Metabolomic Analysis Reveals Contributions of Citric and Citramalic Acids to Rare Earth Bioleaching by a Paecilomyces Fungus.

Conventional methods for extracting rare earth elements from monazite ore require high energy inputs and produce environmentally damaging waste streams. Bioleaching offers a potentially more environmentally friendly alternative extraction process. In order to better understand bioleaching mechanisms, we conducted an exo-metabolomic analysis of a previously isolated rare earth bioleaching fungus from the genus Paecilomyces (GenBank accession numbers KM874779 and KM 874781) to identify contributions of compounds exuded by this fungus to bioleaching activity. Exuded compounds were compared under two growth conditions: growth with monazite ore as the only phosphate source, and growth with a soluble phosphate source (K2HPO4) added. Overall metabolite profiling, in combination with glucose consumption and biomass accumulation data, reflected a lag in growth when this organism was grown with only monazite. We analyzed the relationships between metabolite concentrations, rare earth solubilization, and growth conditions, and identified several metabolites potentially associated with bioleaching. Further investigation using laboratory prepared solutions of 17 of these metabolites indicated statistically significant leaching contributions from both citric and citramalic acids. These contributions (16.4 and 15.0 mg/L total rare earths solubilized) accounted for a portion, but not all, of the leaching achieved with direct bioleaching (42 ± 15 mg/L final rare earth concentration). Additionally, citramalic acid released significantly less of the radioactive element thorium than did citric acid (0.25 ± 0.01 mg/L compared to 1.18 ± 0.01 mg/L), suggesting that citramalic acid may have preferable leaching properties for a monazite bioleaching process

Biomining of Rare Earth Elements from Phosphate Ores and Minerals

Rare earth elements (REEs) are important for establishing a technology based society, however are difficult to process. The use of biomining for the extraction of REEs minerals offers a benign alternative to conventional hydrometallurgical routes with more selective solubilisation of REEs over radionuclides. The use of phosphate solubilising microorganisms in the bioleaching of REEs was investigated to gain a better understanding of the leaching behaviour of individual REEs and the mechanism attributed to their mobilisation

Rare Earth Elements Biorecovery from Mineral Ores and Industrial Wastes

Rare earth elements (REEs) are critical raw materials and are attracting interest because of their applications in novel technologies and green economy. Biohydrometallurgy has been used to extract other base metals; however, bioleaching studies of REE mineral extraction from mineral ores and wastes are yet in their infancy. Mineral ores have been treated with a variety of microorganisms. Phosphate-solubilizing microorganims are particularly relevant in the bioleaching of monazite because transform insoluble phosphate into more soluble form which directly and/or indirectly contributes to their metabolism. The increase of wastes containing REEs turns them into an important alternative source. The application of bioleaching techniques to the treatment of solid wastes might contribute to the conversion towards a more sustainable and environmental friendly economy minimizing the amount of tailings or residues that exert a harmful impact on the environment

Study of Biofilm Formation by Phosphate Solubilising Bacteria on Rare Earth Elements Phosphate Minerals

Klebsiella aerogenes, a phosphate-solubilising microorganism, formed biofilm on monazite in three stages: initial attachment, mature biofilm, and dispersion. The eDNA produced aids in initial attachment and mechanical stability. Biofilm was formed on and around physical imperfections, leading to mineral surface erosion. Secondary ion mass spectrometry analysis showed evidence of complex formation between monazite’s rare earth content and organic acid residues produced by the bacteria

Comparison of heterotrophic bioleaching and ammonium sulfate ion exchange leaching of Rare Earth Elements from a Madagascan Ion-Adsorption Clay

