Fungal-induced CaCO3 and SrCO3 precipitation: a potential strategy for bioprotection of concrete.

Biomineralization of CaCO3 by microorganisms is a well-documented process considered applicable to concrete self-healing and metal bioremediation. Urea hydrolysis is the most widely explored and efficient pathway regarding concrete bioprotection. However, the potential of fungi has received relatively little attention compared to bacteria. In this work, we show that Fusarium cerealis, Phoma herbarum and Mucor hiemalis, isolated from concrete, could produce 828.6-941.3 mg L-1 ammonium­nitrogen in liquid media through urea hydrolysis indicating significant urease activity, and could grow in moderate (pH 8.3) or even extremely alkaline (pH 10.6) conditions. After culture in media containing 50 mM CaCl2, at least 48.8% Ca2+ was removed from solution by the selected fungi as calcite. The accumulation of Ca by the biomass was around 83.64-114.21 mg g-1. In addition, all fungi could mediate strontium carbonate formation with F. cerealis processing the highest ability for Sr removal, with ~61% added Sr being removed from solution. Scanning electron microscopy showed carbonate biominerals were encrusted on hyphae or aggregated in fungal pellets. When equivalent concentrations of Ca2+ and Sr2+ were supplemented to the media, CaCO3 with incorporated Sr formed with F. cerealis and M. hiemalis, and Sr(Sr, Ca)(CO3)2 with P. herbarum. Our results demonstrate the potential of fungi in providing carbonate coatings for concrete surfaces and simultaneous immobilization of Sr. We anticipate our work will promote further practical field research on porous cementitious materials protection by fungi and immobilization of potentially toxic metals from metal-laden ingredients, such as fly ash and granulated ground blast furnace slag.

Dredging alleviates cyanobacterial blooms by weakening diversity maintenance of bacterioplankton community.

Disentangling ecological mechanisms behind dredging is meaningful to implement environmental policy for improving water quality. However, environmental adaptation and community assembly processes of bacterioplankton in response to dredging disturbance are poorly understood. Based on Illumine MiSeq sequencing and multiple statistical analyses, we estimated interactions, functions, environmental breadths, phylogenetic signals, phylogenetic clustering, and ecological assembly processes of bacterioplankton community before and after dredging. We found distinct change in community composition, comparable decreases in diversity, functional redundancy and conflicting interaction, relatively low phylogenetic clustering, and relatively weak environmental adaptation after dredging. The bacterioplankton community assembly was affected by both stochastic and deterministic processes before dredging, but dominated by stochasticity after dredging. Sediment total phosphorus was a decisive factor in balancing determinism and stochasticity for bacterioplankton community assembly before and after dredging. Consequently, taxonomic and phylogenetic α-diversities of bacterioplankton exhibited higher contributions to the water trophic level represented by chlorophyl α before dredging than afterwards. Our results emphasized bacterioplankton in response to environmental changes caused by dredging, with nutrient loss and ecological drift playing important roles. These findings extend knowledge of contribution of bacterioplankton diversity to water trophic level and decipher mechanisms of bacterioplankton diversity maintenance in response to dredging, which is useful for guiding mitigation of cyanobacterial blooms.

Characterisation of selenium and tellurium nanoparticles produced by Aureobasidium pullulans using a multi-method approach.

