Colonization and bioweathering of monazite by Aspergillus niger: solubilization and precipitation of rare earth elements

Geoactive fungi play a significant role in bioweathering of rock and mineral substrates. Monazite is a phosphate mineral containing the rare earth elements (REE) cerium, lanthanum and neodymium. Little is known about geomicrobial transformations of REE-bearing minerals which are also relevant to REE biorecovery from terrestrial and extra-terrestrial reserves. The geoactive soil fungus Aspergillus niger colonized monazite in solid and liquid growth media without any apparent growth inhibition. In a glucose-minerals salts medium, monazite enhanced growth and mycelium extensively covered rock particle surfaces, probably due to the provision of phosphate and essential trace metals. Teeth-like and pagoda-like etching patterns indicated monazite dissolution, with extensive precipitation of secondary oxalate minerals. Biomechanical forces ensued causing aggressive bioweathering effects by tunnelling, penetration and splitting of the ore particles. High amounts of oxalic acid (~46 mM) and moderate amounts of citric acid (~5 mM) were produced in liquid media containing 2% (wt./vol.) monazite, and REE and phosphate were released. Correlation analysis suggested that citric acid was more effective than oxalic acid in REE mobilization, although the higher concentration of oxalic acid also implied complexant activity, as well as the prime role in REE-oxalate precipitation.     

Colonization,penetration and transformation of manganese oxide nodules by Aspergillus niger

In 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.     

Biotransformation of struvite by Aspergillus niger: phosphate release and magnesium biomineralization as glushinskite

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.     

Fungal transformation of natural and synthetic cobalt-bearing manganese oxides and implications for cobalt biogeochemistry

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.     

Selective fungal bioprecipitation of cobalt and nickel for multiple-product metal recovery

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 near-total Co recovery (>99%), while Ni phosphate yields were also high with a recovery maximum of 83.0%.     

Transformation of vanadinite [Pb5(VO4)3Cl] by fungi

Saprotrophic fungi were investigated for their bioweathering effects on the vanadium‐ and lead‐containing insoluble apatite group mineral, vanadinite [Pb₅(VO₄)₃Cl]. Despite the insolubility of vanadinite, fungi exerted both biochemical and biophysical effects on the mineral including etching, penetration and formation of new biominerals. Lead oxalate was precipitated by Aspergillus niger during bioleaching of natural and synthetic vanadinite. Some calcium oxalate monohydrate (whewellite) was formed with natural vanadinite because of the presence of associated ankerite [Ca(Fe²⁺,Mg)(CO₃)₂]. Aspergillus niger also precipitated lead oxalate during growth in the presence of lead carbonate, vanadium(V) oxide and ammonium metavanadate, while abiotic tests confirmed the efficacy of oxalic acid in solubilizing vanadinite and precipitating lead as oxalate. Geochemical modelling confirmed the complexity of vanadium speciation, and the significant effect of oxalate. Oxalate–vanadium complexes markedly reduced the vanadinite stability field, with cationic lead(II) and lead oxalate also occurring. In all treatments and geochemical simulations, no other lead vanadate, or vanadium minerals were detected. This research highlights the importance of oxalate in vanadinite bioweathering and suggests a general fungal transformation of lead‐containing apatite group minerals (e.g. vanadinite, pyromorphite, mimetite) by this mechanism. The findings are also relevant to remedial treatments for lead/vanadium contamination, and novel approaches for vanadium recovery.     

