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Geochemical Constraints on the Element Enrichments of Microbially Mediated Manganese and Iron Ores – an Overview

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Geochemical Constraints on the Element Enrichments of Microbially Mediated Manganese and Iron Ores – an Overview Ore Geology Reviews 136 (2021) 104203 Contents lists available at ScienceDirect Ore Geology Reviews journal homepage: www.elsevier.com/locate/oregeorev Geochemical constraints on the element enrichments of microbially mediated manganese and iron ores – An overview Marta´ Polgari´ a,b,*, Ildiko´ Gyollai a a Institute for Geological and Geochemical Research, Research Centre for Astronomy and Earth Sciences, ELRN, Budapest, Hungary b Eszterhazy´ Karoly´ University, Dept. of Natural Geography and Geoinformatics, Eger, Hungary ARTICLE INFO ABSTRACT Keywords: The role of biogenicity in the mineral world is larger than many might assume. Biological processes interact with Biomineralization physical and chemical processes at the Earth’s surface and far below underground, leading to the formation, for Cell mineralization instance, of banded iron formations and manganese deposits. Microbial mats can form giant sedimentary ore EPS mineralization deposits, which also include enrichment of further elements. Microorganisms play a basic role in catalyzing Ore-forming processes of Fe- and Mn geochemical processes of the Earth and in the control, regularization and leading of cycles of elements. Microbial Diagenesis mats and other biosignatures can be used as indicators for environmental reconstruction in geological samples. This article reviews the many ways that microbially controlled or mediated processes contribute to minerali­ zation and examines some published case studies for clues of what might have been missed in the analysis of sedimentary rocks when biogenicity was not taken into account. Suggestions are made for tests and analyses that will allow the potential role of biomineralization to be investigated in order to obtain a more complete view of formation processes and their implications. 1. Introduction interpretation of datasets. One typical approach is hydrothermal models that overlook the basic role of microbial processes in the sequestration of To understand the main and rare element content of sedimentary ore metal ions from geofluidsinto solid form as minerals and in the selective formations like iron and manganese ores, it is important to consider the enrichments of particular elements. One example is huge formations of role of microbial life (in particular bacteria and fungi) in the geological extreme K-rich altered pyroclastic rock masses (Varga, 1992; Nagy, context of mineralization and mobilization processes, because the 2006). Polgari´ et al. (2019) summarized the important role of micro­ mechanisms governing such activities often supersede purely inorganic bially mediated ore-forming processes and cell mineralization in gen­ reactions. Microbially mediated mineralization is a special metabolic eral. This is explained by case studies such as those of Úrkút in Hungary process resulting in the formation of particular minerals. This includes (Polgari´ et al., 2012a), Datangpo in China (Yu et al., 2019), and Urucum microbially controlled mineralization, a direct connection between mi­ in Brazil) (Biondi et al., 2020). Deposits are the result of complex crobes and minerals. However, indirect connections cannot be excluded; diagenetic processes, which include the decomposition and minerali­ in this case the microbial activity acts on the environment, which then zation of cell and extracellular polymeric substances of Fe and Mn results in mineralization. This is called microbially induced minerali­ bacteria and cyanobacteria. These processes supply bioessential ele­ zation. Microbially mediated minerals are very fine-grained (µm scale) ments depending on the store of elements, the type of metabolism, mi­ and microbial processes are very effective when compared with chem­ crobial species, and the mineralogical characteristics. The ical processes (up to 105 – 106 times more effective). Further details on mineralization of the cells and the extracellular polymeric substances geomicrobiological background on the mineral assemblage of ore de­ material contribute significantly to the material of ore deposits and posits are given in Polgari´ et al. (2019) and in this volume. other rock types, both in terms of quantity and of varied mineral Sources of metals and accompanying elements and the selective composition. enrichment processes that result in the deposits of iron and manganese This paper aims to call attention to the role of microbial processes are often debated, leading to disharmony and controversy in the and to provide a short overview of the role of microbial processes in the * Corresponding author at: Institute for