Overcoming the inhibitory effects of urea to improve the kinetics of microbial-induced calcium carbonate precipitation (MICCP) by Lysinibacillus sphaericus strain MB284.

Among different microbial-induced calcium carbonate precipitation (MICCP) mechanisms utilized for biomineralization, ureolysis leads to the greatest yields of calcium carbonate. Unfortunately, it is reported that urea-induced growth inhibition can delay urea hydrolysis but it is not clear how this affects MICCP kinetics. This study investigated the impact of urea addition on the MICCP performance of Lysinibacillus sphaericus MB284 not previously grown on urea (thereafter named bio-agents), compared with those previously cultured in urea-rich media (20 g/L) (hereafter named bio-agents+ or bio-agents-plus). While it was discovered that initial urea concentrations exceeding 3 g/L temporarily hindered cell growth and MICCP reactions for bio-agents, employing bio-agents+ accelerated the initiation of bacterial growth by 33% and led to a 1.46-fold increase in the initial yield of calcium carbonate in media containing 20 g/L of urea. The improved tolerance of bio-agents+ to urea is attributed to the presence of pre-produced endogenous urease, which serves to reduce the initial urea concentration, alleviate growth inhibition, and expedite biomineralization. Notably, elevating the initial concentration of bio-agents+ from OD600 of 0.01 to 1, housing a higher content of endogenous urease, accelerated the initiation of MICCP reactions and boosted the ultimate yield of biomineralization by 2.6 times while the media was supplemented with 20 g/L of urea. These results elucidate the advantages of employing bio-agents+ with higher initial cell concentrations to successfully mitigate the temporary inhibitory effects of urea on biomineralization kinetics, offering a promising strategy for accelerating the production of calcium carbonate for applications like bio self-healing of concrete.

Biomineralization and remineralizing potential of toothpastes containing nanosized ß-calcium glycerophosphate: an in vitro study.

To evaluate the effect of 1100 ppm F toothpastes supplemented with micrometric or nanosized ß-CaGP (ß-CaGPm/ß-CaGPn) on artificial enamel remineralization, using a pH cycling model. Enamel blocks with artificial caries were randomly allocated into ten groups (n = 10), according to the toothpastes: without fluoride/ß-CaGPm/ß-CaGPn (negative control); 1100 ppm F (1100F); 1100F plus 0.125%, 0.25%, 0.5%, and 1.0% of ß-CaGPm or ß-CaGPn. The blocks were treated 2×/day with slurries of toothpastes. After pH cycling, the percentage of surface hardness recovery (%SHR); integrated loss of subsurface hardness (ΔKHN); integrated mineral loss (ΔIMR); fluoride (F), calcium (Ca), and phosphorus (P) concentrations in the enamel; polydispersity index (PdI); and zeta potential (Zp) were determined. The data were analyzed by ANOVA (p < 0.001). For Zp/PdI, no significance was observed when comparing the means (p > 0.001). The treatment with 1100F-0.25%ß-CaGPn led to %SHR ∼57 higher when compared to the 1100F group (p < 0.001). The lowest ΔKHN was observed for the 1100F-0.25%ß-CaGPn group (p < 0.001). The ΔIMR was lower (∼201%) for the 1100F-0.25%ß-CaGPn when compared to 1100F (p < 0.001). The association of ß-CaGPm and ß-CaGPn to 1100F did not influence its F concentration (p > 0.001). The highest increase in Ca and P was observed for 1100F-0.25%ß-CaGPn (p < 0.001). The addition of 0.25%ß-CaGPn to 1100F toothpaste was able to promote an additional remineralizing effect of artificial caries lesions.

Modulation of calcium-influx by carboxymethyl tamarind­gold nanoparticles promotes biomineralization for tissue regeneration.

Gold nanoparticles (AuNPs) have been reported to modulate bone tissue regeneration and are being extensively utilized in biomedical implementations attributable to their low cytotoxicity, biocompatibility and simplicity of functionalization. Lately, biologically synthesized nanoparticles have acquired popularity because of their environmentally acceptable alternatives for diverse applications. Here we report the green synthesis of AuNPs by taking the biopolymer Carboxymethyl Tamarind (CMT) as a unique reducing as well as a stabilizing agent. The synthesized CMT-AuNPs were analyzed by UV-vis spectrophotometer, DLS, FTIR, XRD, TGA, SEM and TEM. These results suggest that CMT-AuNPs possess an average size of 19.93 ± 8.52 nm and have long-term stability. Further, these CMT-AuNPs promote the proliferation together with the differentiation and mineralization of osteoblast cells in a "dose-dependent" manner. Additionally, CMT-AuNPs are non-toxic to SD rats when applied externally. We suggest that the CMT-AuNPs have the potential to be a suitable and non-toxic agent for differentiation and mineralization of osteoblast cells in vitro and this can be tested in vivo as well.

