Unravelling the mechanisms underlying marine redox shifts during sedimentary manganese metallogenesis: insights from the Carboniferous Muhu deposit, China

Abstract

Sedimentary manganese (Mn) mineralization requires a switch between anoxic and oxic water column conditions, which is commonly explained by the “bathtub ring” model and more recently interpreted by the emerging “episodic ventilation” model. To date, however, it remains unclear regarding how to distinguish between these two mechanisms, profoundly influencing Mn ore prospecting. Here, we conducted a comprehensive investigation on the Muhu Mn deposit in northwestern China. The upward lithological variations from breccia-dominated to fine-grained siliciclastic units (e.g., black shales) are typical of sequence characteristics of rifted basins. Black shales were deposited in deep waters due to continued tectonic subsidence that resulted in hydrographic restriction and bottom water euxinia, as indicated by their high ratios of Fe_HR/Fe_T and Fe_Py/Fe_HR, as well as relatively low Mo/TOC ratios. The Mn ore beds are interbedded with black shales and consist of divalent Mn minerals (e.g., rhodochrosite). They display shale-normalized positive cerium anomalies and negative inorganic carbon isotopes and Mo isotopes, suggesting that these Mn carbonate minerals originated from the diagenetic conversion of primary buried Mn oxides deposited under oxic benthic conditions. Taken together, the intimate spatial association between Mn ore beds and black shales records a dynamic temporal redox change. Such a redox shift is consistent with the “episodic ventilation” scenario, where incursions of oxygenated seawater triggered the deposition of initial Mn oxides. In contrast with the “bathtub ring” model, the ventilation scenario represents distinct spatial-temporal configurations of redox-hydrological conditions. Therefore, deciphering the detailed redox variations of Mn-hosting sedimentary successions, in conjunction with paleogeographic reconstruction, is the key to distinguishing between these two mechanisms.