Competitive Scavenging of Trace Metals by HFO and HMO during Redox-driven Early Diagenesis of Ferromanganese Nodules (11 pp)

Abstract

Dedicated to Prof. Dr. Ulrich Forstner on his 65th birthday Surface complexation models (SCM) alone have yet less successfully reproduced sorption isotherms of hydrous manganese oxides (HMO). This is in part due to the fact that the HMO structure may vary with pH, and also because microbially formed natural HMO has an oxidation number O/Mn 〈 2, i.e. is of non-stoichiometrical composition. The former effect has often led to severe artefacts, such as an under-prediction of metal sequestration at low pH, and non-comparable pK and pHZPC values in literature. The latter effect is of particular importance for environments of varying redox conditions like sediments. We propose therefore a new sorption model comprising of amphoteric site SCM, ion exchange due to permanent charge compensation, and solid solution formation, in order to comply at least in part with the redox complexity of HMO phases of stable birnessite- and buserite-type structures. The model is run by a new Gibbs energy minimization code which is shown to be particularly suitable for such a sorption continuum approach. Initial calibration of the model was performed by experimental literature data on simple laboratory systems. Thus parameterised, we simulated on the basis of available field data the effect of redox-driven dissolution of a ferromanganese nodule on the partitioning of metals between the interacting HMO, HFO, and marine water phases. Our scenario model suggests that significant fraction of Mn and other metals, probably 50% or more, may be recycled to water column from the surface of the ferromanganese nodule upon gradual development of the bottom water stagnation, except of Zn for which a by far stronger net retention was found. Our model, even if only a first approximation, clearly shows that stagnation in the marine bottom water, once occurring, can drastically change primary element proxy records in ferromanganese nodules, smoothing out any anomalous patterns in the most recent record.