Halogens Geochemistry in Ferromanganese Crusts – Does The Electrochemical Model Apply?

"INTRODUCTIONThe majority of studies on the genesis of ferromanganese crusts focus on the adsorption and accumulation of metals, and therefore cations, especially those of economic interest. From these studies, a first-order electrochemical model has been proposed based on the zero point of charge of the manganese and iron oxides at typical seawater pH, which assumes that positively charged ions will bind to the negatively charged manganese oxide phase and neutral and negatively charged ions will bind to the slightly positively charged iron oxide phase (e.g. Koschinsky and Halbach,1995; Hein et al., 2013). While the theory behind this model is sound, and it has been consistent for many elements, other elements may not follow the model (Koschinsky and Hein, 2003), and thus requires additional investigation and validation. As a new approach to understanding element accumulation in ferromanganese crusts and to test the proposed electrochemical model, this study investigates the surface chemistry of the halogens, which occur as negatively charged ions in seawater and have high and consistent concentrations in seawater.ResultsBulk Halogen ConcentrationsTo determine the distribution of halogens in ferromanganese crusts, an initial dataset of 24 FeMn crusts (24 bulk and 19 layer samples) from throughout the global ocean, including the Arctic and the Southern Oceans, has been analyzed for chlorine and fluorine content using ion-selective electrode. Although both Cl and F are conservative in seawater, their content in crusts shows striking variability (Cl: 326 - 13310 ppm; F: 146 – 1048 ppm for non-phosphatized crusts) and has no obvious geographic relationship to ocean basin and no correlation with water depth, latitude, or longitude. We plan to have bromine concentration data to present at the time of this conference."