Antimicrobial study on trivalent lighter rare-earth complexes of 2-pyrazinecarboxylate with hydrazinium cation

The hydrazinium lanthanide metal complexes of 2-pyrazinecarboxylic acid (HpyzCOO) of the formulae (N₂H₅)₂[Ln(pyzCOO)₅]·2H₂O, where Ln=La or Ce and (N₂H₅)₃[Ln(pyzCOO)₄(H₂O)]·2NO₃, where Ln=Pr, Nd, Sm or Dy have been synthesized by the addition of an aqueous solution of the corresponding metal nitrate hydrates to an aqueous mixture of the respective carboxylic acids and hydrazine hydrate. The in vitro antibacterial screening of the free acid and its metal complexes has been carried out against Escherichia coli, Salmonella typhi and Vibrio cholerae. Antifungal activities of all the synthesized compounds were screened for in vitro growth inhibitory activity against Aspergillus fumigatus and Aspergillus niger by using the disc diffusion method. The antimicrobial activities of the prepared metal complexes show more promising activity than the corresponding free acid, its hydrazinium salts, and the standard control antibiotics, Co-trimoxazole and Carbendazim.     

Fungal biotransformation of zinc silicate and sulfide mineral ores

In this work, several fungi with geoactive properties, including Aspergillus niger, Beauveria caledonica and Serpula himantioides, were used to investigate their potential bioweathering effects on zinc silicate and zinc sulfide ores used in zinc extraction and smelting, to gain understanding of the roles that fungi may play in transformations of such minerals in the soil, and effects on metal mobility. Despite the recalcitrance of these minerals, new biominerals resulted from fungal interactions with both the silicate and the sulfide, largely resulting from organic acid excretion. Zinc oxalate dihydrate was formed through oxalate excretion by the test fungi and the mineral surfaces showed varying patterns of bioweathering and biomineral formation. In addition, calcium oxalate was formed from the calcium present in the mineral ore fractions, as well as calcite. Such metal immobilization may indicate that the significance of fungi in effecting metal mobilization from mineral ores such as zinc silicate and zinc sulfide is rather limited, especially if compared with bacterial sulfide leaching. Nevertheless, important bioweathering activities of fungi are confirmed which could be of local significance in soils polluted by such materials, as well as in the mycorrhizosphere.     

Lanthanide chelate complexes of salicyloyl hydrazide-salicylaldehyde schiff base (SHSASB) and anthranilic acid-salicylaldehyde schiff base (AASASB)

New lanthanide complexes of salicylaldehyde- Schiff bases with salicyloyl hydrazide and anthranilic acid, were synthesized by a novel method consisting of refluxing the mixtures of Schiff base ligands and lanthanide trichloroacetate in acetone. Solid complexes of formulae Ln(SHSASB)₃·2H₂O and Ln₂(AASASB)₃·2H₂O where Ln = La---Yb and Y, were isolated. Pronto NMR and IR spectra for the complexes reveal the bidentate binding of both the Schiff base ligands to the lanthanide ion. Electronic spectra along with the conductance data for the complexes indicate a coordination number of six for the lanthanide ion in the complexes of both the Schiff bases.     

The mononuclear and dinuclear dimethoxyethane adducts of lanthanide trichlorides [LnCl3(DME)2]n, n=1 or 2, fundamental starting materials in lanthanide chemistry: preparation and structures

Some new dimethoxyethane (DME) adducts of lanthanide trichlorides of formula [LnCl₃(DME)₂]_n, n=1 or 2; (n=2, Ln=La, Ce, Pr, Nd; n=1, Ln=Eu, Tb, Ho, Tm, Lu) have been prepared by treating Ln₂O₃, or LnCl₃ · nH₂O, or Ln₂(CO₃)₃, in DME as medium, with thionyl chloride at room temperature, eventually in the presence of water in the case of Ln₂O₃ and Ln₂(CO₃)₃. The complexes from lanthanum to praseodymium included are chloro-bridged dimers. In the case of neodymium, the new results complement the literature data, showing that both the mononuclear and dinuclear species exist: neodymium can therefore be regarded as the turning element from dinuclear to mononuclear structures along the series. Only mononuclear complexes were isolated in the Eu-Lu sequence. The lanthanide contraction has been evaluated on the basis of the Ln-O and Ln-Cl bond distances on the isotypical series of the mononuclear complexes LnCl₃(DME)₂ covering a range of 12 atomic numbers.     

