Manganese oxides are considered an essential component of natural geochemical barriers due to their redox and sorptive reactivity towards essential and potentially toxic trace elements. Despite the perception that they are in a relatively stable phase, microorganisms can actively alter the prevailing conditions in their microenvironment and initiate the dissolution of minerals, a process that is governed by various direct (enzymatic) or indirect mechanisms. Microorganisms are also capable of precipitating the bioavailable manganese ions via redox transformations into biogenic minerals, including manganese oxides (e.g., low-crystalline birnessite) or oxalates. Microbially mediated transformation influences the (bio)geochemistry of manganese and also the environmental chemistry of elements intimately associated with its oxides. Therefore, the biodeterioration of manganese-bearing phases and the subsequent biologically induced precipitation of new biogenic minerals may inevitably and severely impact the environment. This review highlights and discusses the role of microbially induced or catalyzed processes that affect the transformation of manganese oxides in the environment as relevant to the function of geochemical barriers.

Center for Advanced Materials Qatar University Doha P O Box 2713 Qatar

Department of Agraria Mediterranea University of Reggio Calabria Feo di Vito snc 89124 Reggio Calabria Italy

Department of Earth Resources and Environmental Engineering Hanyang University 222 Wangsimni ro Seongdong gu Seoul 04763 Republic of Korea

Department of Environmental Engineering Faculty of Mining and Geology VŠB Technical University of Ostrava 17 Listopadu 15 2172 708 00 Ostrava Czech Republic

Institute of Laboratory Research on Geomaterials Faculty of Natural Sciences Comenius University in Bratislava Mlynská dolina Ilkovičova 6 84215 Bratislava Slovakia

Institute of Molecular Biology Slovak Academy of Sciences Dúbravská Cesta 21 84551 Bratislava Slovakia

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