Involvement of Bacterial and Fungal Extracellular Products in Transformation of Manganese-Bearing Minerals and Its Environmental Impact.

Manganese oxides are considered an essential component of natural geochemical barriers due to their redox and sorptive reactivity towards essential and potentially toxic trace elements. Despite the perception that they are in a relatively stable phase, microorganisms can actively alter the prevailing conditions in their microenvironment and initiate the dissolution of minerals, a process that is governed by various direct (enzymatic) or indirect mechanisms. Microorganisms are also capable of precipitating the bioavailable manganese ions via redox transformations into biogenic minerals, including manganese oxides (e.g., low-crystalline birnessite) or oxalates. Microbially mediated transformation influences the (bio)geochemistry of manganese and also the environmental chemistry of elements intimately associated with its oxides. Therefore, the biodeterioration of manganese-bearing phases and the subsequent biologically induced precipitation of new biogenic minerals may inevitably and severely impact the environment. This review highlights and discusses the role of microbially induced or catalyzed processes that affect the transformation of manganese oxides in the environment as relevant to the function of geochemical barriers.

Solid-Water Interface Interaction of Selenium with Fe(II)-Bearing Minerals and Aqueous Fe(II) and S(-II) Ions in the Near-Field of the Radioactive Waste Disposal System.

Selenium can be highly toxic in excess for both animals and humans. However, since its mobile forms can be easily adsorbed with ferric minerals, its mobility in the natural oxic environment is generally not an issue. Still, the removal and immobilization of the long-lived radioactive isotope 79Se from the contaminated anoxic waters is currently a significant concern. 79Se can be accessible in the case of radionuclides' leaching from radioactive waste disposals, where anoxic conditions prevail and where ferrous ions and Fe(II)-bearing minerals predominate after corrosion processes (e.g., magnetite). Therefore, reductive and adsorptive immobilizations by Fe(II)-bearing minerals are the primary mechanisms for removing redox-sensitive selenium. Even though the information on the sorptive interactions of selenium and Fe(II)-bearing minerals seems to be well documented, this review focuses specifically on the state of the available information on the effects of the redox properties of Fe(II)-bearing solid phases (e.g., ferrous oxides, hydroxides, sulfides, and carbonates) on selenium speciation via redox transformation and co-occurring coprecipitation.

The Effect of High Selenite and Selenate Concentrations on Ferric Oxyhydroxides Transformation under Alkaline Conditions.

Iron-based nanomaterials have high technological impacts on various pro-environmental applications, including wastewater treatment using the co-precipitation method. The purpose of this research was to identify the changes of iron nanomaterial's structure caused by the presence of selenium, a typical water contaminant, which might affect the removal when the iron co-precipitation method is used. Therefore, we have investigated the maturation of co-precipitated nanosized ferric oxyhydroxides under alkaline conditions and their thermal transformation into hematite in the presence of selenite and selenate with high concentrations. Since the association of selenium with precipitates surfaces has been proven to be weak, the mineralogy of the system was affected insignificantly, and the goethite was identified as an only ferric phase in all treatments. However, the morphology and the crystallinity of ferric oxyhydroxides was slightly altered. Selenium affected the structural order of precipitates, especially at the initial phase of co-precipitation. Still, the crystal integrity and homogeneity increased with time almost constantly, regardless of the treatment. The thermal transformation into well crystalized hematite was more pronounced in the presence of selenite, while selenate-treated and selenium-free samples indicated the presence of highly disordered fraction. This highlights that the aftermath of selenium release does not result in destabilization of ferric phases; however, since weak interactions of selenium are dominant at alkaline conditions with goethite's surfaces, it still poses a high risk for the environment. The findings of this study should be applicable in waters affected by mining and metallurgical operations.

Increased Colloidal Stability and Decreased Solubility-Sol-Gel Synthesis of Zinc Oxide Nanoparticles with Humic Acids.

Adding the humic acid coating to the nanoparticles of zinc oxide (ZnO-NP) may improve the properties necessary for their colloidal stability. To show how humic acid coating affects the properties of ZnO-NP, three differently sol-gel synthesized ZnO-NP were synthesized: pristine zinc oxide nanoparticles without coating (p-ZnO-NP) and humic acid coated zinc oxide nanoparticles at two different initial concentrations of 20 mg/L (HA20-ZnO-NP) and 200 mg/L (HA200-ZnO-NP) of humic acids in the starting solution. All ZnO-NP were found to be nanocrystals of mineral zincite exhibiting wurtzite crystal symmetry. Transmission electron microscopy showed that capping by humic acids during synthesis decreased the size of HA20-ZnO-NP and HA200-ZnO-NP compared to p-ZnO-NP nanoparticles. Via experiments, HA20-ZnO-NP were found to dissolve less and have a similar or higher stability than both p-ZnO-NP and HA200-ZnO-NP.