Biomineralization of phosphorus during anaerobic treatment of distillery wastewaters.

This study addresses the pressing environmental concerns associated with the rapidly growing distillery industry, which is a significant contributor to wastewater generation. By focusing on the treatment of distillery wastewater using anaerobic digestion, this research explores the potential to convert organic materials into biofuels (methane). Moreover, the study aims to recover both methane and phosphorus from distillery wastewater in a single anaerobic reactor, which represents a novel and unexplored approach. Laboratory-scale experiments were conducted using mesophilic and thermophilic upflow anaerobic sludge blanket reactors. A key aspect of the study involved the implementation of a unique strategy: the mixing of centrate and spent caustic wastewater streams. This approach was intended to enhance treatment performance, manipulate the microbial community structure, and thereby optimizing the overall treatment performance. The integration of the centrate and spent caustic streams yielded remarkable co-benefits, resulting in significant biomethane production and efficient phosphorus precipitation. The study demonstrated a phosphorus removal efficiency of ∼60 % throughout the 130-140 days operation period. The recovery of phosphorus via the reactor sludge offers exciting opportunities for its utilization as a fertilizer or as a raw material within the phosphorus refinery industry. The biomethane produced during the treatment exhibits significant energy potential, estimated at 0.5 GJ/(m3 distillery wastewater).

Chelating Effect of Siderophore Desferrioxamine-B on Uranyl Biomineralization Mediated by Shewanella putrefaciens.

In contaminated water and soil, little is known about the role and mechanism of the biometabolic molecule siderophore desferrioxamine-B (DFO) in the biogeochemical cycle of uranium due to complicated coordination and reaction networks. Here, a joint experimental and quantum chemical investigation is carried out to probe the biomineralization of uranyl (UO22+, referred to as U(VI) hereafter) induced by Shewanella putrefaciens (abbreviated as S. putrefaciens) in the presence of DFO and Fe3+ ion. The results show that the production of mineralized solids {hydrogen-uranium mica [H2(UO2)2(PO4)2·8H2O]} via S. putrefaciens binding with UO22+ is inhibited by DFO, which can both chelate preferentially UO22+ to form a U(VI)-DFO complex in solution and seize it from U(VI)-biominerals upon solvation. However, with Fe3+ ion introduced, the strong specificity of DFO binding with Fe3+ causes re-emergence of biomineralization of UO22+ {bassetite [Fe(UO2)2(PO4)2·8(H2O)]} by S. putrefaciens, owing to competitive complexation between Fe3+ and UO22+ for DFO. As DFO possesses three hydroxamic functional groups, it forms hexadentate coordination with Fe3+ and UO22+ ions via these functional groups. The stability of the Fe3+-DFO complex is much higher than that of U(VI)-DFO, resulting in some DFO-released UO22+ to be remobilized by S. putrefaciens. Our finding not only adds to the understanding of the fate of toxic U(VI)-containing substances in the environment and biogeochemical cycles in the future but also suggests the promising potential of utilizing functionalized DFO ligands for uranium processing.

Enhancing La(III) biosorption and biomineralization with Micromonospora saelicesensis: Involvement of phosphorus and formation of monazite nano-minerals.

