Formation Of Biogenic Minerals Research Articles

Application of Biogenic Mineral Formation for the Preservation of Limestone Masonry at the Eski-Kermen Archeological Site

Minimal interference with historical material and maximum preservation is one of the basic principles of the scientific restoration and conservation of monuments of historical and cultural heritage. The creation of nanoscale and microscale inorganic coatings is a promising way to protect limestone and marble cultural heritage objects. We conducted a laboratory testing of a method for stimulating biogenic mineral formation on the surface of limestone-masonry samples from the medieval cave town on the Eski-Kermen plateau (Crimea, Russia). The results showed the formation of a layer of crystallites of 0.4 to 1.3 µm on the surface of the limestone, an increase in the average strength values of the samples by 28% from 12.3 ± 2.8 to 15.8 ± 2.6 MPa, a 42% increase in the specific surface area of limestone, an 86% increase in salt attack resistance, and preservation of the capillary water-absorption level. The obtained results show the potential of using biogenic mineral formation for the conservation and restoration of limestone.

A Macromolecular Drug for Cancer Therapy via Extracellular Calcification

AbstractCancer chemotherapy typically relies on drug endocytosis and inhibits tumor cell proliferation via intracellular pathways; however, severe side effects may arise. In this study, we performed a first attempt to develop macromolecular‐induced extracellular chemotherapy involving biomineralization by absorbing calcium from the blood through a new type of drug, polysialic acid conjugated with folate (folate‐polySia), which selectively induces biogenic mineral formation on tumor cells and results in the pathological calcification of tumors. The macromolecule‐initiated extracellular calcification causes cancer cell death mainly by intervening with the glycolysis process in cancer cells. Systemic administration of folate‐polySia inhibited cervical and breast tumor growth and dramatically improved survival rates in mice. This study provides an extracellular therapeutic approach for malignant tumor diseases via calcification that is ready for clinical trials and offers new insights into macromolecular anticancer drug discovery.

A Macromolecular Drug for Cancer Therapy via Extracellular Calcification.

Cancer chemotherapy typically relies on drug endocytosis and inhibits tumor cell proliferation via intracellular pathways; however, severe side effects may arise. In this study, we performed a first attempt to develop macromolecular-induced extracellular chemotherapy involving biomineralization by absorbing calcium from the blood through a new type of drug, polysialic acid conjugated with folate (folate-polySia), which selectively induces biogenic mineral formation on tumor cells and results in the pathological calcification of tumors. The macromolecule-initiated extracellular calcification causes cancer cell death mainly by intervening with the glycolysis process in cancer cells. Systemic administration of folate-polySia inhibited cervical and breast tumor growth and dramatically improved survival rates in mice. This study provides an extracellular therapeutic approach for malignant tumor diseases via calcification that is ready for clinical trials and offers new insights into macromolecular anticancer drug discovery.

Arsenic biomineralization by iron oxidizing strain (Ochrobactrum sp.) isolated from a paddy soil in Hunan, China

AbstractThe biogeochemistry of iron (Fe) could affect arsenic (As) fate and change its availability. Fe(II) oxidation mediated by Fe oxidizing bacteria (FeOB) has the potential for As contamination remediation due to the formation of biogenic minerals. However, microbial Fe(II) oxidation coupled with the immobilization of As and the effect of FeOB on As remediation in soils has not been thoroughly investigated. In this study, a FeOB was isolated from a paddy soil and identified as Ochrobactrum sp. EEELCW01. The kinetics reactions were used to investigate how biological and chemical reactions were involved in the Fe(II)‐NO3−‐FeOB system. Microbial Fe(II) oxidation coupled As mineralization, as well as its application in As contaminated paddy soils was studied. The results suggested that biological pathway contributed to the Fe(II) oxidation and NO3− reduction in the whole process, in which the chemical Fe(II) oxidation by biogenic NO2− was involved. Meanwhile, Fe(II) facilitated the reduction of NO2− while inhibited the reduction of NO3−. Adding 2% or more bacteria led to a significant removal effect for aqueous As, resulting in the formation of lepidocrocite and two As‐containing minerals (angelellite, loellingite). With the simultaneous application of FeOB and NO3−, the available As content in soils decreased by 37.6% and stabilized at 0.80 mg kg−1 finally. In addition, the immobilization showed long‐term effect compared to the treatment with Fe(II) or NO3− alone. The study proved that the isolated FeOB had a significant ability for As mineralization and immobilization, which provided theoretical and application basis for the remediation of As contaminated soils.

