Thrusting and faulting in metamorphic and sedimentary units of Ligurian Alps: an example of integrated field work and geochemical analyses

In a sector placed in the SE part of the Alps–Apennine junction, a kilometre-scale shear zone has been identified as the Grognardo thrust zone (GTZ), which caused the NE-directed thrusting of metaophiolites (Voltri Group) and polymetamorphic continental crust slices (Valosio Unit) of Ligurian Alps onto Oligocene sediments of an episutural basin known as “Tertiary Piemonte Basin”. The structural setting of the GTZ is due to syn- to late-metamorphic deformation, followed by a brittle thrusting that occurred in the Late Aquitanian times and can thus be related to one of the main contractional tectonic events suffered by northern Apennines. The GTZ was then sealed by Lower Burdigalian carbonate platform sediments (Visone Formation). Transtensive faulting followed in post-Burdigalian times along NW–SE regional faults and displaced the previously coupled sedimentary and metamorphic units. The GTZ thus underwent a plastic-to-brittle evolution, during which carbonate-rich fluids largely sustained the deformation. In these stages, a complex vein network originated within both the metamorphic and sedimentary rocks. Field data and stable isotopic analyses (¹³C and ¹⁸O) of bulk rocks and veins show that fluid–rock interaction caused the carbonatisation of the rocks in the late-metamorphic stages and the cataclasis and recementation, by the action of isochemical cold carbonate groundwater during the thrusting events. Carbonate veins largely developed also during the transtensive faulting stages, with composition clearly different from that of the veins associated to thrust faults, as indicated by the strong depletion in ¹³C of carbonate fillings, suggesting the presence of exotic fluids, characterised by a high content of organic matter.     

Isotopic constraints on the Si-biogeochemical cycle of the Antarctic Zone in the Kerguelen area (KEOPS)

Estimation of the silicon (Si) mass balance in the ocean from direct measurements (Si uptake-dissolution rates …) is plagued by the strong temporal and spatial variability of the surface ocean as well as methodological artifacts. Tracers with different sensitivities toward physical and biological processes would be of great complementary use. Silicon isotopic composition is a promising proxy to improve constraints on the Si-biogeochemical cycle, since it integrates over longer timescales in comparison with direct measurements and since the isotopic balance allows to resolve the processes involved, i.e. uptake, dissolution, mixing. Si-isotopic signatures of seawater Si(OH)₄ and biogenic silica (bSiO₂) were investigated in late summer 2005 during the KEOPS experiment, focusing on two contrasting biogeochemical areas in the Antarctic Zone: a natural iron-fertilized area above the Kerguelen Plateau (< 500 m water depth) and the High Nutrient Low Chlorophyll area (HNLC) east of the plateau (> 1000 m water depth). For the HNLC area the Si-isotopic constraint identified Upper Circumpolar Deep Water as being the ultimate Si-source. The latter supplies summer mixed layer with 4.0 ± 0.7 mol Si m^? 2 yr^? 1. This supply must be equivalent to the net annual bSiO₂ production and exceeds the seasonal depletion as estimated from a simple mixed layer mass balance (2.5 ± 0.2 mol Si m^? 2 yr^? 1). This discrepancy reveals that some 1.5 ± 0.7 mol Si m^? 2 yr^? 1 must be supplied to the mixed layer during the stratification period. For the fertilized plateau bloom area, a low apparent mixed layer isotopic fractionation value (?³⁰Si) probably reflects (1) a significant impact of bSiO₂ dissolution, enriching the bSiO₂ pool in heavy isotope; and/or (2) a high Si uptake over supply ratio in mixed layer at the beginning of the bloom, following an initial closed system operating mode, which, however, becomes supplied toward the end of the bloom (low Si uptake over supply ratio) with isotopically light Si(OH)₄ from below when the surface Si(OH)₄ pool is significantly depleted. We estimated a net integrated bSiO₂ production of 10.5 ± 1.4 mol Si m^? 2 yr^? 1 in the AASW above the plateau, which includes a significant contribution of bSiO₂ production below the euphotic layer. However, advection which could be significant for this area has not been taken into account in the latter estimation based on a 1D approach of the plateau system. Finally, combining the KEOPS Si-isotopic data with those from previous studies, we refined the average Si-isotopic fractionation factor to ? 1.2 ± 0.2‰ for the Antarctic Circumpolar Current.     

δ30Si and δ29Si Determinations on USGS BHVO-1 and BHVO-2 Reference Materials with a New Configuration on a Nu Plasma Multi-Collector ICP-MS

We report silicon isotopic determinations for USGS rock reference materials BHVO-1 and BHVO-2 using a Nu Plasma multi-collector (MC)-ICP-MS, upgraded with a new adjustable entrance slit, to obtain medium resolution, as well as a stronger primary pump and newly designed sampler and skimmer cones ("B" cones). These settings, combined with the use of collector slits, allowed a resolution to be reached that was sufficient to overcome the ¹⁴N¹⁶O and ¹⁴N₂ interferences overlying the ³⁰Si and the ²⁸Si peaks, respectively, in an earlier set-up. This enabled accurate measurement of both δ³⁰Si and δ²⁹Si. The δ value is expressed in per mil variation relative to the NBS 28 quartz reference material. Based on data acquired from numerous sessions spread over a period of six months, we propose a recommended average δ³⁰Si of −0.33 ± 0.05‰ and −0.29 ± 0.11‰ (2se) for BHVO-1 and BHVO-2, respectively. Our BHVO grand mean silicon isotope composition (δ³⁰Si =−0.31 ± 0.06‰) is significantly more negative than the only published value for BHVO-2, but is in very good agreement with the recently established average value of ocean island basalts (OIB), confirming the conclusion that the OIB reservoir has a distinct isotopic composition from the solar reservoir as sampled by chondrites.     

Petrographic evidence of the past occurrence of gas hydrates in the Tertiary Piedmont Basin (NW Italy)

Methane-derived rocks in Monferrato and the Tertiary Piedmont Basin (NW Italy) consist of seep carbonates, formed by gas seepage at the seafloor, and macroconcretions resulting from the cementation of buried sediments crossed by gas-rich fluids. These rocks are characterized by both negative δ¹³C values and a marked enrichment in δ¹⁸O. Petrographic features not commonly described and that point to enigmatic depositional and diagenetic conditions have been observed in both types of rocks: inhomogeneous distribution of cements within cavities; dolomite crystals floating within cavity-filling calcite spar; non-gravitational fabrics of internal sediments plastering cavity walls; open framework within microbial crusts. These features suggest the former presence of gas hydrates in sediments. During their dissociation, new space was formed and filled with authigenic carbonates or injected sediments. Analogous mechanisms of clathrate freeze-and-thaw processes have been inferred for the genesis of zebra and stromatactis structures and particular kinds of carbonate breccias. The term melt-seal structure is proposed for this kind of diagenetic structure. The fabrics of gas hydrates and the geochemical conditions of sediments, in turn depending on the relative rates of supply of methane-rich fluids and normal seawater, conditioned the final aspect of the rocks.