Optimisation of biomineral precipitation in chemoorganotrophic systems for metal recovery

Lead Research Organisation: University of Dundee
Department Name: School of Life Sciences

Abstract

Background
Biologically-induced mineralization is common in microbes (1). Fungi are capable of precipitating minerals including oxides, carbonates, phosphates and oxalates by differing mechanisms but all dependent on chemoorganotrophic metabolism, and varying nutritional and environmental conditions (2-4). Such processes receive little attention in the contexts of metal biogeochemistry or biorecovery. Through manipulation of growth conditions, it is possible to promote metal bioprecipitation which provides a means of biorecovery of metals. Further, biominerals can be of nanoscale dimensions in spherical, nanocrystalline, rod and tube-like forms (1). This provides further applied interest in view of the very high surface area to volume ratio and reactivity of such preparations. Oxalates and carbonates, for example, are important in many industrial contexts including as precursors of other useful compounds, e.g. oxides. Industry seeks improved means of making nanoscale preparations of such substances (5,6). There is a dearth of information in this area and this PhD project therefore provides an excellent opportunity to obtain fundamental data and increase understanding of biomineralization in the biogeochemistry of Co and other metals, and applied significance in bioprocessing and production of useful biomineral products.

Workplan
This project will investigate the ability of selected geoactive fungal species to biomineralize Co as insoluble biominerals (primarily oxalates, phosphates, carbonates) with the aim being characterisation and optimisation of each process for maximum yield. A range of nutritional and physico-chemical variables, e.g. carbon and nitrogen source, and pH, will be investigated for the different biomineral systems, along with the mechanisms involved in biomineral precipitation. The overall objective is to optimise the maximal yield of desired biominerals, and to understand conditions that enable bioprecipitation at various scales including nano- and microscale. Conditions necessary for selective recovery of Co from metal mixtures in leachates will be determined, as well as the possibility of obtaining other precipitates from liquors, such as those of Ni. The student will work alongside the PDRA, and will directly interact with other research groups through receipt of materials and leachates, chemical analyses of ores and leachates, and comparison of results with chemolithotrophic metal leaching and bioprecipitation studies. The student will receive cross-disciplinary training in geomicrobiology and geomycology, environmental geochemistry and mineralogy, and will interact with other ongoing research projects and training networks, e.g. Geo-Rep-Net, Geomicrobiology Network, that are concerned with metal mobility in the environment.

References
(1) Gadd, G.M. Metals, minerals and microbes: geomicrobiology and bioremediation. Microbiology 156, 609 - 643 (2010).
(2) Gadd, G.M. Geomycology: biogeochemical transformations of rocks, minerals, metals and radionuclides by fungi, bioweathering and bioremediation. Mycological Research 111, 3-49 (2007).
(3) Rhee, Y.J., Hillier, S. & Gadd, G.M. Lead transformation to pyromorphite by fungi. Current Biology 22, 237-241 (2012).
(4) Wei, Z., Liang, X., Pendlowski, H., Hillier, S., Suntornvongsagul, K., Sihanonth, P. & Gadd, G.M. Fungal biotransformation of zinc silicate and sulfide mineral ores. Environmental Microbiology 15, 2173-2186 (2013).
(5) Aimable, A., Torres Puentes, A. & Bowen, P. Synthesis of porous and nanostructured particles of CuO via a copper oxalate route. Powder Technology 208, 467-471 (2011).
(6) Zhang, S., Wang, F., He, D. & Jia, R. Batch-to-batch control of particle size distribution in cobalt oxalate synthesis process based on hybrid model. Powder Technology 224, 253-259 (2012).