Aspergillus niger Decreases Bioavailability of Arsenic(V) via Biotransformation of Manganese Oxide into Biogenic Oxalate Minerals.

The aim of this work was to evaluate the transformation of manganese oxide (hausmannite) by microscopic filamentous fungus Aspergillus niger and the effects of the transformation on mobility and bioavailability of arsenic. Our results showed that the A. niger strain CBS 140837 greatly affected the stability of hausmannite and induced its transformation into biogenic crystals of manganese oxalates—falottaite and lindbergite. The transformation was enabled by fungal acidolysis of hausmannite and subsequent release of manganese ions into the culture medium. While almost 45% of manganese was bioextracted, the arsenic content in manganese precipitates increased throughout the 25-day static cultivation of fungus. This significantly decreased the bioavailability of arsenic for the fungus. These results highlight the unique A. niger strain’s ability to act as an active geochemical factor via its ability to acidify its environment and to induce formation of biogenic minerals. This affects not only the manganese speciation, but also bioaccumulation of potentially toxic metals and metalloids associated with manganese oxides, including arsenic.

Influence of medium composition on biomineralization and morphology of newgrowths

The research presents rational (from the point of view of processability) types of bacteria, nutrient media, biochemical agents and their quantities for biogenic mineral formation under specified conditions. The principles of the influence of metabolism processes of microorganisms on the change in the alkalinity of medium are established. The dependences of morphological parameters (size, shape) of mineral components formed during biomineralization in simulated media on the type of nutrient in the crystallization medium are established. The authors formed a phenomenological model of the processes occurring as a result of the bacterial activity of various strains, nutrient components and precursors of crystallization initiation as stages of structure formation during the production of building materials.

Fungal Nanophase Particles Catalyze Iron Transformation for Oxidative Stress Removal and Iron Acquisition

Microbe-mineral interactions have shaped the surface of the Earth and impacted the evolution of plants and animals. Although more than two-thirds of known mineral species have biological imprints, how the biotransformation of minerals may have benefited microbial development, beyond nutritional and energetic use, remains enigmatic. In this research, we have shown that biogenic ferrihydrite nanoparticles are extensively formed at the interface between an actively growing fungus and an iron-containing mineral, hematite. These biogenic nanoparticles formed through the fungus-hematite interactions can behave as mimetic catalysts, similar to nanozymes that imitate peroxidase, which scavenges hydrogen peroxide for the mitigation of potential cytotoxicity. Evidence from various X-ray spectroscopic analyses indicated that non-lattice oxygen in the nanomaterials was chiefly responsible for this catalytic activity, rather than through the conventional mechanisms of iron redox chemistry. Cryo-scanning electron microscopy, high-resolution (∼30nm) 3D volume rendering, and biomass analyses further confirmed that the organism was active and capable of mediating the catalytic reactions. We therefore hypothesize that this confers an advantage to the organism in terms of protection from oxidative stress and ensuring the acquisition of essential iron. This work raises new questions about the roles of biogenic nanomaterials in the coevolution of the lithosphere and biosphere and provides a step toward understanding the feedback pathways controlling the evolution of biogenic mineral formation.

Iron Bacteria Gallionella in Archean of India

This is the first report on the fossilized fibers found in the Archean banded manganese formations of the Chitradurga Greenstone Belt (2.8 Ga, South India), which are similar to the stalk fibers of modern Gallionella ferruginea Ehrenberg, 1838. We have therefore concluded that the intertwined and assembled stalk fibers provide indirect evidence for the presence of bacteria and biogenic mineral formation, but should not be considered as microorganisms.

Investigation of Biogenic Passivating Layers on Corroded Iron.

This study evaluates mechanisms of biogenic mineral formation induced by bacterial iron reduction for the stabilization of corroded iron. As an example, the Desulfitobacterium hafniense strain TCE1 was employed to treat corroded coupons presenting urban natural atmospheric corrosion, and spectroscopic investigations were performed on the samples’ cross-sections to evaluate the corrosion stratigraphy. The treated samples presented a protective continuous layer of iron phosphates (vivianite Fe2+3(PO4)2·8H2O and barbosalite Fe2+Fe3+2(PO4)2(OH)2), which covered 92% of the surface and was associated with a decrease in the thickness of the original corrosion layer. The results allow us to better understand the conversion of reactive corrosion products into stable biogenic minerals, as well as to identify important criteria for the design of a green alternative treatment for the stabilization of corroded iron.

