Summary Struvite (magnesium ammonium phosphate‐MgNH4PO4·6H2O), which can extensively crystallize in wastewater treatments, is a potential source of N and P as fertilizer, as well as a means of P conservation. However, little is known of microbial interactions with struvite which would result in element release. In this work, the geoactive fungus Aspergillus niger was investigated for struvite transformation on solid and in liquid media. Aspergillus niger was capable of solubilizing natural (fragments and powder) and synthetic struvite when incorporated into solid medium, with accompanying acidification of the media, and extensive precipitation of magnesium oxalate dihydrate (glushinskite, Mg(C2O4).2H2O) occurring under growing colonies. In liquid media, A. niger was able to solubilize natural and synthetic struvite releasing mobile phosphate (PO43−) and magnesium (Mg2+), the latter reacting with excreted oxalate resulting in precipitation of magnesium oxalate dihydrate which also accumulated within the mycelial pellets. Struvite was also found to influence the morphology of A. niger mycelial pellets. These findings contribute further understanding of struvite solubilization, element release and secondary oxalate formation, relevant to the biogeochemical cycling of phosphate minerals, and further directions utilizing these mechanisms in environmental biotechnologies such as element biorecovery and biofertilizer applications.

In this research, the capabilities of culture supernatants generated by the oxalate-producing fungus Aspergillus niger for the bioprecipitation and biorecovery of cobalt and nickel were investigated, as was the influence of extracellular polymeric substances (EPS) on these processes. The removal of cobalt from solution was >90% for all tested Co concentrations: maximal nickel recovery was >80%. Energy-dispersive X-ray analysis (EDXA) and X-ray diffraction (XRD) confirmed the formation of cobalt and nickel oxalate. In a mixture of cobalt and nickel, cobalt oxalate appeared to predominate precipitation and was dependent on the mixture ratios of the two metals. The presence of EPS together with oxalate in solution decreased the recovery of nickel but did not influence the recovery of cobalt. Concentrations of extracellular protein showed a significant decrease after precipitation while no significant difference was found for extracellular polysaccharide concentrations before and after oxalate precipitation. These results showed that extracellular protein rather than extracellular polysaccharide played a more important role in influencing the biorecovery of metal oxalates from solution. Excitation-emission matrix (EEM) fluorescence spectroscopy showed that aromatic protein-like and hydrophobic acid-like substances from the EPS complexed with cobalt but did not for nickel. The humic acid-like substances from the EPS showed a higher affinity for cobalt than for nickel.

SummaryIn this study, the ability of the geoactive fungus Aspergillus niger to colonize and transform manganese nodules from the Clarion‐Clipperton Zone in both solid and liquid media was investigated. Aspergillus niger was able to colonize and penetrate manganese nodules embedded in solid medium and effect extensive transformation of the mineral in both fragmented and powder forms, precipitating manganese and calcium oxalates. Transformation of manganese nodule powder also occurred in a liquid medium in which A. niger was able to remove the fine particles from suspension which were accumulated within the central region of the resulting mycelial pellets and transformed into manganese oxalate dihydrate (lindbergite) and calcium oxalate dihydrate (weddellite). These findings contribute to an understanding of environmental processes involving insoluble manganese oxides, with practical relevance to chemoorganotrophic mineral bioprocessing applications, and, to the best of our knowledge, represent the first demonstration of fundamental direct and indirect interactions between geoactive fungi and manganese nodules.

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There are a need for novel, economical and efficient metal processing technologies to improve critical metal sustainability, particularly for cobalt and nickel which have extensive applications in low-carbon energy technologies. Fungal metal biorecovery processes show potential in this regard and the products of recovery are also industrially significant. Here we present a basis for selective biorecovery of Co and Ni oxalates and phosphates using reactive spent Aspergillus niger culture filtrate containing mycogenic oxalate and phosphate solubilized from struvite. Selective precipitation of oxalates was achieved by adjusting phosphate-laden filtrates to pH 2.5 prior to precipitation. Co recovery at pH 2.5 was high with a maximum of~96% achieved, while~60% Ni recovery was achieved, yielding microscale polyhedral biominerals. Co and Ni phosphates were precipitated at pH 7.5, following prior oxalate removal, resulting in neartotal Co recovery (>99%), while Ni phosphate yields were also high with a recovery maximum of 83.0%.

Manganese oxide minerals can become enriched in a variety of metals through adsorption and redox processes, and this forms the basis for a close geochemical relationship between Mn oxide phases and Co. Since oxalate-producing fungi can effect geochemical transformation of Mn oxides, an understanding of the fate of Co during such processes could provide new insights on the geochemical behaviour of Co. In this work, the transformation of Mn oxides by Aspergillus niger was investigated using a Co-bearing manganiferous laterite, and a synthetic Co-doped birnessite. A. niger could transform laterite in both fragmented and powder forms, resulting in formation of biomineral crusts that were composed of Mn oxalates hosting Co, Ni and, in transformed laterite fragments, Mg. Total transformation of Co-doped birnessite resulted in precipitation of Co-bearing Mn oxalate. Fungal transformation of the Mn oxide phases included Mn(III,IV) reduction by oxalate, and may also have involved reduction of Co(III) to Co(II). These findings demonstrate that oxalate-producing fungi can influence Co speciation in Mn oxides, with implications for other hosted metals including Al and Fe. This work also provides further understanding of the roles of fungi as geoactive agents which can inform potential applications in metal bioremediation, recycling and biorecovery.

Geoactive fungi such as Aspergillus niger play a significant role in bioweathering processes and element cycling. These organisms are able to secrete a range of organic acids, such as oxalic acid, into their microenvironment. This enables them to mediate mineral dissolution, leading to metal solubilization and precipitation in the form of secondary biominerals. In this investigation, such biotransformation processes were explored as a means of cobalt bioprocessing, an E-tech element identified as being of key strategic importance, in addition to other mineralogically related metals. A range of Co-bearing mineral phases were investigated, including a Co-bearing lithiophorite [(Al,Li)MnO2(OH)2] and erythrite (Co3(AsO4)2·8H2O), in addition to seafloor ferromanganese nodules. Bioleaching and bioprecipitation studies were carried out to investigate the ability of A. nigerto leach cobalt and related metals from Co-bearing minerals, and to precipitate them in biomineral form as a means of cobalt biorecovery. The objective of the work is to investigate the natural biotransformation of cobalt-bearing minerals, to investigate the factors that influence cobalt bioprocessing and to optimise the maximal yield of cobalt biominerals.