Chiroptical Spectra of Tetrakis (+)‐3‐Heptafluorobutylrylcamphorate Ln(III) Complexes with an Encapsulated Alkali Metal Ion: Solution Structures as Revealed by Chiroptical Spectra

The preparation of tetrakis((+)‐hfbc) lanthanide(III) complexes with an encapsulated alkali metal and ammonium ions M[Ln((+)‐hfbc)₄] (hereafter abbreviated as M‐Ln : (+)‐hfbc, (+)‐heptafluorobutyrylcamphorate; M, ammonium or benzyl ammonium ions as well as alkali metal ions) was reported and discussed. The electronic circular dichroism (CD) spectra in the intraligand π?π* transition of M–Ln were examined in view of the solvent effect. Here, the concentration, alkali metal, and ammonium ion dependences are compared with the solid CD, ⁵D₀ ← ⁷F₀(Eu(III)) excitation spectra, circularly polarized luminescence, and vibrational circular dichroism. It has been revealed that the dodecahedral eight coordinate DD‐8‐M‐Ln complexes in crystals are equilibrated between the diastereoselectively formed square antiprism eight coordinate SAPR‐8‐M‐Ln and [Ln((+)‐hfbc)₃] in EtOH and CH₃CN solutions or between the SAPR‐8‐M‐Ln and DD‐D_2d(mmmm)‐8‐M‐Ln complexes in CHCl₃ solution. The observed CD couplets are found to reflect the exciton CD couplets which are useful to determine the four‐bladed SAPR‐(llll) absolute configuration around the lanthanide(III) ion. Chirality 24:1055–1062, 2012. © 2012 Wiley Periodicals, Inc.     

Interactions of phosphate solubilising microorganisms with natural rare-earth phosphate minerals: a study utilizing Western Australian monazite

Many microbial species are capable of solubilising insoluble forms of phosphate and are used in agriculture to improve plant growth. In this study, we apply the use of known phosphate solubilising microbes (PSM) to the release of rare-earth elements (REE) from the rare-earth phosphate mineral, monazite. Two sources of monazite were used, a weathered monazite and mineral sand monazite, both from Western Australia. When incubated with PSM, the REE were preferentially released into the leachate. Penicillum sp. released a total concentration of 12.32 mg L⁻¹ rare-earth elements (Ce, La, Nd, and Pr) from the weathered monazite after 192 h with little release of thorium and iron into solution. However, cultivation on the mineral sands monazite resulted in the preferential release of Fe and Th. Analysis of the leachate detected the production of numerous low-molecular weight organic acids. Gluconic acid was produced by all microorganisms; however, other organic acids produced differed between microbes and the monazite source provided. Abiotic leaching with equivalent combinations of organic acids resulted in the lower release of REE implying that other microbial processes are playing a role in solubilisation of the monazite ore. This study demonstrates that microbial solubilisation of monazite is promising; however, the extent of the reaction is highly dependent on the monazite matrix structure and elemental composition.

     

Direct and Indirect Bioleaching of Cobalt from Low Grade Laterite and Pyritic Ores by Aspergillus niger

Abstract

The bioleaching efficiency and mechanism of recovery of cobalt (Co) and nickel from laterites and pyritic ores by Aspergillus niger were investigated. Recoveries of Co from laterites and pyritic ores by direct bioleaching were 65.9?±?1.8% and 4.9?±?2.7%, respectively, while 30.9?±?0.6% and 10.9?±?6.2% recovery of Ni were obtained from laterites and pyritic ores, respectively. Recovery of Co via indirect bioleaching in the absence of the fungal biomass from laterite was significantly lower when compared with Co released by direct bioleaching. In the latter, hyphal penetration and colonization of the laterites were clearly observed by scanning electron microscopy (SEM). X-ray powder diffraction (XRPD) analysis of mineral phases before and after bioleaching indicated that cobalt-bearing goethite was the main phase bioleached in the laterites. No significant difference was found between Co recoveries from synthesized cobalt-bearing goethite by both direct and indirect bioleaching. Therefore, we propose that two processes are involved in bioleaching from laterites: (1) cobalt-bearing goethite was exposed via direct interactions between the fungus and the minerals and (2) cobalt-bearing goethite was dissolved by released metabolites of A. niger, such as organic acids. An incongruent pattern of Co and Fe bioleaching from the laterites was also a feature of the metal recovery process.     