Geological and Geochemical Research, Research Centre for Astronomy and Earth Sciences, ELRN, Budapest, Hungary. E-mail addresses: [email protected] (M. Polgari),´ [email protected] (I. Gyollai). https://doi.org/10.1016/j.oregeorev.2021.104203 Received 26 November 2020; Received in revised form 21 April 2021; Accepted 27 April 2021 Available online 30 April 2021 0169-1368/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). M. Polgari´ and I. Gyollai Ore Geology Reviews 136 (2021) 104203 main and trace element content of sedimentary iron and manganese ores in general. These deposits have high economic value, and the informa­ tion they can provide on the role and development of biomineralization is also valuable. Through re-examining some earlier case studies that overlooked microbial processes in different sedimentary environments, we also aim to demonstrate how the analysis of biomineralization – and particularly the roles of microbially mediated metallization – can contribute to and expand the original conclusions of the study. 2. Historical background What happened before biomineralization spread over the planet and became an important factor in building up the crust? What are the re­ sults of biomineralization on the global level on the planet Earth? 2.1. Before the spread of biomineralization In the beginning, reduced rocks and a reducing atmosphere (90% N2, 10% CO2, low amounts of H2 and traces of O2, CH4, NH3, HCHO, and noble gases) characterized the conditions on the planet, but what happened before biomineralization spread on Earth? One of the most important factors is the appearance of elemental oxygen. As a firststep, photodissociation resulted in oxygen accumulation in the atmosphere till the Urey level, 0.001 Present Atmospheric Level (PAL). The increase of oxygen concentration in the atmosphere is the result of biological activity; there are no other processes that could achieve this. Cyano­ bacteria, living in marine environments, are therefore responsible for the oxygen-bearing atmosphere. The genesis of life and the oxygenic atmosphere are strongly dependent on each other. This increase of ox­ ygen in the atmosphere started around 3.5 Ga years ago, and reached a level at 2.4 Ga years ago, called the Great Oxygenation Event (GOE). The oxygenation of the planet caused dramatic changes in all geospheres. The first biosignatures did not represent geologically important masses. After the appearance of oxygen the first biostructures were stromatolites. Stromatolites are geological structures of variable size (micrometer-scale to meter-scale) that are formed by microbial media­ tion (Fig. 1). These structures are common even today, and can involve signs of biomineralization. Though these structures are widespread in some environments they can mainly be considered as local occurrences. The most common mineral composition of stromatolites is carbonate, but economically important, specific metal-bearing travertine-stromat­ olites also occur (Fe-, Mn-oxides and carbonates, As-bearing stromato­ lites) (Polgari´ et al., 2012a; 2012b). But what happened with the forming oxygen? At first it did not accumulate in the atmosphere; instead, it dissolved in seawater and oxidized the reducted compounds, which was an important role con­ cerning elements with changing valence state. Looking at the Periodic Table, most of its elements are involved with biological cycles (Wackett et al., 2004). These biological cycles could begin only after the appearance of oxygen in the system, as this allows redox changes in many of the metals, which are favored by microbial metabolism. These cycles presented the right set of circumstances for biomineralization processes on a global level. This was followed by a complex diagenetic mineralization of cell and extracellular polymeric substances (EPS). The Fig. 1. Stromatolites. (A-C) Stromatolite in chalcedony and opal, in S-Matra´ evolution of the metal utilization of biota is discussed in the following Mts., Hungary (thin section by optical rock microscopy, 1 N; Müller, 2009). section. What were these chemical compounds for oxidation, and what was years ago (Lyons and Reinhard, 2009). the result of these processes? Why do Fe and Mn play such an important role? Fe is the most frequent heavy metal, with 5% crustal abundance, while Mn accounts - Fe(II) and Mn(II) in the rocks, sediments and oceans for about 0.1% (Turekian, 1969). The answer is that Fe(II) and Mn(II) + + - Compounds of atmosphere mineralized (precipitated) and formed were oxidized to Fe3 and Mn4 forming solid phases (minerals), which rocks precipitated fractionally depending on the available oxygen. Fe precip­ - Composition of oceans changed itation in the form of banded iron formations (BIF) started under suboxic conditions, while Mn precipitation continued to increase oxygen content After the oxidation
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