Aureobasidium pullulans was grown in liquid culture media amended with selenite and tellurite and selenium (Se) and tellurium (Te) nanoparticles (NPs) were recovered after 30 d incubation. A separation method was applied to recover and characterise Se and Te NPs by asymmetric flow field flow fractionation (AF4) with online coupling to multi-angle light scattering (MALS), ultraviolet visible spectroscopy (UV-Vis), and inductively coupled plasma mass spectrometry (ICP-MS) detectors. Additional characterisation data was obtained from transmission electron microscopy (TEM), and dynamic light scattering (DLS). Solutions of 0.2% Novachem surfactant and 10 mM phosphate buffer were compared as mobile phases to investigate optimal AF4 separation and particle recovery using Se-NP as a model sample. 88% recovery was reported for 0.2% Novachem solution, compared with 50% recovery for phosphate buffer. Different crossflow (Cflow) rates were compared to further investigate optimum separation, with recoveries of 88% and 30% for Se-NPs, and 90% and 29% for Te-NPs for 3.5 mL min-1 and 2.5 mL min-1 respectively. Zeta-potential (ZP) data suggested higher stability for NP elution in Novachem solution, with increased stability attributed to minimised NP-membrane interaction due to PEGylation. Detection with MALS showed monodisperse Se-NPs (45-90 nm) and polydisperse Te-NPs (5-65 nm).Single particle ICP-MS showed mean particle diameters of 49.7 ±â€¯2.7 nm, and 135 ±â€¯4.3 nm, and limit of size detection (LOSD) of 20 nm and 45 nm for Se-NPs and Te-NPs respectively. TEM images of Se-NPs and Te-NPs displayed a spherical morphology, with the Te-NPs showing a clustered arrangement, which suggested electrostatic attraction amongst neighbouring particles. Particle hydrodynamic diameters (dH) measured with dynamic light scattering (DLS) further suggested monodisperse Se-NPs and polydisperse Te-NPs distributions, showing good agreement with AF4-MALS for Se-NPs, but suggests that the Rg obtained from AF4-MALS for Te-NP was unreliable. The results demonstrate a complementary application of asymmetric flow field-flow fractionation (AF4), ICP-MS, light scattering, UV-Vis detection, and microscopic techniques to characterise biogenic Se and Te NPs.

Fungal bioremediation of soil co-contaminated with petroleum hydrocarbons and toxic metals.

Much research has been carried out on the bacterial bioremediation of soil contaminated with petroleum hydrocarbons and toxic metals but much less is known about the potential of fungi in sites that are co-contaminated with both classes of pollutants. This article documents the roles of fungi in soil polluted with both petroleum hydrocarbons and toxic metals as well as the mechanisms involved in the biotransformation of such substances. Soil characteristics (e.g., structural components, pH, and temperature) and intracellular or excreted extracellular enzymes and metabolites are crucial factors which affect the efficiency of combined pollutant transformations. At present, bioremediation of soil co-contaminated with petroleum hydrocarbons and toxic metals is mostly focused on the removal, detoxification, or degradation efficiency of single or composite pollutants of each type. Little research has been carried out on the metabolism of fungi in response to complex pollutant stress. To overcome current bottlenecks in understanding fungal bioremediation, the potential of new approaches, e.g., gradient diffusion film technology (DGT) and metabolomics, is also discussed. KEY POINTS: • Fungi play important roles in soil co-contaminated with TPH and toxic metals. • Soil characteristics, enzymes, and metabolites are major factors in bioremediation. • DGT and metabolomics can be applied to overcome current bottlenecks.

Influence of metals and metalloids on the composition and fluorescence quenching of the extracellular polymeric substances produced by the polymorphic fungus Aureobasidium pullulans.

Aureobasidium pullulans is a ubiquitous and widely distributed fungus in the environment, and exhibits substantial tolerance against toxic metals. However, the interactions between metals and metalloids with the copious extracellular polymeric substances (EPS) produced by A. pullulans and possible relationships to tolerance are not well understood. In this study, it was found that mercury (Hg) and selenium (Se), as selenite, not only significantly inhibited growth of A. pullulans but also affected the composition of produced EPS. Lead (Pb) showed little influence on EPS yield or composition. The interactions of EPS from A. pullulans with the tested metals and metalloids depended on the specific element and their concentration. Fluorescence intensity measurements of the EPS showed that the presence of metal(loid)s stimulated the production of extracellular tryptophan-like and aromatic protein-like substances. Examination of fluorescence quenching and calculation of binding constants revealed that the fluorescence quenching process for Hg; arsenic (As), as arsenite; and Pb to EPS were mainly governed by static quenching which resulted in the formation of a stable non-fluorescent complexes between the EPS and metal(loid)s. Se showed no significant interaction with the EPS according to fluorescence quenching. These results provide further understanding of the interactions between metals and metalloids and EPS produced by fungi and their contribution to metal(loid) tolerance. KEY POINTS: • Metal(loid)s enhanced production of tryptophan- and aromatic protein-like substances. • Non-fluorescent complexes formed between the EPS and tested metal(loid)s. • EPS complexation and binding of metal(loid)s was dependent on the tested element. • Metal(loid)-induced changes in EPS composition contributed to metal(loid) tolerance.

Effect of depleted uranium on a soil microcosm fungal community and influence of a plant-ectomycorrhizal association.