Planned Impact

This project has already built a consortium of unrivalled depth and breadth with the skillset needed to deliver evidence for the decision-making needed to secure the supply of cobalt for the 21st century and beyond. The project will deliver a range of answers to the key science questions that delay such security, delivering a range of tools that can be applied to the identification and definition of new cobalt resources and the application of novel and benign bioprocessing options to the extraction and recovery of cobalt from a range of mineralization types found in Europe and elsewhere in the world.
This project has the ambitious plans of providing (i) New geological and mineralogical knowledge from existing and potential deposits of cobalt that will underpin new, more efficient exploration and mining activities (ii) A clearer understanding of the natural biochemical cycle of cobalt better defining the pathways that make and break cobalt-bearing compounds in natural systems (iii) An assessment of a range of bioprocessing pathways, at a range of scales, in both reduced and oxidized ore systems, targeted towards more benign biorecovery methods for cobalt (iv) Insights into new methods capable of (bio)engineering compounds for use by the broader the downstream cobalt user community.
The project will provide new knowledge relevant to both UK and international researchers as well as cobalt producing companies and end users of specific cobalt products. The research is also relevant to an understanding of the geology, mineralogy and biogeochemistry of the terrestrial environment, specifically the processes that underpin the biogeochemical cycling of metals. The project will also lead to cross-disciplinary awareness and will train a cohort of new scientists with skills to take the research further.
Commercial development with one or more industrial partners will lead to obvious economic and societal benefit. In addition, various national environmental agencies could benefit from the results of our study, particularly those concerned with land management. User groups and the public will be engaged through organised workshops as well as specific meetings. The primary mechanism for knowledge exchange with academic colleagues will be publication of papers in international refereed journals and conference presentations. We will also organise symposia through selected learned societies. We will establish a project website that describes the research in accessible terms and project members will be able to add new material to the website on a regular basis. We will specifically engage with the public through the public learning programmes at individual consortium institutions and we will engage with schools targeted at Key Stages 3 and 4, encouraging pupils to engage with research science via direct relationships with individual young researchers in the SoS programme.

Publications

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Studentship Projects

Project Reference Relationship Related To Start End Student Name
NE/M011275/1 01/05/2015 31/03/2021
1807872 Studentship NE/M011275/1 05/09/2016 04/06/2020
 
Description Overall this project involved research into the role of fungi in the transformation of metal-bearing minerals that are considered important future resources of critical metals essential for clean energy technologies, in addition to efficient, environmentally-friendly and low-cost metal bioprocessing systems.

A paper regarding colonisation and penetration of seafloor manganese nodules by Aspergillus niger was published (March, 2019). In this work the ability of A. niger to grow into and colonise manganese nodule fragments on malt extract agar was investigated. Using scanning electron microscopy (SEM) fungal hyphae were observed growing through cracks and fissures in the mineral. Furthermore, the formation of secondary minerals was observed, which had precipitated on the mineral surface due to the action of mycogenic organic acids, such as oxalic acid. Using energy-dispersive X-ray analysis (EDXA) and X-ray diffraction (XRD) these secondary minerals were determined to be calcium oxalates and manganese oxalate.

Similar work has been carried out in which the transformation of further metal-rich mineral phases by aspergillus niger was investigated, including manganese-rich lateritic material (from Nkamouna laterite, Cameroon), a synthetic Co-containing birnessite and erythrite (Co3(AsO4)2 · 8(H2O)), among others.


Furthermore, research into the ability of geoactive fungi such as aspergillus niger to bioleach (i.e. extract metals from minerals into solution) cobalt-bearing mineral phases using organic acids has been completed. This research focused on the bioleaching of deep-sea manganese nodules and manganese-rich laterites by Aspergillus niger and has provided new insight into the efficacy of such processes.

Other work has focused on the recovery of metals from simulated leach solutions as carbonates, oxalates and phosphates using filtered fungal growth supernatants. The metals investigated include cobalt and nickel. Efficient precipitation was observed at high metal concentrations, and the precipitation of mixed Co-Ni precipitates was demonstrated. This research has developed new, highly efficient systems for removing metals from solution in industrially useful forms.
Exploitation Route Further contributions to the field by other researchers may involve improving the efficiency of/ scaling up bioprocessing approaches which have been demonstrated in proof-of-concept by this work, or to extend the research to include other fungal processes involving additional minerals and metals.
Sectors Electronics,Energy,Environment,Manufacturing, including Industrial Biotechology

URL https://sfamjournals.onlinelibrary.wiley.com/doi/full/10.1111/1462-2920.14591