Solid State Phenomena Vol. 262

Abstract: The FAME (Flexible and Mobile Economic Processing Technologies) project targets the development of flexible and economic processing technologies for small and low-grade European ore deposits with complex mineralogy, targeting greisen, skarn and pegmatite ores. Amongst the valuable elements to be recovered are W, Sn, Li and minor constituents like In, Ge, Ga, Nb or Ta. To improve the processing of by-product sulfides to recover critical elements like In or Ga and to develop innovative processing strategies for raw materials, biohydrometallurgical technologies are investigated. There are different approaches in FAME for the biohydrometallurgical recovery of valuable metals from low grade ores: 1) the extraction of Li from zinnwaldite and lepidolite, 2) the heap leaching of low grade sulfide ore unsuitable for conventional processing to recover Zn and In, and 3) the bioleaching of sulfide concentrates in a two-stage tank process for recovery of Zn and Cu. So far the most promising results were achieved for heap-leaching of low-grade Zn-In ores achieving 7.4 ppm In in the leaching solution and for Li extraction (28%) from zinnwaldite.

Abstract: Magnetic MnFe₂O₄ nanoparticles (MNPs) were fabricated and entrapped in amine-rich chitosan (CS) sorbents containing multi-walled carbon nanotubes (MWCNTs) or polyethyleneimine (PEI). Magnetic polymer composite sponges (MPCSs) and magnetic polymer composite fibers (MPCFs) were prepared through mixing each of MWCNT and PEI with MNPs-CS solution. The successful fabrication of MPCSs and MPCFs was confirmed through FTIR and VSM analyses. The as-fabricated MPCSs and MPCFs were used for adsorptive recovery of Pt (IV) from acidic solution. The maximum uptakes of Pt (IV) ions by the MPCSs and MPCFs were estimated to be 218.2 ± 8.3 and 371.4 ± 16.8 mg/g, respectively. Moreover, the Pt (IV)-loaded MPCSs and MPCFs were easily separated from aqueous solution under magnetic field after sorption process.

Abstract: As mineralogy has become more complex in the long history of hydrometallurgical processing, the process routes and equipment used had to adapt to the changing conditions [1]. Hydrometallurgical bioleaching processes have been developed for different key metals such as gold, nickel and copper amongst others, to overcome the limitations of leaching sulphidic ores. The core of such a hydrometallurgical bioleaching plant is a cascade of stirred atmospheric tank reactors. Large volumes of air that are blown into these tanks must be dispersed by the agitator in order to provide the necessary oxygen mass transfer rates. At the same time the agitator system must be able to properly suspend all solids, homogenize the vessel contents and remove the exothermic reaction heat by inner tube bundles to achieve optimal reaction conditions. Besides the ‘economies of scale’ and advances in process results, cost optimization of such systems is fundamental. Therefore EKATO has developed the Combijet⁺ technology which has significantly reduced power requirements, compared to conventional agitators. Another advantage of the Combijet⁺ technology is that the gas is injected directly into the highest shear zones, at the impeller blades. As a result the oxygen mass transfer is improved and also substantial cost savings for compressor power are possible. The technical paper will present EKATO’s Combijet technologies which support the next step towards a new generation of biohydrometallurgical processing plants. It will also give examples of large scale commercial applications where this technology is successfully in operation.

Abstract: This article presents as follows the most recent progresses of our group on in-situ characterization and evaluation of the molecular mechanisms of interfacial interaction of minerals and bioleaching microorganisms. (1) By studying the speciation transformation of iron/copper/sulfur on the mineral surface, the evolution of cell surface properties and EPS composition, the evolution of microbial community structure, and the evolution of expression of key oxidase genes during bioleaching, to characterize the adaptation process and therein the effects of it on the specific sulfur oxidation efficiency of bioleaching; (2) by in-situ characterization of the evolution of chalcopyrite surface microstructure, chemical speciation and the biofilm formation, to illustrate the specific adsorption and the relationship between cell growth/biofilm formation and the structure and speciation on the defect mineral surface; (3) by studying the utilization, transformation and activation of S⁰, which is one of the major intermediates during bioleaching, and the distribution of extracellular thiol groups and iron speciation, to evaluate in situ the sulfur activation mechanism; and (4) by comparative proteomics study of the extracellular and outmembrane proteins and looking up the genome sequence, to screen sulfur activation/transportation relevant proteins and genes.

Abstract: Bioleaching of copper sulfides is catalyzed by iron-and sulfur-oxidizing acidophilic microorganisms attached to the mineral surface forming a biofilm. However, the link between copper sulfides bioleaching and biofilm formation is not yet fully understood. Understanding the factors that are limiting the bioleaching kinetics for different copper sulfide minerals through exhaustive mineralogical analysis of the mineral surface with concomitant biofilm formation during the leaching process will deliver new process conditions with enhanced kinetics and higher copper recovery. In this work we have developed and standardized a reproducible flow cell method able to mimic heap/dump bioleaching laminar flow conditions to study the mineralogical dynamics by advanced mineralogical analysis including QEMSCAN and SEM-EDS coupled to biofilm formation analysis. Based on this method, the bioleaching mineralogical dynamics of primary copper sulfides (enargite (Cu₃AsS₄), chalcopyrite (CuFeS₂) and bornite (Cu₅FeS₄)) have been determined in the presence of biofilm formation. Supported by the observed mineralogical dynamics, different mechanisms of dissolution for bioleaching were observed as well as selective biofilm formation over the mineral surface, showing enhanced conditions for copper recovery.