The release of rare earth elements (REEs) from mining wastes and their applications has significant environmental implications, necessitating the development of effective prevention and reclamation strategies. The mobility of REEs in groundwater due to microorganisms has garnered considerable attention. In this study, a La(III) resistant actinobacterium, Micromonospora saelicesensis KLBMP 9669, was isolated from REE enrichment soil in GuiZhou, China, and evaluated for its ability to adsorb and biomineralize La(III). The findings demonstrated that M. saelicesensis KLBMP 9669 immobilized La(III) through the physical and chemical interactions, with immobilization being influenced by the initial La(III) concentration, biomass, and pH. The adsorption kinetics followed a pseudo-second-order rate model, and the adsorption isotherm conformed to the Langmuir model. La(III) adsorption capacity of this strain was 90 mg/g, and removal rate was 94 %. Scanning electron microscope (SEM) coupled with energy dispersive X-ray spectrometer (EDS) analysis revealed the coexistence of La(III) with C, N, O, and P. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) investigations further indicated that carboxyl, amino, carbonyl, and phosphate groups on the mycelial surface may participate in lanthanum adsorption. Transmission electron microscopy (TEM) revealed that La(III) accumulation throughout the M. saelicesensis KLBMP 9669, with some granular deposits on the mycelial surface. Selected area electron diffraction (SAED) confirmed the presence of LaPO4 crystals on the M. saelicesensis KLBMP 9669 biomass after a prolonged period of La(III) accumulation. This post-sorption nano-crystallization on the M. saelicesensis KLBMP 9669 mycelial surface is expected to play a crucial role in limiting the bioimmobilization of REEs in geological repositories.

Uranium biomineralization by immobilized Chryseobacterium sp. strain PMSZPI cells for efficient uranium removal.

Uranium (U) contamination is hazardous to human health and the environment owing to its radiotoxicity and chemical toxicity and needs immediate attention. In this study, the immobilized biomass of Chryseobacterium sp. strain PMSZPI isolated from U enriched site, was investigated for U(VI) biomineralization in batch and column set-up. Under batch mode, the fresh or lyophilized cells successfully entrapped in calcium alginate beads demonstrated effectual U precipitation under acid and alkaline conditions. The maximum removal was detected at pH 7 wherein ∼98-99% of uranium was precipitated from 1 mM uranyl carbonate solution loading ∼350 mg U/g of biomass within 24 h in the presence of organic phosphate substrate. The resulting uranyl phosphate precipitates within immobilized biomass loaded beads were observed by SEM-EDX and TEM while the formation of U biomineral was confirmed by FTIR and XRD. Retention of phosphatase activity without any loss of uranium precipitation ability was observed for alginate beads with lyophilized biomass stored for 90 d at 4 °C. Continuous flow through experiment with PMSZPI biomass immobilized in polyacrylamide gel exhibited U loading of 0.8 g U/g of biomass at pH 7 using 1 l of 1 mM uranyl solution. This investigation established the feasibility for the application of immobilized PMSZPI biomass for field studies. ENVIRONMENTAL IMPLICATION: Uranium contamination is currently a serious environmental concern owing to anthropogenic activities and needs immediate attention. We have developed here a biotechnological method for successful uranium removal using immobilized cells of a uranium tolerant environmental bacterium, Chryseobacterium sp. strain PMSZPI isolated from U ore deposit via phosphatase enzyme mediated uranium precipitation. The ability of immobilized PMSZPI cells to precipitate U(VI) as long-term stable U phosphates under environmental conditions relevant for contaminated waters containing high concentrations of U that exerts toxicity for biological systems is explored here. The long term stability of the immobilized biomass without compromising its U removal capacity shows the relevance of the bioremediation strategy for uranium contamination proposed in this work.

Neutrophils-mediated bioinspired nanoagents for noninvasive monitoring of inflammatory recruitment dynamics and navigating phototherapy in rheumatoid arthritis.

Neutrophils play a crucial role in inflammatory immune responses, but their in vivo homing to inflammatory lesions remains unclear, hampering precise treatment options. In this study, we employed a biomineralization-inspired multimodal nanoagent to label neutrophils, enabling noninvasive monitoring of the dynamic process of inflammatory recruitment and guiding photothermal therapy in rheumatoid arthritis. Our nanoagents allowed visualization of neutrophil fate through magnetic resonance imaging, photoacoustic imaging, and fluorescence imaging in the first and second near-infrared windows. Histopathology and immunofluorescence analysis revealed pronounced inflammatory cell infiltration in rheumatoid arthritis compared to the normal limb. Furthermore, the recruitment quantity of neutrophils positively correlated with the inflammatory stage. Additionally, the inherent photothermal effect of the nanoagents efficiently ablated inflammatory cells during the optimal homing time and inflammatory phase. This neutrophil imaging-guided photothermal therapy precisely targeted inflammatory nuclei in rheumatoid arthritis and downregulated pro-inflammatory cytokines in serum. These results demonstrate that in vivo tracking of inflammatory immune response cells can significantly optimize the treatment of inflammatory diseases, including rheumatoid arthritis.

