Iodine ages of pore water at Hydrate Ridge, Cascadian continental margin

Hydrate Ridge off the coast of Oregon, USA, is a prime example for gas hydrate occurrences in active margin settings. It is part of the Cascadia Margin and was the focus of Ocean Drilling Program (ODP) Leg 204, which successfully recovered fluids from nine sites from the southern part of the ridge. Iodide concentrations in pore fluids associated with gas hydrates are strongly enhanced, by factors up to 5000 compared to seawater, which allows the use of this biophilic element as tracer for organic source regions. We applied the cosmogenic isotope 129I (T1/2=15.7 Ma) system to determine the age of the organic source formation responsible for the iodide enrichment. In all sites at ODP Leg 204, 129I/I ratios were found to decrease with depth to values around 250x10**-15, corresponding to minimum ages of 40 Ma, but in several sites, maxima in the 129I/I ratios point to the local addition of young iodide. The results indicate that a large amount of iodide was derived from deep accreted sediments of Eocene age, and that additional source regions provide iodide of Late Miocene age. The presence of old iodide in the pore waters suggests that fluid pathways are open to allow transport over large distances into the gas hydrate fields. The strong correlation between iodide and methane in hydrate fields coupled with the similarity in transport parameters in aqueous solutions suggests that a large fraction of methane in gas hydrates also has old sources and is transported into the present locations from source regions of Eocene age.

Major and trace element compositions of the Buendnerschiefer samples

The Bündnerschiefer of the Swiss-Italian Alps is a large sedimentary complex deposited on the Piemonte-Liguria and Valais oceans and associated continental margins from the upper Jurassic to Eocene. It is made of a large variety of sequences associated or not with an ophiolitic basement. The Bündnerschiefer makes an accretionary prism that developed syn-tectonically from the onset of alpine subduction, and it records orogenic metamorphism following episodes of HP metamorphism. The Bündnerschiefer shares important similarities with the Otago schists of New Zealand and with the Wepawaug schists of Connecticut, both of which form accretionary prisms and have an orogenic metamorphic imprint. With the aim of testing the hypothesis of mobility of chemical components as a function of metamorphic grade, in this work I present fifty-five bulk chemical analyses of various lithological facies of the Bündnerschiefer collected along the well-studied field gradient of the Lepontine dome of Central Switzerland, in the Prättigau half window of East Switzerland, and in the Tsaté Nappe of Valle d'Aosta (Italy). The dataset includes the concentration of major components, large ion lithophile elements (Rb, Sr, Ba, Cs), high field strength elements (Zr, Ti, Nb, Th, U, Ta, Hf), fluid-mobile light elements (B, Li), volatiles (CO2, S), REEs, and Y, V, Cr, Co, Sn, Pb, Cu, Zn, Tl, Sb, Be, and Au. These data are compared against the compositions of the global marine sediment reservoir, typical crustal reservoirs, and against the previously measured compositions of Otago and Wepawaug schists. Results reveal that, irrespective of their metamorphic evolution, the bulk chemical compositions of orogenic metasediments are characterized by mostly constant compositional ratios (e.g., K2O/Al2O3, Ba/Al2O3, Sr/CaO, etc.), whose values in most cases are undistinguishable from those of actual marine sediments and other crustal reservoirs. For these rocks, only volatile concentrations decrease dramatically as a function of metamorphic temperature, and significant deviations from the reservoir signatures are evident for SiO2, B, and Li. These results are interpreted as an indication of residual enrichment in the sediments, a process taking place during syn-metamorphic dehydration from the onset of metamorphism in a regime of chemical immobility. Residual enrichment increased the absolute concentrations of the chemical components of these rocks, but did not modify significantly their fundamental ratios. This poor compositional modification of the sediments indicates that orogenic metamorphism in general does not promote significant mass transfer from accretionary prisms. In contrast, mass transfer calculations carried out in a shear zone crosscutting the Bündnerschiefer shows that significant mass transfer occurs within these narrow zones, resulting in gains of H2O, SiO2, Al2O3, K2O, Ba, Y, Rb, Cu, V, Tl, Mo, and Ce during deformation and loss of Na2O, CO2, S, Ni, B, U, and Pb from the rock. These components were presumably transported by an aquo-carbonic fluid along the shear zone. These distinct attitudes to mobilize chemical elements from orogenic sediments may have implications for a potentially large number of geochemical processes in active continental margins, from the recycling of chemical components at plate margins to the genesis of hydrothermal ore deposits.