Complexes of dibenzylsulfoxide with lanthanide nitrate

A new series of dibenzylsulfoxide (DBSO) compounds of empirical formula [Ln(DBSO)_x(NO₃)₃] are reported, where x = 3 for Ln = Pr; x = 2.5 for Ln = Nd, Sm, Eu, Gd, Er and La; and x=2 for Ln = Dy. The compounds were synthesized from a non-aqueous solvent and isolated as dibenzylsulfoxide salts. Infrared spectral data established coordination by the anion groups and also that coordination of DBSO is through the oxygen. Additional information based on the nature of bonding and geometrical structure was obtained from the electronic absorption spectra, X-ray diffraction analysis, molecular conductivities and molecular weight measurements (as well as magnetic susceptibility measurements). All these physical measurements indicate octahedral coordination. The 20% decrease in the metal ion radius across the lanthanide series and the competition between DBSO and nitrate groups for the coordination site affect the number of DBSO molecules bonded to a tripositive lanthanide ion.     

Structures and luminescent sensors of mixed‐counterions based salen‐type lanthanide coordination polymers

Reactions of N,N′‐bis (salicylidene)‐1,2‐cyclohexanediamine (H₂L) with mixed lanthanide counterions of LnCl₃·6H₂O and Ln (NO₃)₃·6H₂O afford six H₂L lanthanide coordination polymers, e.g. {[Pr(H₂L)₂(NO₃)₂Cl]·2CH₂Cl₂}_n ( 1 ); {[Ln(H₂L)_1.5(NO₃)₃]₂·5CHCl₃·mCH₃OH}_n [Ln = Sm ( 2 ), Eu ( 3 ), Gd ( 4 ), Tb ( 5 ) and Yb ( 6 ); m = 1 ( 2 – 5 ); m = 0 ( 6 )]. X‐ray crystallographic analysis reveals that complex 1 exhibits three‐dimensional diamondoid topologic structure and complexes 2 – 6 are of two‐dimensional structure. Luminescent spectra show that complexes 1 and 6 have characteristic near‐infrared (NIR) emission of praseodymium (III) and ytterbium (III) ions and complexes 2 – 5 emit luminescence in the visible region. Complexes 3 and 6 reveal sensitive luminescence responses to formaldehyde.     

Bis(undecatungstogermanate) lanthanates of potassium

The K₁₃[Ln(GeW₁₁O₃₉)₂]·nH₂O (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, Yb) have been prepared. Some properties of these compounds have been studied. The change of main bands in their IR spectra with reference to α-GeW₁₂O₄₀⁴⁻ is discussed. v_as (W---O_d) is shifted toward low wavenumber and v_as (W---O_b---W), δ(O---Ge---O) each appear as two distinct bands. X-ray powder diffraction shows that the molecular symmetry of K₁₃[Ln(GeW₁₁O₃₉)₂] is lower than that of α-K₈(GeW₁₁O₃₉). XPS determinations reveals that the Ln---O bond has coordination character and that the shifts of W_4f and O_ls are between K₁₃Ln (GeW₁₁O₃₉₂ and α-H₄(GeW₁₂O₄₀). Magnetic measurement confirms that the lanthanide elements are +3 valent in this complexes and the magnetic moments are very close to the values found by Van Vleck.     

