homoionic clay was tested. The smectite/humic acid mixtures containing from 10% to 100% humic acid allowed us to identify the progressive disappearance or appearance of specific compounds after PyGC–MS.n-Alk-1-enes disappear when the clay proportion is higher than 67%. For higher contents of Na-smectite, n-alkanes become less and less abundant with a preferential consumption of high molecular weight n-alkanes, whereas the aromatic hydrocarbon proportion increases. Moreover, the distribution of each aromatic hydrocarbon family (alkylbenzenes and alkylnaphthalenes) has been investigated. The pyrogram of pure humic acid exhibits a specific distribution of alkylbenzenes and alkylnaphthalenes reflecting the structure of the organic macromolecule. With the increase in clay proportion, these distributions are modified and lead to other distributions with a preferential predominance of thermally stable isomers.Pyrograms of humic acid and undecanoic acid in the presence of 90% of Na-smectite are similar, especially concerning alkylbenzene and alkylnaphthalene distributions. Therefore, clays (Na-smectite in our experiments) in high proportion modify initial organic products by recombination reactions and lead to the generation of new compounds of very similar distribution, whatever the nature of the initial organic matter. Such results underline the very important catalytic properties of clay minerals on functionalized organic matter during flash pyrolysis.     

Genesis of the Dordogne (France) high-purity silica placers

This article describes the formation of the principal French high-purity silica placer (source for electrometallurgy of silicon and ferrosilicon), the Boudeau deposit in Dordogne, and of one of its subordinate deposits, the Pays Brûlé deposit. Boudeau has always been considered to be a colluvial deposit, formed in a trap produced by extensional tectonism. The present work suggests a new genetic interpretation, based on a combined study of the deposits and their underlying rocks. It shows that the quartz gravel deposits, laid down by stream flow within braided channels, were reworked by karstic progressive sinking, and that the mechanism responsible for the increase in the thickness of the economic formations is cryptokarstic corrosion. This undercovers weathering process, which involves dissolution of karstifiable rocks (oolitic and bioclastic limestones) at their interface with a permeable, non-karstifiable cover composed of chemically pure quartz gravels in a sandy-argillaceous matrix. A typological study of the gravels provides a basis for tackling the problem of their origin and their purity. They seem to be derived mainly from the synmetamorphic quartz mobilisates of the stripped metamorphic units (the lower and upper gneiss units forming the western edge of the Massif Central). Lastly, a dynamic model is suggested for the genesis of the high-purity silica deposits of Dordogne.