Microscopic fungi sorption of chemical elements from multicomponent solution

The data of micromycetes species and strain specificity in the process of toxic elements extracting from multicomponent solutions were obtained as results of modal experiments. The results also indicate the capability of biogenic mineral formation in organic strata.

Biosorption of Chemical Elements from Multicomponent Solutions by Microfungal Biomass

Data on the species and strain specificity of micromycetes in the processes of toxic elements extraction from multicomponent solutions are obtained as results of modal experiments. The results also indicate the possibility of biogenic mineral formation in organic strata.

Morphological and textural evolution of the prismatic ultrastructure in mollusc shells: A comparative study of Pinnidae species

Molluscan shells, exhibiting a variety of complex three-dimensional architectures, are an exemplar model system to study biogenic mineral formation by living organisms. Recent studies have demonstrated that the deposition process of some shell ultrastructures can be described using classical analytical models borrowed from materials physics, which were developed to predict the structural evolution of man-made and geological polycrystalline composite assemblies. In the current study, we use this newly developed capacity to quantitatively describe the morphogenesis of the prismatic ultrastructure in three shells from the bivalve family Pinnidae towards establishing a correlation between structure, texture, growth kinetics, topology and phylogeny of the species. Using data collected by electron microscopy, synchrotron-based microtomography, electron backscatter diffraction analysis (EBSD) and X-ray diffraction we demonstrate that the prismatic ultrastructures in Pinnidae are formed following either ideal or triple-junction-controlled kinetics, which are shown to be closely linked to the morphological and topological characteristics, as well as crystallographic texture of these biocomposites. The experimental and analytical framework presented in this comparative study can serve as an additional tool for classifying molluscan shell ultrastructures on the levels of structural and textural morphogenesis. Statement of SignificanceThe ability to quantitatively describe the structural evolution of the prismatic architecture in mollusc shells is used for the first time to derive and compare between analytical parameters that define the growth kinetics and morphological and topological evolution during the growth of three shells from the family Pinnidae from two different genera. Furthermore, these parameters are linked to the evolution of crystallographic texture in the studied architectures. The developed experimental and analytical framework not only enables us to quantitatively describe species-specific growth mechanisms but also suggests a direct correlation between the evolution of morphology and texture.

Bacterial iron reduction and biogenic mineral formation for the stabilisation of corroded iron objects

Exploiting bacterial metabolism for the stabilisation of corroded iron artefacts is a promising alternative to conventional conservation-restoration methods. Bacterial iron reduction coupled to biogenic mineral formation has been shown to promote the conversion of reactive into stable corrosion products that are integrated into the natural corrosion layer of the object. However, in order to stabilise iron corrosion, the formation of specific biogenic minerals is essential. In this study, we used the facultative anaerobe Shewanella loihica for the production of stable biogenic iron minerals under controlled chemical conditions. The biogenic formation of crystalline iron phosphates was observed after iron reduction in a solution containing Fe(III) citrate. When the same biological treatment was applied on corroded iron plates, a layer composed of iron phosphates and iron carbonates was formed. Surface and cross-section analyses demonstrated that these two stable corrosion products replaced 81% of the reactive corrosion layer after two weeks of treatment. Such results demonstrate the potential of a biological treatment in the development of a stabilisation method to preserve corroded iron objects.