Removal of aluminium from aqueous solution by four wild-type strains of Aspergillus niger.

This paper provides a unique comparison of the performance of four wild-type Aspergillus niger strains in remediation of aluminium(III)-contaminated aqueous solutions. The direct fungal aluminium removal via biosorption and bioaccumulation was compared among all fungal strains, including bioaccumulation efficiency during dynamic and static cultivation. Our results indicate that aluminium bioaccumulation by living biomass outperformed biosorption, although biosorption by non-living biomass is a less time-demanding process. Among others, only one strain significantly differed regarding comparison of dynamic and static bioaccumulation. In this case, a significantly higher removal performance was achieved under dynamic cultivation conditions at initial aluminium(III) concentrations over 2.5 mg L-1. Although the fungal sensitivity towards aluminium(III) differed among selected fungal strains, there was no apparent correlation between the strains' removal performance and their adaptive mechanisms.

Mercury in mercury(II)-spiked soils is highly susceptible to plant bioaccumulation.

Heavy metal phytotoxicity assessments usually use soluble metal compounds in spiked soils to evaluate metal bioaccumulation, growth inhibition and adverse effects on physiological parameters. However, exampling mercury phytotoxicity for barley (Hordeum vulgare) this paper highlights unsuitability of this experimental approach. Mercury(II) in spiked soils is extremely bioavailable, and there experimentally determined bioaccumulation is significantly higher compared to reported mercury bioaccumulation efficiency from soils collected from mercury-polluted areas. Our results indicate this is not affected by soil sorption capacity, thus soil ageing and formation of more stable mercuric complexes with soil fractions is necessary for reasonable metal phytotoxicity assessments.

Bismuth(III) volatilization and immobilization by filamentous fungus Aspergillus clavatus during aerobic incubation.

As with many metals, bismuth can be accumulated or transformed by microorganisms. These interactions affect microbial consortia and bismuth environmental behaviour, mobility, and toxicity. Recent research focused specifically on bismuth anaerobic transformation by bacteria and archaea has inspired the evaluation of the mutual interactions between bismuth and filamentous fungi as presented in this article. The Aspergillus clavatus fungus proved resistant to adverse effects from bismuth contamination in culture medium with up to a concentration of 195 µmol L(-1) during static 15- and 30-day cultivation. The examined resistance mechanism includes biosorption to the fungal surface and biovolatilization. Pelletized fungal biomass has shown high affinity for dissolved bismuth(III). Bismuth biosorption was rapid, reaching equilibrium after 50 min with a 0.35 mmol g(-1) maximum sorption capacity as calculated from the Langmuir isotherm. A. clavatus accumulated ≤70 µmol g(-1) of bismuth after 30 days. Preceding isotherm study implications that most accumulated bismuth binds to cell wall suggests that biosorption is the main detoxification mechanism. Accumulated bismuth was also partly volatilized (≤1 µmol) or sequestrated in the cytosol or vacuoles. Concurrently, ≤1.6 µmol of bismuth remaining in solution was precipitated by fungal activity. These observations indicate that complex mutual interactions between bismuth and filamentous fungi are environmentally significant regarding bismuth mobility and transformation.

Structural disorder and local order of hNopp140.

Human nucleolar phosphoprotein p140 (hNopp 140) is a highly phosphorylated protein inhibitor of casein kinase 2 (CK2). As in the case of many kinase-inhibitor systems, the inhibitor has been described to belong to the family of intrinsically disordered proteins (IDPs), which often utilize transient structural elements to bind their cognate enzyme. Here we investigated the structural status of this protein both to provide distinct lines of evidence for its disorder and to point out its transient structure potentially involved in interactions and also its tendency to aggregate. Structural disorder of hNopp140 is apparent by its anomalous electrophoretic mobility, protease sensitivity, heat stability, hydrodynamic behavior on size-exclusion chromatography, (1)H NMR spectrum and differential scanning calorimetry scan. hNopp140 has a significant tendency to aggregate and the change of its circular dichroism spectrum in the presence of 0-80% TFE suggests a tendency to form local helical structures. Wide-line NMR measurements suggest the overall disordered character of the protein. In all, our data suggest that this protein falls into the pre-molten globule state of IDPs, with a significant tendency to become ordered in the presence of its partner as demonstrated in the presence of transcription factor IIB (TFIIB).