Physical Phenomena Governing Mineral Morphogenesis in Molluscan Nacre.

Mollusks, as well as many other living organisms, have the ability to shape mineral crystals into unconventional morphologies and to assemble them into complex functional mineral-organic structures, an observation that inspired tremendous research efforts in scientific and technological domains. Despite these, a biochemical toolkit that accounts for the formation of the vast variety of the observed mineral morphologies cannot be identified yet. Herein, phase-field modeling of molluscan nacre formation, an intensively studied biomineralization process, is used to identify key physical parameters that govern mineral morphogenesis. Manipulating such parameters, various nacre properties ranging from the morphology of a single mineral building block to that of the entire nacreous assembly are reproduced. The results support the hypothesis that the control over mineral morphogenesis in mineralized tissues happens via regulating the physico-chemical environment, in which biomineralization occurs: the organic content manipulates the geometric and thermodynamic boundary conditions, which in turn, determine the process of growth and the form of the biomineral phase. The approach developed here has the potential of providing explicit guidelines for the morphogenetic control of synthetically formed composite materials.

Functional mimicry of sea urchin biomineralization proteins with CaCO3-binding peptides selected by phage display.

The intricate process of biomineralization, e.g. in sea urchins, involves the precise interplay of highly regulated mineralization proteins and the spatiotemporal coordination achieved through compartmentalization. However, the investigation of biomineralization effector molecules, e.g. proteins, is challenging, due to their very low abundance. Therefore, we investigate the functional mimicry in the bioinspired precipitation of calcium carbonate (CaCO3) with artificial peptides selected from a peptide library by phage display based on peptide-binding to calcite and aragonite, respectively. The structure-directing effects of the identified peptides were compared to those of natural protein mixes isolated from skeletal (test) structures of two sea urchin species (Arbacia lixula and Paracentrotus lividus). The calcium carbonate samples deposited in the absence or presence of peptides were analyzed with a set of complementary techniques with regard to morphology, polymorph, and nanostructural motifs. Remarkably, some of the CaCO3-binding peptides induced morphological features in calcite that appeared similar to those obtained in the presence of the natural protein mixes. Many of the peptides identified as most effective in exerting a structure-directing effect on calcium carbonate crystallization were rich in basic amino acid residues. Hence, our in vitro mineralization study further highlights the important, but often neglected, role of positively charged soluble organic matrices associated with biological and bioinspired CaCO3 deposition.

Assessment of the induced effect of selected iron hydroxysulfates biosynthesized using Acidithiobacillus ferrooxidans for biomineralization of acid mine drainage.

Soluble iron and sulfate in acid mine drainage (AMD) can be greatly removed through the formation of minerals facilitated by seed crystals. However, the difference in the effects of jarosite and schwertmannite as endogenous seed crystals to induce AMD mineralization remains unclear. This paper intends to study the effect of Fe2+ oxidation and Fe3+ mineralization in the biosynthesis of minerals using different addition amounts and methods of jarosite or schwertmannite. The results showed that the addition amount and method of different seed crystals had no effect on the Fe2+ bio-oxidation but would change the Fe3+ mineralization efficiency. With the same amount of seed crystals added, jarosite exhibited a higher capacity to promote Fe3+ mineralization than schwertmannite. Adding seed crystals before the initiation of Fe2+ oxidation (0 h) could significantly promote Fe3+ mineralization efficiency. With the increase of seed crystals, jarosite could not only shorten the time required for mineral synthesis but also improve the final mineral yield, whereas schwertmannite could only shorten the time required for mineral synthesis. When Fe2+ was completely oxidized to Fe3+ (48 h), the supplementary of jarosite could still effectively improve Fe3+ mineralization efficiency, but the addition of schwertmannite no longer affected the final mineralization degree.

Ocean acidification, warming and feeding impacts on biomineralization pathways and shell material properties of Magallana gigas and Mytilus spp.