Rare earth elements (REE) are considered to be a critical resource, because of their importance in green energy applications and the overdependence on Chinese imports. REE rich ion-adsorption deposits (IAD) result from tropical weathering of REE enriched igneous rocks. Commercial REE leaching from IAD, using salt solutions occurs via an ion-exchange mechanism. Bioleaching of IAD by Aspergillus or Bacillus, was compared to Uninoculated Control and Salt leaching (0.5 M ammonium sulfate) over 60 days. Salt leaching was most effective, followed by Aspergillus, Bacillus then Uninoculated Control. Most of the REE and major elements released by Salt leaching occurred before day 3. With bioleaching, REE and major elements release increased with time and had a greater heavy to light REE ratio. Similar total heavy REE release was observed in Salt leaching and Aspergillus (73.1% and 70.7% Lu respectively). In bioleaching experiments, pH was inversely correlated with REE release (R2 = 0.947 for Lu) indicating leaching by microbially produced acids. These experiments show the potential for bioleaching of REE from IAD, but dissolution of undesirable elements could cause problems in downstream processing. Further understanding of the bioleaching mechanisms could lead to optimization of REE recover

Comparison of Three Approaches for Bioleaching of Rare Earth Elements from Bauxite

Approximately 300 million tonnes of bauxite are processed annually, primarily to extract alumina, and can contain moderate rare earth element (REE) concentrations, which are critical to a green energy future. Three bioleaching techniques (organic acid, reductive and oxidative) were tested on three karst bauxites using either Aspergillus sp. (organic acid bioleaching) or Acidithiobacillus ferrooxidans (reductive and oxidative bioleaching). Recovery was highest in relation to middle REE (generally Nd to Gd), with maximum recovery of individual REE between 26.2% and 62.8%, depending on the bauxite sample. REE recovery occurred at low pH (generally < 3), as a result of organic acids produced by Aspergillus sp. or sulphuric acid present in A. ferrooxidans growth media. Acid production was seen when A. ferrooxidans was present. However, a clear increase in REE recovery in the presence of A. ferrooxidans (compared to the control) was only seen with one bauxite sample (clay-rich) and only under oxidative conditions. The complex and varied nature of REE-bearing minerals in bauxite provides multiple targets for bioleaching, and although the majority of recoverable REE can be leached by organic and inorganic acids, there is potential for enhanced recovery by bioleaching

MINERALOGY CHARACTERS OF CIJULANG PHOSPHATE ROCKS RELATED TO BIOLEACHING PROCESS

Research on potency test of selected phosphate solubilizing microfungi (PSM) isolates had been conducted. The purpose was to obtain the most potential indigenous microfungi to solubilizing phosphate in bioleaching process. Identification with moist chamber showed that the selected PSM belonged to Penicillium genera. Bioleaching process through measuring process growth and oxalic acid production was effective on the 8th day. Chemical analysis showed that bioleaching process using selected indigenous PSM of phosphate rock was able to increase P2O5 content from 38.40 to 49.70% or improve around 11.30%. Experimental condition for such a recovery was -140+200# of sample size an 5% of percent solid. Mineralogy characters of the leached phosphate rocks showed some micro cracks as well as encapsulation by clay minerals. Not all phosphor element was leached by oxalic acid produced by microfungi

Biotechnology Processes for Scalable, Selective Rare Earth Element Recovery

Biorecovery of rare earth elements (REE) from wastes and ores is achieved by bacteria using biogenic phosphates. One approach uses an enzyme that biomineralises REE phosphate crystals into the extracellular polymeric matrix (EPM). The enzyme, co-localised in the EPM, provides a continuous phosphate feed into biomineralisation. The bacteria can be immobilised in a column, allowing continuous metal removal. Metals biocrystallise at different rates. By choosing suitable conditions and column flow rates selective recovery of REE against uranium and thorium can potentially overcome a bottleneck in recovery of REE from mine tailings and ore leachates co-contaminated with these radionuclides. Another approach to REE recovery first lays down calcium phosphate as hydroxyapatite (Bio-HA) using the enzymatic process. Bio-HA then captures REE, loading REE of up to 84% of the HA-mass. REE3+ first localises at the grain boundaries of the small bio-crystallites and then substitutes for Ca2+ stoichiometrically within the HA. After REE capture the bio-HA/REE hybrid can be separated magnetically. A wider concept: using a ‘priming’ deposit of one mineral to facilitate the capture of REEs, has been shown, potentially providing a basis for selective REE recovery which would provide advantages over the > 100 steps currently used in commercial REE refining