In-situ Raman spectroscopy of amorphous calcium phosphate to crystalline hydroxyapatite transformation

Amorphous calcium phosphate (Ca3(PO4)2xnH2O; n?=?3–4.5; ACP) is a precursor phase of the mineral hydroxyapatite (Ca5(PO4)3(OH); HAP) that in natural settings occurs during both authigenic and biogenic mineral formation. In aqueous solutions ACP transforms rapidly to the crystalline phase. The transformation rate is highly dependent on the prevailing physico-chemical conditions, most likely on: Ca & PO4 concentration, pH and temperature. In this study, we conducted a calcium phosphate precipitation experiment at 20?°C and pH 9.2, in order to study the temporal evolution of the phosphate mineralogy. We monitored and assessed the transformation process of ACP to crystalline HAP using highly time-resolved in-situ Raman spectroscopy at 100 spectra per hour, in combination with solution chemistry and XRD data. Transformation of ACP to crystalline HAP occurred within 18?h, as it is illustrated in a clear peak shift in Raman spectra from 950?cm-1 to 960?cm-1 as well as in a sharpening of the 960?cm-1 peak. The advantages of this method are:•In-situ Raman spectroscopy facilitates quasi – continuous monitoring of phase transitions.•It is an easy to handle and non-invasive method.

Use of Bacteria To Stabilize Archaeological Iron.

Iron artifacts are common among the findings of archaeological excavations. The corrosion layer formed on these objects requires stabilization after their recovery, without which the destruction of the item due to physicochemical damage is likely. Current technologies for stabilizing the corrosion layer are lengthy and generate hazardous waste products. Therefore, there is a pressing need for an alternative method for stabilizing the corrosion layer on iron objects. The aim of this study was to evaluate an alternative conservation-restoration method using bacteria. For this, anaerobic iron reduction leading to the formation of stable iron minerals in the presence of chlorine was investigated for two strains of Desulfitobacterium hafniense (strains TCE1 and LBE). Iron reduction was observed for soluble Fe(III) phases as well as for akaganeite, the most troublesome iron compound in the corrosion layer of archaeological iron objects. In terms of biogenic mineral production, differential efficiencies were observed in assays performed on corroded iron coupons. Strain TCE1 produced a homogeneous layer of vivianite covering 80% of the corroded surface, while on the coupons treated with strain LBE, only 10% of the surface was covered by the same mineral. Finally, an attempt to reduce iron on archaeological objects was performed with strain TCE1, which led to the formation of both biogenic vivianite and magnetite on the surface of the artifacts. These results demonstrate the potential of this biological treatment for stabilizing archaeological iron as a promising alternative to traditional conservation-restoration methods.IMPORTANCE Since the Iron Age, iron has been a fundamental material for the building of objects used in everyday life. However, due to its reactivity, iron can be easily corroded, and the physical stability of the object built is at risk. This is particularly true for archaeological objects on which a potentially unstable corrosion layer is formed during the time the object is buried. After excavation, changes in environmental conditions (e.g., higher oxygen concentration or lower humidity) alter the stability of the corrosion layer and can lead to the total destruction of the object. In this study, we demonstrate the feasibility of an innovative treatment based on bacterial iron reduction and biogenic mineral formation to stabilize the corrosion layer and protect these objects.

From urban municipalities to polar bioremediation: the characterisation and contribution of biogenic minerals for water treatment.

Minerals of biological origin have shown significant potential for the separation of contaminants from water worldwide. This study details the contribution of biologically derived minerals to water treatment operations, with a focus on filtration media from urban municipalities and remote cold regions. The results support biofilm-embedded iron and manganese to be the building blocks of biogenic mineral development on activated carbon and nutrient-amended zeolites. The presence of similar iron and manganese oxidising bacterial species across all filter media supports the analogous morphologies of biogenic minerals between sites and suggests that biological water treatment processes may be feasible across a range of climates. This is the first time the stages of biogenic mineral formation have been aligned with comprehensive imaging of the biofilm community and bacterial identification; especially with respect to cold regions. Where biogenic mineral formation occurs on filter media, the potential exists for enhanced adsorption for a range of organic and inorganic contaminants and improved longevity of filter media beyond the adsorption or exchange capacities of the raw material.

Biogene Eisenminerale kontrollieren das Umweltverhalten toxischer Metalle

Some microorganisms oxidize iron(II) and reduce iron(III) for energy gain and growth. These redox processes lead to the formation of microbially formed (biogenic) iron minerals, which are small and have a large surface area for the sorption of other metals. Here, we provide an overview of microbially catalyzed iron redox reactions and the properties of biogenic iron minerals and discuss the consequences of biogenic mineral formation for the environmental fate of toxic metals.