Molluscs are among the organisms affected by ocean acidification (OA), relying on carbon for shell biomineralization. Metabolic and environmental sourcing are two pathways potentially affected by OA, but the circumstances and patterns by which they are altered are poorly understood. From previous studies, mollusc shells grown under OA appear smaller in size, brittle and thinner, suggesting an important alteration in carbon sequestration. However, supplementary feeding experiments have shown promising results in offsetting the negative consequences of OA on shell growth. Our study compared carbon uptake by δ13C tracing and deposition into mantle tissue and shell layers in Magallana gigas and Mytilus species, two economically valuable and common species. After subjecting the species to 7.7 pH, +2 °C seawater, and enhanced feeding, both species maintain shell growth and metabolic pathways under OA without benefitting from extra feeding, thus, showing effective acclimation to rapid and short-term environmental change. Mytilus spp. increases metabolic carbon into the calcite and environmental sourcing of carbon into the shell aragonite in low pH and high temperature conditions. Low pH affects M. gigas mantle nitrogen isotopes maintaining growth. Calcite biomineralization pathway differs between the two species and suggests species-specific response to OA.

Studies on geochemical characteristics and biomineralization of Cambrian phosphorites, Zhijin, Guizhou Province, China.

Phosphate rocks, an important ore resource in Guizhou Province, China, are mainly hosted within the Sinian Doushantuo Formation and the Cambrian Meishucun Formation. In addition, the phosphate rocks of the Cambrian Meishucun Formation are rich in biological fossils. Although numerous studies investigating the genesis of phosphate deposits have been performed, the relationship between biological activity and the formation of phosphate deposits in the lower Cambrian Meishucun Formation has not been convincingly explained. This study focuses on the biological fossil assemblage, the characteristics of phosphorus, and the relationship between biological and phosphorus enrichment of the lower Cambrian phosphorites. The primary objectives of our study are to analyze the role of organisms in the formation of phosphorites, restore the phosphorus-formation environment of the Cambrian Meishucun Formation, and construct a sedimentary model of the phosphorites in the Meishucun Formation. The results indicate that there is a significant positive correlation between biological activity and the deposition of phosphorites, that is, the higher the degree of biological enrichment and differentiation, the stronger the deposition. The geochemical analysis of several profiles in the Zhijin phosphorite block shows that the phosphorite block was deposited in an oxygen-rich environment and was affected by a high-temperature hydrothermal fluid. Upwelling ocean currents supplied abundant phosphorus and other nutrients, which provided the conditions for small shells and algae to flourish. Biochemical activity was a crucial factor in the deposition of the phosphorite.

Extracellular biomineralization of uranium and its toxicity alleviation to Bacillus thuringiensis X-27.

Uranium biomineralization can slow uranium migration in the environment and thus prevent it from further contaminating the surroundings. Investigations into the uranium species, pH, inorganic phosphate (Pi) concentration, and microbial viability during biomineralization by microorganisms are crucial for understanding the mineralization mechanism. In this study, Bacillus thuringiensis X-27 was isolated from soil contaminated with uranium and was used to investigate the formation process of uranium biominerals induced by X-27. The results showed that as biomineralization proceeded, amorphous uranium-containing deposits were generated and transformed into crystalline minerals outside cells, increasing the overall concentration of uramphite. This is a cumulative rather than abrupt process. Notably, B. thuringiensis X-27 precipitated uranium outside the cell surface within 0.5 h, while the release of Pi into the extracellular environment and the change of pH to alkalescence further promoted the formation of uramphite. In addition, cell viability determination showed that the U(VI) biomineralization induced by B. thuringiensis X-27 was instrumental in alleviating the toxicity of U(VI) to cells. This work offers insight into the mechanism of U(VI) phosphate biomineralization and is a reference for bioremediation-related studies.

Poly-thymine DNA templated MnO2 biomineralization as a high-affinity anchoring enabling tumor targeting delivery.

