Reaction of seawater with fresh mid-ocean ridge gabbro creates ';atypical' REE pattern and high REE fluid fluxes: Experiments at 425 and 475 °C, 400 and 1000 bar

High-temperature MOR hydrothermalism significantly affects ocean chemistry. The Sisters Peak (SP) hydrothermal field at 5°S on the slow-spreading Mid-Atlantic Ridge (MAR) emanates fluids >400°C [1] that have high concentrations of H2, transition metals, and rare earth elements (REE) exhibiting ';atypical' REE pattern characterized by depletions of LREE and HREE relative to MREE and no Eu anomaly [2]. This is in contrast to the ';typical' LREE enrichment and strong positive Eu anomaly known from many MOR vent fluids observed world-wide [e.g., 3]. Besides temperature, the seawater-to-rock ratio (w/r ratio) has significant control on the fluid chemistry [e.g., 4, 5]. To understand how vent fluid REE-signatures are generated during water-rock interaction processes we reacted unaltered gabbro with natural bottom seawater at 425 °C and 400 bar and at 425 and 475 °C at 1000 bar at variable w/r (mass) ratios ranging from 0.5-10 by using cold seal pressure vessels (CSPV). The run durations varied from 3-72 h. Reacted fluids were analysed for major and trace elements by ICP-OES and ICP-MS. In our experiments, ';atypical' REE fluid pattern similar to those of SP fluids were obtained at high w/r ratio (5 and 10) that might be characteristic for focused fluid-flow along e.g., detachment faults at slow-spreading MOR [6]. In contrast, more ';typical'-like REE pattern with elevated LREE and slightly positive Eu anomalies have been reproduced at low w/r ratio (0.5-1). Results of numerical simulations imply that strong positive Eu anomalies of fluids and altered gabbro from high temperature MOR hydrothermal systems can be created by intense rock leaching processes at high w/r ratio (5-10). This suggests that hydrothermal circulation through the ocean crust creates ';typical' REE fluid pattern with strong positive Eu anomalies if seawater reacts with gabbroic host rock that has been already leached in REE at high fluid fluxes. Simulations of the temporal chemical evolution of high temperature MOR hydrothermal systems reveal that rock and fluid REE contents can rapidly decrease within several months particularly at high fluid fluxes. In contrast, the reaction with ';fresh', unaltered rock is evident from the high REE concentration of SP fluids. Both, fluid access to fresh rock and the fluid flux should therefore significantly control chemical fluxes to the ocean. Thus, high chemical fluxes can be expected in particular from early stage high-temperature MOR hydrothermal systems that are assumed to be not uncommon along the slow-spreading MAR. [1] Koschinsky A., Garbe-Schönberg D., Sander S., Schmidt K., Gennerich H.-H., and Strauss H. (2008) Geology 36, 615-618. [2] Schmidt K., Garbe-Schönberg D., Bau M., and Koschinsky A. (2010) Geochim. Cosmochim. Acta 74, 4058-4077. [3] Douville E., Bienvenu P., Charlou J. L., Donval J. P., Fouquet Y., Appriou P., and Gamo T. (1999). Geochim. Cosmochim. Acta 63, 627-643. [4] Seyfried [Jr.] W. E. and Bischoff J. L. (1977) Earth. Planet. Sci. Lett. 34, 71-77. [5] Hajash A. and Chandler G. W. (1981) Contrib. Mineral. Petrol. 78, 240-254. [6] McCaig A.M. and Harris M. (2012) Geology 40, 367-370.