Review on Performance of Aspergillus and Penicillium Species in Biodegradation of Organochlorine and Organophosphorus Pesticides.

The use of pesticides in agricultural practices raises concerns considering the toxic effects they generate in the environment; thus, their sustainable application in crop production remains a challenge. One of the frequently addressed issues regarding their application includes the development of a sustainable and ecofriendly approach for their degradation. Since the filamentous fungi can bioremediate various xenobiotics owing to their efficient and versatile enzymatic machinery, this review has addressed their performance in the biodegradation of organochlorine and organophosphorus pesticides. It is focused particularly on fungal strains belonging to the genera Aspergillus and Penicillium, since both are ubiquitous in the environment, and often abundant in soils contaminated with xenobiotics. Most of the recent reviews on microbial biodegradation of pesticides focus primarily on bacteria, and the soil filamentous fungi are mentioned only marginally there. Therefore, in this review, we have attempted to demonstrate and highlight the exceptional potential of aspergilli and penicillia in degrading the organochlorine and organophosphorus pesticides (e.g., endosulfan, lindane, chlorpyrifos, and methyl parathion). These biologically active xenobiotics have been degraded by fungi into various metabolites efficaciously, or these are completely mineralized within a few days. Since they have demonstrated high rates of degradation activity, as well as high tolerance to pesticides, most of the Aspergillus and Penicillium species strains listed in this review are excellent candidates for the remediation of pesticide-contaminated soils.

Microbial involvement in iodine cycle: mechanisms and potential applications.

Stable iodine isotopes are essential for humans as they are necessary for producing thyroid gland hormones. However, there are hazardous radioactive iodine isotopes that are emitted into the environment through radioactive waste generated by nuclear power plants, nuclear weapon tests, and medical practice. Due to the biophilic character of iodine radionuclides and their enormous biomagnification potential, their elimination from contaminated environments is essential to prevent the spread of radioactive pollution in ecosystems. Since microorganisms play a vital role in controlling iodine cycling and fate in the environment, they also can be efficiently utilized in solving the issue of contamination spread. Thus, this paper summarizes all known on microbial processes that are involved in iodine transformation to highlight their prospects in remediation of the sites contaminated with radioactive iodine isotopes.

Analytical application of nano-sized titanium dioxide for the determination of trace inorganic antimony in natural waters.

In this work, solid phase extraction (SPE) using nano-sized TiO2 as a solid sorbent was used for separation/preconcentration of total inorganic antimony (iSb) before its determination by electrothermal atomic absorption spectrometry (ETAAS). After adsorption of iSb onto nano-sized TiO2, direct TiO2-slurry sampling was used for sample injection into a graphite tube. The conditions for the reliable slurry sampling together with careful control of the temperature program for the slurry solutions were worked out. Extraction conditions for both inorganic antimony species (Sb(III) and Sb(V)) and interference studies of coexisting ions were studied in detail. The accuracy of the optimized method was checked by the certified reference material (CRM) for trace elements in lake water TMDA-61. Finally, the optimized method was used for the determination of trace inorganic antimony in synthetic and natural waters.

Optimization of determination of platinum group elements in airborne particulate matter by inductively coupled plasma mass spectrometry.

Determination of automotive traffic-emitted platinum group metals (PGM) by inductively coupled plasma quadrupole mass spectrometry (ICP-MS) was optimized. The interferences from Sr, Cu, Pb, Y, Cd, Zr and Hf were evaluated using model solutions. Plasma radiofrequency (RF) power and nebulizer gas flow were optimized for 103Rh, 105Pd, 108Pd and 195Pt. Two standard reference materials were analyzed: SARM-7 Platinum ore and BCR-723 Road dust. The optimized procedure was used to analyze samples of airborne particulate matter collected in the urban site with heavy automotive traffic in the centre of Bratislava, Slovakia.

Prospects of Biogenic Xanthan and Gellan in Removal of Heavy Metals from Contaminated Waters.

Biosorption is considered an effective technique for the treatment of heavy-metal-bearing wastewaters. In recent years, various biogenic products, including native and functionalized biopolymers, have been successfully employed in technologies aiming for the environmentally sustainable immobilization and removal of heavy metals at contaminated sites, including two commercially available heteropolysaccharides-xanthan and gellan. As biodegradable and non-toxic fermentation products, xanthan and gellan have been successfully tested in various remediation techniques. Here, to highlight their prospects as green adsorbents for water decontamination, we have reviewed their biosynthesis machinery and chemical properties that are linked to their sorptive interactions, as well as their actual performance in the remediation of heavy metal contaminated waters. Their sorptive performance in native and modified forms is promising; thus, both xanthan and gellan are emerging as new green-based materials for the cost-effective and efficient remediation of heavy metal-contaminated waters.