Structure and magnetic properties of Ln2[Cu(opba)]3(DMSO)6(H2O) · (H2O) compounds with LnLa-Lu exhibiting ladder-like molecular motifs

The reaction of Ln(III) ions with the precursor [Cu(opba)]²⁻ in DMSO has afforded a series of isostructural compounds of general chemical formula Ln₂[Cu(opba)]₃(DMSO)₆(H₂O) · (H₂O), where Ln(III) stands for a lanthanide ion and opba stands for ortho-phenylenebis(oxamato). The crystal structure has been solved for the Gd(III) containing compound. It crystallizes in the orthorhombic system, space group Pbn2₁ (No. 33) with a = 9.4183(2) Å, b = 21.2326(4) Å, c = 37.9387(8) Å and Z = 4. The structure consists of ladder-like molecular motifs parallel to each other. To the best of our knowledge, this is the first Ln(III)Cu(II) coordination polymer family exhibiting the same crystal structure over the whole lanthanide series. The magnetic properties of the compounds have been investigated and the magnetic behavior of the Gd(III) containing compound was studied in more detail.     

Oxalate digestibility in Neotoma albigula and Neotoma mexicana

Summary The cactus specialist, Neotoma albigula, tolerates high concentrations of potentially harmful oxalate compounds in its diet. Previous research has shown that oxalate compounds are broken down by intestinal micro-organisms. Thus the ability of N. albigula to utilize a diet high in oxalates may be a consequence of the adaptation of the microflora rather than its own evolution. To test this hypothesis, the oxalate degradation ability of N. albigula was compared with that of N. mexicana, a generalist herbivore. Apparent oxalate digestibility was not significantly different in the two species, when tested using field-acclimated individuals. Analysis of scats recovered from traps indicated that both species were consuming oxalates in the wild. I conclude that the ability of these herbivores to tolerate oxalates is a natural consequence of the utilization of microbial fermentation to degrade the structural carbohydrates of plants coupled with the high adaptive and evolutionary potential of the microflora.     

Use of GEOCHEM-PC to predict rare earth element (REE) species in nutrient solutions

The interpretation of results of some experiments examining effects of rare earth elements (REE) on plant growth may have been complicated by rare earth phosphate precipitation. Simulations were undertaken using the computer model GEOCHEM-PC to define REE solubility limits and predict REE species in low and high ionic strength nutrient solutions. In low ionic strength solutions containing 5 M P, lanthanum phosphate (LaPO₄) precipitation is predicted to occur at solution pH>4.0, reaching a maximum (>95% of total) at pH 5.5. In high ionic strength solutions (1000 M P) over 95% of the La is predicted to precipitate as phosphate at pH>4.0. The predicted behaviour of cerium (Ce) was closely similar to that for La.At pH 5.5, the concentration of REE species in solution can be increased only after virtually all the P has been precipitated. Consequently, it is important to consider REE-P interactions in nutrient solutions when investigating REE effects on plant growth.     

Solubilisation of some naturally occurring metal-bearing minerals, limescale and lead phosphate by Aspergillus niger

The ability of the soil fungus Aspergillus niger to tolerate and solubilise seven naturally occurring metal-bearing minerals, limescale and lead phosphate was investigated. A. niger was able to solubilise four of the test insoluble compounds when incorporated into solid medium: cuprite (CuO₂), galena (PbS), rhodochrosite (Mn(CO₃)_x) and limescale (CaCO₃). A. niger was able to grow on all concentrations of all the test compounds, whether solubilisation occurred or not, with no reduction in growth rate from the control. In some cases, stimulation of growth occurred, most marked with the phosphate-containing mineral, apatite. Precipitation of insoluble copper and manganese oxalate crystals under colonies growing on agar amended with cuprite and rhodochrosite was observed after 1–2 days growth at 25°C. This process of oxalate formation represents a reduction in bioavailability of toxic cations, and could represent an important means of toxic metal immobilisation of physiological and environmental significance.