Fungi are one of the most biogeochemically active components of the soil microbiome, becoming particularly important in metal polluted terrestrial environments. There is scant information on the mycobiota of uranium (U) polluted sites and the effect of metallic depleted uranium (DU) stress on fungal communities in soil has not been reported. The present study aimed to establish the effect of DU contamination on a fungal community in soil using a culture-independent approach, fungal ribosomal intergenic spacer analysis (F-RISA). Experimental soil microcosms also included variants with plants (Pinus silvestris) and P. silvestris/Rhizopogon rubescens ectomycorrhizal associations. Soil contamination with DU resulted in the appearance of RISA bands of the ITS fragments of fungal metagenomic DNA that were characteristic of the genus Mortierella (Mortierellomycotina: Mucoromycota) in pine-free microcosms and for ectomycorrhizal fungi of the genus Scleroderma (Basidiomycota) in microcosms with mycorrhizal pines. The precise taxonomic affinity of the ITS fragments from the band appearing for non-mycorrhizal pines combined with DU remained uncertain, the most likely being related to the subphylum Zoopagomycotina. Thus, soil contamination by thermodynamically unstable metallic depleted uranium can cause a significant change in a soil fungal community under experimental conditions. These changes were also strongly affected by the presence of pine seedlings and their mycorrhizal status which impacted on DU biocorrosion and the release of bioavailable uranium species.

Fungal transformation of selenium and tellurium located in a volcanogenic sulfide deposit.

Microbial reduction of soluble selenium (Se) or tellurium (Te) species results in immobilization as elemental forms and this process has been employed in soil bioremediation. However, little is known of direct and indirect fungal interactions with Se-/Te-bearing ores. In this research, the ability of Phoma glomerata to effect transformation of selenite and tellurite was investigated including interaction with Se and Te present in sulfide ores from the Kisgruva Proterozoic volcanogenic deposit. Phoma glomerata could precipitate elemental Se and Te as nanoparticles, intracellularly and extracellularly, when grown with selenite or tellurite. The nanoparticles possessed various surface capping molecules, with formation being influenced by extracellular polymeric substances. The presence of sulfide ore also affected the production of exopolysaccharide and protein. Although differences were undetectable in gross Se and Te ore levels before and after fungal interaction using X-ray fluorescence, laser ablation inductively coupled plasma mass spectrometry of polished flat ore surfaces revealed that P. glomerata could effect changes in Se/Te distribution and concentration indicating Se/Te enrichment in the biomass. These findings provide further understanding of fungal roles in metalloid transformations and are relevant to the geomicrobiology of environmental metalloid cycling as well as informing applied approaches for Se and Te immobilization, biorecovery or bioremediation.

Transport and retention of biogenic selenium nanoparticles in biofilm-coated quartz sand porous media and consequence for elemental mercury immobilization.

Bacterial biofilms are structured cell communities embedded in a matrix of extracellular polymeric substances (EPS) and a ubiquitous growth form of bacteria in the environment. A wide range of interactions between biofilms and nanoparticles have been reported. In the present study, the influence of a mixed bacterial biofilm on retention of biogenic selenium nanoparticles (BioSeNPs) and consequences for immobilization of elemental mercury (Hg0) in a porous quartz sand system were examined. BioSeNPs were significantly retained in the presence of a biofilm through electrical double layer effects, hydrogen bonding, and hydrophobic, steric and bridging interactions. Moreover, enhanced surface roughness, pore clogging, sieving and entrapment effects mediated by the biofilm also contributed to deposition of BioSeNPs. Whereas, thiol groups associated with the biofilm is a little helpful for the capture of Hg0. It is proposed that oxidative complexation between Hg0 and thiol compounds or S containing organic matter in the biofilm may result in the formation of Hg2+-thiolate complexes and HgS during the binding of Hg0 with BioSeNPs. The formation of mercury selenide was also involved in Hg0 immobilization in the porous quartz sand system.

Immobilization of elemental mercury by biogenic Se nanoparticles in soils of varying salinity.

Salinity can be a significant environmental stress which can govern the fate of nanoparticles in the environment as well as other factors such as pH, natural organic matter and minerals. In this research, the effects of salinity on the behavior of biogenic selenium nanoparticles (BioSeNPs) and consequences for elemental mercury (Hg0) immobilization in soil and soil solutions were investigated. It was found that homoaggregation and sedimentation of BioSeNPs were enhanced significantly with increasing salinity. Compression of the electric double layers of BioSeNPs at high ionic strengths resulted in attractive van der Waals forces dominating and leading to enhanced aggregation. Moreover, neutralization of the surface negative charge of BioSeNPs by divalent cations and the bridging of BioSeNPs via calcium binding to surface functional groups were also associated with enhanced aggregation. Such enhanced aggregation exerted inhibition of Hg0 immobilization in soil solutions/soils of varying salinity. These results indicate that salinity is an important environmental factor governing aggregation of BioSeNPs and therefore influencing the efficiency of Hg0 immobilization, and possible remediation treatments, as a consequence.

