Iron mineralogy across the oxycline of a lignite mine lake

Abstract

Iron-rich pelagic aggregates of microbial origin named “iron snow” are formed in the water column of some acidic lignite mine lakes. We investigated the evolution of Fe mineralogy across the oxycline of the Lusatian lake 77, Germany at two sampling sites differing by their pH and mixing profiles. The central basin (CB) of this lake shows a dimictic water regime with a non-permanent anoxic deep layer and a homogeneous acidic pH all over the water column (pH3). In contrast, the northern basin (NB) is meromictic with a permanently anoxic bottom layer and a pH increase from pH3 in the mixolimnion (superficial part of the lake) to pH5.5 in the monimolimnion (anoxic bottom layer). Fe minerals above and below the oxycline were identified using X-ray Absorption Spectroscopy (XAS) at the Fe K-edge and further characterized down to the atomic scale by High Resolution Transmission Electron Microscopy (HRTEM) and Scanning Transmission Electron Microscopy (STEM) coupled to Energy Dispersive X-ray Spectroscopy (EDXS). We explored local Fe redox state and C speciation using Scanning Transmission X-ray Microscopy (STXM) at the Fe L2,3-edges and C K-edge. Schwertmannite [Fe8O8(OH)8-2x(SO4)x] identified as the sole Fe mineral in CB, was polycrystalline, consisting in the aggregation of nanodomains of 2–3nm each one exhibiting the crystal structure of schwertmannite. In contrast, schwertmannite was partly (40%) converted to aluminous ferrihydrite when reaching the oxycline in NB. This mineralogical transformation was most probably due to a combination of abiotic and microbial anaerobic processes promoting pH increase and release of Fe(II) (e.g. via heterotrophic Fe(III) reduction) that induce the catalytic hydrolysis of schwertmannite to ferrihydrite. Mineral products were stabilized in the monimolimnion by the adsorption of aluminum, silicate and organic matter. Noteworthy, local Fe redox state heterogeneities were observed, with a few areas enriched in Fe(II) as evidenced by STXM analyses at the Fe L2,3-edges. These local redox heterogeneities could arise from microbial activity (e.g. Fe(III) and/or sulfate reduction). All these results provide an in-depth mineralogical overview of iron phases forming in lake 77 as a basis for future investigations of microbial vs. abiotic parameters controlling their stability and transformation.