Manganese oxide nanomaterials (MONs) are emerging as a type of highly promising nanomaterials for diseases diagnosis, and surface modification is the basis for colloidal stability and targeting delivery of the nanomaterials. Here, we report the in-situ functionalization of MnO2 with DNA through a biomineralization process. Using adsorption-oxidation method, DNA templated Mn2+ precursor to biomineralize into nano-cubic seed, followed by the growth of MnO2 to form cube/nanosheet hybrid nanostructure. Among four types of DNA homopolymers, poly-thymine (poly-T) was found to stably attach on MnO2 surface to resist various biological displacements (phosphate, serum, and complementary DNA). Capitalized on this finding, a di-block DNA was rationally designed, in which the poly-T block stably anchored on MnO2 surface, while the AS1411 aptamer block was not only an active ligand for tumor targeting delivery, but also a carrier for photosensitizer (Ce6) loading. Upon targeting delivery into tumor cells, the MnO2 acted as catalase-mimic nanozyme for oxygenation to sensitize photodynamic therapy, and the released Mn2+ triggered chemodynamic therapy via Fenton-like reaction, achieving synergistic anti-tumor effect with full biocompatibility. This work provides a simple yet robust strategy to functionalize metal oxides nanomaterials for biological applications via DNA-templated biomineralization.

Acidity-Triggered Transformable Polypeptide Self-Assembly to Initiate Tumor-Specific Biomineralization.

Biomineralization is a normal physiological process that includes nucleation, crystal growth, phase transformation, and orientation evolution. Notably, artificially induced biomineralization in the tumor tissue has emerged as an unconventional yet promising modality for malignancy therapy. However, the modest ion-chelating capabilities of carboxyl-containing biomineralization initiators lead to a deficient blockade, thus compromising antitumor efficacy. Herein, a biomineralization-inducing nanoparticle (BINP) is developed for blockade therapy of osteosarcoma. BINP is composed of dodecylamine-poly((γ-dodecyl-l-glutamate)-co-(l-histidine))-block-poly(l-glutamate-graft-alendronate) and combines a cytomembrane-insertion moiety, a tumor-microenvironment (TME)-responsive component, and an ion-chelating motif. After intravenous injection into osteosarcoma-bearing mice, BINP responds to the acidic TME to expose the dodecyl group on the surface of the expanded nanoparticles, facilitating their cytomembrane insertion. Subsequently, the protruding bisphosphonic acid group triggers continuous ion deposition to construct a mineralized barrier around the tumor, which blocks substance exchange between the tumor and surrounding normal tissues. The BINP-mediated blockade therapy displays tumor inhibition rates of 59.3% and 52.1% for subcutaneous and orthotopic osteosarcomas, respectively, compared with the Control group. In addition, the suppression of osteoclasts by the alendronate moiety alleviates bone dissolution and further inhibits pulmonary metastases. Hence, the BINP-initiated selective biomineralization provides a promising alternative for clinical osteosarcoma therapy.

Enhanced Cd(II) biomineralization induced by microalgae after cultivating modification in high-phosphorus culture.

In this study, high-phosphorus beared microalgae was prepared by cultivating modification in high-phosphorus culture, and used for the enhanced Cd(II) biomineralization in soil. Batch experiment results showed that Chlorella sorokiniana FK was modified successfully in highly phosphate culture. Both intracellular P (Poly-P, 29.7 mg/kg) and surface P (phosphoryl based functional groups, 3.7 mol/kg) were greatly enhanced, and the Cd(II) removal capacity surged to 45.98 mg/g at equilibrium in the Langmuir simulation. The EXAFS analysis indicated that Cd tended to form a more stable bidentate complex (RPO4)2Cd when bounding with phosphate groups on the surface of the high-phosphorus microalgae. Moreover, high-phosphorus beared microalgae not only had higher immobilization amount of Cd(II), but also promoted immobilized Cd from adsorbed state to mineralized state. After high-phosphate cultured, increased density of P-related groups provided more adsorption sites, while the decomposition of intracellular Poly-P released phosphate ions into cell surface microenvironment, which combined and promoted the formation of Cd3(PO4)2/Cd(H2PO4)2 on cell surface. Cd-contaminated soil remediation experiments applying high-surface-phosphate beared microalgae further showed that more Cd stabilized as a residue fraction within 49 days. This study proposes that the high-phosphate culture strategy is a good way to improve the immobilization of heavy metals in soil induced by microorganisms.

Biomineralization and AHLs-guided quorum sensing enhanced phosphorus recovery in the alternating aerobic/anaerobic biofilm system under metal ion stress.