Heteroaggregation of soil particulate organic matter and biogenic selenium nanoparticles for remediation of elemental mercury contamination.

Particulate organic matter (POM), composed of fine root fragments and other organic debris, is an important fraction of soil organic matter which can affect the fate of nanoparticles and influence their performance in nanoparticle-based remediation technologies due to aggregation. Effects of POM are not well studied compared with those of dissolved organic matter. In this research, POM was extracted from black soil by sieving, and heteroaggregation of selenium nanoparticles (SeNPs) with POM and consequences for elemental mercury (Hg0) immobilization were investigated. It was found that low concentrations of more negatively charged POM (0-60 mg L-1) inhibited homoaggregation as well as heteroaggregation with SeNPs which had a lower negative charge through electrostatic repulsion. In the presence of high concentrations of POM (80-100 mg L-1), SeNPs were more likely to attach to POM with more Hg0 remaining in the POM since a larger concentration of nanoparticles would lead to more effective collisions. However, Hg0 immobilization efficiency using SeNPs was not significantly influenced by the addition of POM. This work is helpful to further understand the nanoparticle's behaviour in the environment and consequences for toxic metal remediation.

Soil dissolved organic matter affects mercury immobilization by biogenic selenium nanoparticles.

Molecular weight (MW) heterogeneity is a fundamental property of dissolved organic matter (DOM) in soil, which has been demonstrated to influence the binding behaviour between DOM and engineered nanoparticles. In the present study, DOM, extracted from black soil, was dialyzed into four fractions: above 10,000 Da, 3500-10,000 Da, 1000-3500 Da and 100-1000 Da. Homoaggregation and fluorescence quenching titration of selenium nanoparticles (SeNPs) was examined in the presence of the different DOM fractions, as well as the consequences for immobilization of elemental mercury. It was found that the intermediate MW fraction (3500-10,000 Da) rather than the high MW DOM fraction was likely to adsorb to SeNPs. Generally, low MW DOM was expected to adsorb initially due to faster diffusion and these compounds would be displaced by high MW DOM over longer time period. However, the electrostatic barrier imparted by adsorbed DOM limited such displacement, leading to preferential adsorption of the intermediate MW fraction over the high MW fraction. Adsorbed DOM fractions, especially that of intermediate MW, enhanced the stability of SeNPs which favoured immobilization of elemental mercury. These findings show that MW exerts an important impact on DOM binding with SeNPs which, in consequence, governs the fate of SeNPs and mercury bioremediation performance.

A survey of uranium levels in urine and hair of people living in a coal mining area in Yili, Xinjiang, China.

Recent reports have drawn attention to the uranium contamination arising from coal mining activities in the Yili region of Xinjiang, China due to the mixed distribution of uranium and coal mines, and some of the coal mines being associated with a high uranium content. In this study, we have collected water samples, solid samples such as soil, mud, coal, and coal ash, and hair and urine samples from local populations in order to evaluate the uranium level in this environment and its implications for humans in this high uranium coal mining area. Our results showed that uranium concentrations were 8.71-10.91 µg L-1 in underground water, whereas lower levels of uranium occurred in river water. Among the solid samples, coal ash contained fairly high concentrations of uranium (33.1 µg g-1) due to enrichment from coal burning. In addition, uranium levels in the other solid samples were around 2.8 µg g-1 (the Earth's average background value). Uranium concentrations in hair and urine samples were 22.2-634.5 ng g-1 (mean: 156.2 ng g-1) and 8.44-761.6 ng L-1 (mean: 202.6 ng L-1), respectively, which are significantly higher than reference values reported for unexposed subjects in other areas. Therefore, these results indicate that people living in this coal mining area have been subjected to uranium exposure for long periods of time.

Uranium Bioreduction and Biomineralization.