Water in the formation of biogenic minerals: Peeling away the hydration layers

Minerals of biogenic origin form and crystallize from aqueous environments at ambient temperatures and pressures. The in vivo environment either intracellular or intercellular, contains many components that modulate both the activity of the ions which associate to form the mineral, as well as the activity and structure of the crowded water. Most of the studies about the mechanism of mineralization, that is, the detailed pathways by which the mineral ions proceed from solution to crystal state, have been carried out in relatively dilute solutions and clean solutions. These studies have considered both thermodynamic and kinetic controls. Most have not considered the water itself. Is the water a passive bystander, or is it intimately a participant in the mineral ion densification reaction? A wide range of experiments show that the mineralization pathways proceed through a series of densification stages with intermediates, such as a "dense liquid" phase and the prenucleation clusters that form within it. This is in contrast to the idea of a single step phase transition, but consistent with the Gibbs concept of discontinuous phase transitions from supersaturated mother liquor to crystal. Further changes in the water structure at every surface and interface during densification guides the free energy trajectory leading to the crystalline state. In vertebrates, mineralization takes place in a hydrated collagen matrix, thus water must be considered as a direct participant. Although different in detail, the crystallization of calcium phosphates, as apatite, and calcium carbonates, as calcite, are mechanistically identical from the viewpoint of water.

Molecular evidence for microorganisms participating in Fe, Mn, and S biogeochemical cycling in two low‐temperature hydrothermal fields at the Southwest Indian Ridge

AbstractWe examined two low‐temperature hydrothermal deposits rich in Fe‐Si‐Mn collected from the recently discovered hydrothermal fields at the Southwest Indian Ridge using mineralogical, geochemical, and molecular biological techniques. The mineralogical and geochemical analyses indicated that the low‐temperature hydrothermal fields would provide a warm and chemical species‐rich habitat for chemosynthetic‐based hydrothermal ecosystems. Analyses of 16S rRNA sequences showed that ζ‐Proteobacteria, Pseudoalteromonas, Leptothrix, and Pseudomonas were potential Fe and Mn oxidizers in the low‐temperature hydrothermal environments, but they were not present in equal abundance among the subniches. Some potential Fe and Mn reducers were also recovered; they were more commonly found in the exterior black Fe‐Mn oxides. The difference between the exterior black Fe‐Mn oxides and the interior Opal‐A could be related to differences in in situ physicochemical conditions. We also identified microbial players that may participate in sulfur (S) geochemical cycling in these low‐temperature hydrothermal environments via analyses of 16S rRNA sequences and the aprA functional gene. The results indicated that members of γ‐Proteobacteria and α‐Proteobacteria were involved in the S oxidation process, while members of δ‐Proteobacteria, Nitrospirae, Firmicutes, and Archaea might participate in the S reduction process. Fe, Mn, and S oxidizers and reducers might actively participate in hydrothermal biogeochemical processes, which could influence the transfer of chemical species and the formation of biogenic minerals.

From rainfall to throughfall in a maritime vineyard

This study deals with the characteristics of throughfall produced by vine (Vitis vinifera L.) in one of the most common pedoclimatic conditions for grape production: a soil derived from marine sediments under a temperate Mediterranean climate, and located rather close to the seacoast. To distinguish the contribution of the plant from that of the atmospheric deposition, the throughfall was collected for more than one year under real and artificial (plastic) vines; for the same period, also the bulk precipitation was collected. The solution collected were analysed for pH, electrical conductivity, and concentration of cations and anions. For each event, the ionic fluxes of bulk precipitation and throughfall were calculated.Results indicated that the chemical composition of the bulk precipitation was strongly influenced by the proximity of the seashore and, to a lesser extent, by local anthropic activities and windblown material coming from distant areas. The chemical composition of the throughfall was affected by the same factors of bulk precipitation, but also by solubilisation of dry deposition trapped by the canopies, agronomic practices, plant, and living-on-the-leaves microorganisms.The comparison of the characteristics of the throughfall of the real with the artificial vines revealed that the vines are a source of Mg and K. During winter season, the reduction of Ca, NH4 and PO4 from bulk precipitation to throughfall was ascribed to the formation of biogenic minerals on the plant surface. The presence of these minerals was proved by X-ray diffraction on the powders collected during the winter season on the surface of cordons and fruiting canes. We conclude that an approach to the estimation of the nutritional potentiality of the soil that includes the contribution of the throughfall is functional to the management of the agro-ecosystem.