The alternating aerobic/anaerobic biofilm system had been applied for phosphorus (P) enrichment and recovery because of the advantage of low energy consumption and high efficiency. The metal ions and N-acyl-L-homoserine lactones (AHLs) in system were studied to better clarify the mechanism of P uptake/release under metal ion stress. The results indicated that the increase of metal ions stimulated the release of AHLs, and AHLs-guided quorum sensing (QS) enhanced P uptake. Moreover, biomineralization could stimulate the increase of P content in biofilm (Pbiofilm). Meanwhile, some ortho-p was converted to short-chain poly-p in extracellular polymer substance (EPS), and others were transferred into cell through EPS to synthesize poly-p. With the Pbiofilm increased, more P could be absorbed/released due to the shift in the metabolic model of polyphosphate accumulating organisms (PAOs). The release of AHLs between microorganisms was also inhibited when PAOs reached the state of P saturation (75.6 ± 2.5 mg/g SS), which meant that the effect of signaling function would tend to stabilize, and the 169.2 ± 2.6 mg/L P concentration in the enriched solution was obtained due to the P release was inhibited. Moreover, P was rapidly transferred to the new enriched solution after the P was recovered, and PAOs restored its capability of P uptake/release. In addition, 31P-NMR analysis demonstrated that EPS played a major role in PAOs compared to cell, and inorganic phosphorus (IP) played an essential role in the uptake/release of P compared to organic phosphorus (OP). Furthermore, the microbiological analysis showed that Candidatus Accumulibacter was positively correlated with AHLs (P < 0.05). This study provided essential support for clarifying the P metabolism mechanism of PAOs.

The remediation of uranium-contaminated groundwater via bioreduction coupled to biomineralization with different pH and electron donors.

Stimulating indigenous microbes to reduce aqueous U(VI) to insoluble U(IV) by adding an electron donor has been applied as an applicable strategy to remediate uranium-contaminated groundwater in situ. However, biogenic U(IV) minerals are susceptible to oxidative remobilization after exposure to oxygen. To enhance the stability of the end product, glycerol phosphate (GP) was selected to treat artificial uranium-containing groundwater at different pH values (i.e., 7.0 and 5.0) with glycerol (GY) as the control group. The results revealed that removal ratios of uranium with GP were all higher than those with GY, and reduced crystalline U(IV)-phosphate and U(VI)-phosphate minerals (recalcitrant to oxidative remobilization) were generated in the GP groups. Although bioreduction efficiency was influenced at pH 5.0, the stability of the end product with GP was elevated significantly compared with that with GY. Mechanism analysis demonstrated that GP could activate bioreduction and biomineralization of the microbial community, and two stages were included in the GP groups. In the early stage, bioreduction and biomineralization were both involved in the immobilization process. Subsequently, part of the U(VI) precipitate was gradually reduced to U(IV) precipitate by microorganisms. This work implied that the formation of U-phosphate minerals via bioreduction coupled with biomineralization potentially offers a more effective strategy for remediating uranium-contaminated groundwater with long-term stability.

Unusual uranium biomineralization induced by green algae: Behavior investigation and mechanism probe.

As a biosorbent, algae are frequently used for the biotreatment or bioremediation of water contaminated by heavy metal or radionuclides. However, it is unclear that whether or not the biomineralization of these metal or radionuclides can be induced by algae in the process of bioremediation and what the mechanism is. In this work, Ankistrodsemus sp. has been used to treat the uranium-contaminated water, and more than 98% of uranium in the solution can be removed by the alga, when the initial uranium concentration ranges from 10 to 80 mg/L. Especially, an unusual phenomenon of algae-induced uranium biomineralization has been found in the process of uranium bioremediation and its mineralization mechanism has been explored by multiple approaches. It is worth noticing that the biomineralization of uranium induced by Ankistrodsemus sp. is significantly affected by contact time and pH. Uranium is captured rapidly on the cell surface via complexation with the carboxylate radical, amino and amide groups of the microalgae cells, which provides nucleation sites for the precipitation of insoluble minerals. Uranium stimulates Ankistrodsemus sp. to metabolize potassium ions (K+), which may endow algae with the ability to biomineralize uranium into the rose-like compreignacite (K2[(UO2)6O4(OH)6]•8H2O). As the time increased, the amorphous gradually converted into compreignacite crystals and a large number of crystals would expand over both inside and outside the cells. To the best of our knowledge, this is the first investigated microalgae with a time-dependent uranium biomineralization ability and superior tolerance to uranium. This work validates that Ankistrodsemus sp. is a promising alga for the treatment of uranium-contaminated wastewater.