Following the development of nuclear science and technology, uranium contamination has been an ever increasing concern worldwide because of its potential for migration from the waste repositories and long-term contaminated environments. Physical and chemical techniques for uranium pollution are expensive and challenging. An alternative to these technologies is microbially mediated uranium bioremediation in contaminated water and soil environments due to its reduced cost and environmental friendliness. To date, four basic mechanisms of uranium bioremediation-uranium bioreduction, biosorption, biomineralization, and bioaccumulation-have been established, of which uranium bioreduction and biomineralization have been studied extensively. The objective of this review is to provide an understanding of recent developments in these two fields in relation to relevant microorganisms, mechanisms, influential factors, and obstacles.

Aerobic and anaerobic biosynthesis of nano-selenium for remediation of mercury contaminated soil.

Selenium (Se) nanoparticles are often synthesized by anaerobes. However, anaerobic bacteria cannot be directly applied for bioremediation of contaminated top soil which is generally aerobic. In this study, a selenite-reducing bacterium, Citrobacter freundii Y9, demonstrated high selenite reducing power and produced elemental nano-selenium nanoparticles (nano-Se0) under both aerobic and anaerobic conditions. The biogenic nano-Se0 converted 45.8-57.1% and 39.1-48.6% of elemental mercury (Hg0) in the contaminated soil to insoluble mercuric selenide (HgSe) under anaerobic and aerobic conditions, respectively. Addition of sodium dodecyl sulfonate enhanced Hg0 remediation, probably owing to the release of intracellular nano-Se0 from the bacterial cells for Hg fixation. The reaction product after remediation was identified as non-reactive HgSe that was formed by amalgamation of nano-Se0 and Hg0. Biosynthesis of nano-Se0 both aerobically and anaerobically therefore provides a versatile and cost-effective remediation approach for Hg0-contaminated surface and subsurface soils, where the redox potential often changes dramatically.

Uranium bioprecipitation mediated by yeasts utilizing organic phosphorus substrates.

In this research, we have demonstrated the ability of several yeast species to mediate U(VI) biomineralization through uranium phosphate biomineral formation when utilizing an organic source of phosphorus (glycerol 2-phosphate disodium salt hydrate (C3H7Na2O6P·xH2O (G2P)) or phytic acid sodium salt hydrate (C6H18O24P6·xNa(+)·yH2O (PyA))) in the presence of soluble UO2(NO3)2. The formation of meta-ankoleite (K2(UO2)2(PO4)2·6(H2O)), chernikovite ((H3O)2(UO2)2(PO4)2·6(H2O)), bassetite (Fe(++)(UO2)2(PO4)2·8(H2O)), and uramphite ((NH4)(UO2)(PO4)·3(H2O)) on cell surfaces was confirmed by X-ray diffraction in yeasts grown in a defined liquid medium amended with uranium and an organic phosphorus source, as well as in yeasts pre-grown in organic phosphorus-containing media and then subsequently exposed to UO2(NO3)2. The resulting minerals depended on the yeast species as well as physico-chemical conditions. The results obtained in this study demonstrate that phosphatase-mediated uranium biomineralization can occur in yeasts supplied with an organic phosphate substrate as sole source of phosphorus. Further understanding of yeast interactions with uranium may be relevant to development of potential treatment methods for uranium waste and utilization of organic phosphate sources and for prediction of microbial impacts on the fate of uranium in the environment.

Fungal transformation of metallic lead to pyromorphite in liquid medium.

Many approaches have been proposed to reduce the toxicity of hazardous substances such as lead in the environment. Several techniques using microorganisms rely on metal removal from solution by non-specific biosorption. However, immobilization of metals through formation of biominerals mediated by metabolic processes offers another solution but which has been given limited attention. In this work, we have investigated lead biomineralization by Paecilomyces javanicus, a fungus isolated from a lead-contaminated soil, in a liquid medium. P. javanicus was able to grow in the presence of metallic lead, supplied as lead shot, and secondary lead minerals were deposited on the lead surfaces as revealed by scanning electron microscopy. Energy dispersive X-ray analysis and X-ray powder diffraction revealed that pyromorphite was formed in the presence of the fungus, but not in abiotic controls. Our results clearly demonstrate that fungal activities can play an important role in lead biocorrosion and biomineralization in an aqueous environment. These findings are relevant to bioremediation approaches for liquid wastes contaminated with lead, or other metals, and also to the immobilization and biorecovery of rare or valuable elements. They also provide further understanding of microbial roles in environmental lead cycling.