Role of Exopolysaccharides of Pseudomonas in Heavy Metal Removal and Other Remediation Strategies.

Pseudomonas biofilms have been studied intensively for several decades and research outcomes have been successfully implemented in various medical and agricultural applications. Research on biofilm synthesis and composition has also overlapped with the objectives of environmental sciences, since biofilm components show exceptional physicochemical properties applicable to remediation techniques. Especially, exopolysaccharides (ExPs) have been at the center of scientific interest, indicating their potential in solving the environmental issues of heavy metal land and water contamination via sorptive interactions and flocculation. Since exposure to heavy metal via contaminated water or soil poses an imminent risk to the environment and human health, ExPs provide an interesting and viable solution to this issue, alongside other effective and green remedial techniques (e.g., phytostabilization, implementation of biosolids, and biosorption using agricultural wastes) aiming to restore contaminated sites to their natural, pollution-free state, or to ameliorate the negative impact of heavy metals on the environment. Thus, we discuss the plausible role and performance of Pseudomonas ExPs in remediation techniques, aiming to provide the relevant available and comprehensive information on ExPs' biosynthesis and their usage in heavy metal remediation or other environmental applications, such as wastewater treatment via bioflocculation and soil remediation.

Exchange Counterion in Polycationic Hydrogels: Tunability of Hydrophobicity, Water State, and Floating Capability for a Floating pH Device.

Smart gel materials are capable of controlling and switching swelling, water state, and wettability properties triggered by external stimuli. In this study, we fabricated a series of polyelectrolyte hydrogels bearing a 3-trimethylammoniumpropyl pendant to a methacrylamide-based backbone and examined the switchability with hydrophobic-like counteranions. The exchange between the initial chloride and camphor sulfate (CaS), dodecyl sulfate (DS), and perfluorooctanoate (PFO) counterions was investigated. The kinetics of the exchange showed that the fast exchange (within 4 h) of PFO allowed for a favorable coordination for ion pairing, resulting in a decrease in hydration. The reversibility of the exchange to the Cl- ion was only enabled for the CaS ion due to its bulkiness, while the PFO and DS hydrogels were unable to exchange, even by using tetrabutylammonium chloride, which is a structurally similar reagent, due to aggregation or the coagulates in the collapsed state of the linear tails of the counterions. The hydrogels exhibited a modulable water state and water swelling. Moreover, the hydrogels containing DS and PFO, as counterions, showed surface hydrophobic (contact angle 90°) and high hydrophobic (110°) behavior, respectively. The Raman spectrometry fluorescence with a pyrene probe indicated an increase in strong hydrogen-bonded water molecules, water confinement, and hydrophobic domains in the PFO hydrogel. Moreover, the PFO-modified hydrogel demonstrated a free-floating ability on the water surface, with a strong water repellency, showing that it has the potential to be applied in a floating pH detection device to distinguish between volatile and nonvolatile bases in a controlled manner.

Mobilisation of hazardous elements from arsenic-rich mine drainage ochres by three Aspergillus species.

Natural ferric ochres that precipitate in streambeds at abandoned mining sites are natural scavengers of various metals and metalloids. Thus, their chemical and structural modification via microbial activity should be considered in evaluation of the risks emerging from probable spread of contamination at mining sites. Our results highlight the role of various aspergilli strains in this process via production of acidic metabolites that affect mobility and bioavailability of coprecipitated contaminants. The Mössbauer analysis revealed subtle structural changes of iron in ochres, while the elemental analysis of non-dissolved residues of ochres that were exposed to filamentous fungi suggest coinciding bioextraction of arsenic and antimony with extensive iron mobilisation. However, the zinc bioextraction by filamentous fungi is less likely dependent on iron leaching from ferric ochres. The strain specific bioextraction efficiency and subsequent bioaccumulation of mobilised metals resulted in distinct tolerance responses among the studied soil fungal strains. However, regardless the burden of bioextracted metal(loid)s on its activity, the Aspergillus niger strain has shown remarkable capability to decrease pH of its environment and, thus, bioextract significant and environmentally relevant amounts of potentially toxic elements from the natural ochres.

Fungal-induced modification of spontaneously precipitated ochreous sediments from drainage of abandoned antimony mine.

