Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

A four-dimensional analysis of the thermal structure in the Gulf of Lion

The Theoretical and Experimental Tomography in the Sea Experiment (THETIS 1) took place in the Gulf of Lion to observe the evolution of the temperature field and the process of deep convection during the 1991-1992 winter. The temperature measurements consist, of moored sensors, conductivity-temperature-depth and expendable bathythermograph surveys, ana acoustic tomography. Because of this diverse data set and since the field evolves rather fast, the analysis uses a unified framework, based on estimation theory and implementing a Kalman filter. The resolution and the errors associated with the model are systematically estimated. Temperature is a good tracer of water masses. The time-evolving three-dimensional view of the field resulting from the analysis shows the details of the three classical convection phases: preconditioning, vigourous convection, and relaxation. In all phases, there is strong spatial nonuniformity, with mesoscale activity, short timescales, and sporadic evidence of advective events (surface capping, intrusions of Levantine Intermediate Water (LIW)). Deep convection, reaching 1500 m, was observed in late February; by late April the field had not yet returned to its initial conditions (strong deficit of LIW). Comparison with available atmospheric flux data shows that advection acts to delay the occurence of convection and confirms the essential role of buoyancy fluxes. For this winter, the deep. mixing results in an injection of anomalously warm water (Delta T similar or equal to 0.03 degrees) to a depth of 1500 m, compatible with the deep warming previously reported.