Abstract: The Acidithiobacillus genus plays a relevant role in bioleaching. The molecular understanding of biofilm formation has been pointed out to design biological strategies to improve the efficiency of this industrial process and to prevent environmental damages caused by acid mine/rock drainages. In Acidithiobacillus spp., the molecular mechanisms involved in biofilm formation are currently emerging. The second messenger cyclic diguanylate (c-di-GMP) appears as a key player for biofilm formation by Acidithiobacillus sp. Here, results obtained from genomic analysis to characterize c-di-GMP pathway in At. thiooxidans are reported. Intracellular levels of c-di-GMP have been previously measured and data indicated that they are higher in adhered cells than planktonic ones. During the course of characterization of c-di-GMP effectors, a complete pel-like gene cluster has been identified in At. thiooxidans. By using total RNA obtained from planktonic and adhered sulfur-grown cells, transcriptomic analysis revealed that pelA belonging to the pel-like gene cluster is overexpressed in adhered cells. Moreover, genetic experiments were performed to compare wild type and null-mutant strains of At. thiooxidans for assessing the role of Pel exopolysaccharide. All together, the results obtained suggest a specific role for Pel machinery in the attachment to solid energy substrates by At. thiooxidans.

Abstract: Recently, a novel acidophilic heterotrophic iron oxidizing bacterium belonging to the newly described genus Acidibacillus (formerly Alicyclobacillus) was isolated from a water drainage ditch in Freiberg, Germany. Bioleaching tests showed that Acidibacillus ferrooxidans Huett2 contributes to the dissolution of minerals. As microbe-mineral interactions play a crucial role in nature and enhance the reaction kinetics of the mineral dissolution, attachment of Ab. ferrooxidans Huett2 on the sulfide minerals pyrite (FeS₂), chalcopyrite (CuFeS₂), and chalcocite (Cu₂S) is in the focus of our current investigations.

Abstract: The family Acidiferrobacteraceae (order Acidiferrobacterales) currently contains three genera of chemolithoautotrophs: Sulfuricaulis (2016), Sulfurifustis (2015) and Acidiferrobacter (2011). While the two former are neutrophilic sulfur oxidizers isolated from lake sediments in Japan, the latter is an extremely acidophilic, moderately osmophilic, thermotolerant iron/sulfur oxidizer known to occur in macroscopic streamers in Rio Tinto, Spain and in acid waters worldwide. The type strains of both Sulfuricaulis limnicola (HA5^T) and Sulfurifustis variabilis (skN76^T) have been sequenced, and the draft genome of the ZJ isolate of Acidiferrobacter thiooxydans (MDCF01) has recently been deposited in public databases. Despite this fact, little evidence on the genomic diversity and evolution of this group has been presented so far. Using comparative genomic analyses and phylogenetic reconstruction strategies, we explored the evolutionary information contained in the available genome sequences to shed light on the taxonomic status of a novel isolate of the genus Acidiferrobacter (SP-III/3; DSM 27195).

Abstract: Recombinant rusticyanin was produced in Pichia pastoris, then purified and immobilized on Sepharose CL-4B with periodate activation. Cellular lysate of acidophilic Acidithiobacillus ferrooxidans was applied to an affinity column with immobilized rusticyanin. Rusticyanin-binding proteins, separated using 1D PAGE and identified by mass spectrometry, included anticipated interacting partners, such as cytochromes Cyc1 and Cyc2, which are involved in the downhill electron pathway from ferrous iron to oxygen. However, the results indicate that rusticyanin’s functional protein-protein interaction (PPI) network could be more complex than expected, including various proteins involved in different cellular processes. Although affinity purification coupled to mass spectrometry should mostly detect proteins that bind stably, and thus are likely participants in functional in vivo PPIs, further verification is needed to exclude non-functional interactants. Nevertheless, our preliminary PPI data confirm some previous experimental findings and indicate potentially fruitful directions for probing additional roles of rusticyanin in sulfur metabolism, copper resistance, anaerobic iron reduction, iron transport, and oxidative stress in extreme acidophiles.

Abstract: Inhibition of iron oxidation by Leptospirillum ferriphilum in the presence of thiocyanate (SCN^-) was studied in small-scale batch experiments. The L. ferriphilum culture was challenged with SCN^- over a range of 0 mg/l to 10 mg/l. The data showed that L. ferriphilum was able to utilise ferrous iron at low-level concentrations of SCN^- (0.25 mg/l to 1.75 mg/l), however exhibited a reduction in oxidation rate relative to the control (0 mg/l). Moreover, introduction of SCN^- at low-level concentrations resulted in a lag in iron oxidation activity, specifically at concentrations of 1 mg/l, 1.25 mg/l and 1.75 mg/l. No iron oxidation was observed at SCN^- concentrations above 1.75 mg/l, indicating complete inhibition. As L. ferriphilum is the dominant iron oxidising bacteria within biooxidation tanks, evidence of sustained iron oxidation activity at low-level SCN^- concentrations affirms the potential of recycling bioremediated cyanidation wastewater within biooxidation circuits in bioprocesses for gold recovery from sulfidic minerals as residual SCN^- concentrations in remediated effluent are reportedly lower than 0.25 mg/l. The inhibition kinetics of this system need to be explored further in order to develop a deeper understanding of the system such that it may be applied to inform process operation.