Iron-containing spontaneously precipitated ochreous sediments serve as natural scavengers of various migrating elements and in this way contribute to removal and immobilization of potentially hazardous elements especially from mine drainage outflows. On the other hand, presence of filamentous fungi in their surroundings triggers biotransformation and contributes to the mobility of these elements. Three groups of samples of spontaneously precipitated ochreous sediments from an abandoned antimony mine in Poproc, Slovakia were studied: as-collected, sterilized at 95 °C for 30 min, and exposed to incubation with filamentous fungus Aspergillus niger which is frequently found in soils. Employing chemical analyses have determined the content of Fe, As, Sb, and Zn in the samples as well as their mobilization among the non-dissolved residue, culture medium of the fungus and/or its biomass. Significant degree of biovolatilization of antimony was unveiled. Speciation of iron was performed by 57Fe Mössbauer spectroscopy performed in a wide temperature range 300-4.2 K and external magnetic field of 6 T. Hyperfine interactions between 57Fe nuclei and their electronic shells have revealed superparamagnetic behavior characteristic for small particles. Their blocking temperatures of 46, 53, and 40 K, respectively, indicate a dependence of the size of the particles upon the sample treatment. While sterilization has supported their growth, incubation with fungus has changed their chemical environment and removed mainly bigger particles.

Bioleaching of Manganese Oxides at Different Oxidation States by Filamentous Fungus Aspergillus niger.

This work aimed to examine the bioleaching of manganese oxides at various oxidation states (MnO, MnO·Mn2O3, Mn2O3 and MnO2) by a strain of the filamentous fungus Aspergillus niger, a frequent soil representative. Our results showed that the fungus effectively disintegrated the crystal structure of selected mineral manganese phases. Thereby, during a 31-day static incubation of oxides in the presence of fungus, manganese was bioextracted into the culture medium and, in some cases, transformed into a new biogenic mineral. The latter resulted from the precipitation of extracted manganese with biogenic oxalate. The Mn(II,III)-oxide was the most susceptible to fungal biodeterioration, and up to 26% of the manganese content in oxide was extracted by the fungus into the medium. The detected variabilities in biogenic oxalate and gluconate accumulation in the medium are also discussed regarding the fungal sensitivity to manganese. These suggest an alternative pathway of manganese oxides' biodeterioration via a reductive dissolution. There, the oxalate metabolites are consumed as the reductive agents. Our results highlight the significance of fungal activity in manganese mobilization and transformation. The soil fungi should be considered an important geoactive agent that affects the stability of natural geochemical barriers.

Fungal Mobilization of Selenium in the Presence of Hausmannite and Ferric Oxyhydroxides.

Bioleaching of mineral phases plays a crucial role in the mobility and availability of various elements, including selenium. Therefore, the leachability of selenium associated with the surfaces of ferric and manganese oxides and oxyhydroxides, the prevailing components of natural geochemical barriers, has been studied in the presence of filamentous fungus. Both geoactive phases were exposed to selenate and subsequently to growing fungus Aspergillus niger for three weeks. This common soil fungus has shown exceptional ability to alter the distribution and mobility of selenium in the presence of both solid phases. The fungus initiated the extensive bioextraction of selenium from the surfaces of amorphous ferric oxyhydroxides, while the hausmannite (Mn3O4) was highly susceptible to biodeterioration in the presence of selenium. This resulted in specific outcomes regarding the selenium, iron, and manganese uptake by fungus and residual selenium concentrations in mineral phases as well. The adverse effects of bioleaching on fungal growth are also discussed.

Aspergillus niger enhances oxalate production as a response to phosphate deficiency induced by aluminium(III).

This paper investigates Aspergillus niger's behaviour in the presence of mobile Al3+ species by evaluating the changes in oxalate exudation at various aluminium contents. When the fungus was exposed to Al3+, no significant changes in oxalate production were observed until 100 mg.L-1 aluminium was reached resulting in oxalate production decrease by 18.2%. By stripping the culture medium completely of phosphate, even more prominent decrease by 34.8% and 67.1% at 10 and 100 mg.L-1 aluminium was observed, respectively, indicating the phosphate's significance instead of Al3+ in oxalate production. Our results suggest that the low phosphate bioavailability, which most likely resulted from its interaction with Al3+, stimulated the overproduction of oxalate by A. niger. Furthermore, when the fungus was incubated in aluminium-free media supplemented with 0.1 mM of phosphate, oxalate production increased up to 281.5 µmol.g-1, while at 1.85 mM of available phosphate only 80.7 µmol.g-1 of oxalate was produced. This indicates that oxalic acid is produced by fungus not as a mean to detoxify aluminium, but as an attempt to gain access to additional phosphate.