Phosphorus-rich biochar modified with Alcaligenes faecalis to promote U(VI) removal from wastewater: Interfacial adsorption behavior and mechanism.

Phosphorus-rich biochar (PBC) has been extensively studied due to its significant adsorption effect on U(VI). However, the release of phosphorus from PBC into solution decreases its adsorption performance and reusability and causes phosphorus pollution of water. In this study, Alcaligenes faecalis (A. faecalis) was loaded on PBC to produce a novel biocomposite (A/PBC). After adsorption equilibrium, phosphorus released into solution from PBC was 2.32 mg/L, while it decreased to 0.34 mg/L from A/PBC (p < 0.05). The U(VI) removal ratio of A/PBC reached nearly 100%, which is 13.08% higher than that of PBC (p < 0.05), and it decreased only by 1.98% after 5 cycles. When preparing A/PBC, A. faecalis converted soluble phosphate into insoluble metaphosphate minerals and extracellular polymeric substances (EPS). And A. faecalis cells accumulated through these metabolites and formed biofilm attached to the PBC surface. The adsorption of metal cations on phosphate further contributed to phosphorus fixation in the biofilm. During U(VI) adsorption by A/PBC, A. faecalis synthesize EPS and metaphosphate minerals by using the internal components of PBC, thus increasing the abundance of acidic functional groups and promoting U(VI) adsorption. Hence, A/PBC can be a green and sustainable material for U(VI) removal from wastewater.

Efficient uranium(VI) adsorbing bioinspired nano-sized hydroxyapatite composites: synthesis, tuning, and adsorption mechanism.

The production of large amounts of uranium-containing wastewater and its potential hazards has stimulated green and efficient material removal of uranium (VI). Inspired by the natural mineralization of bone, a facile and eco-friendly biomimetic synthesis of nano-hydroxyapatite (HAP) was carried out using chitosan (CS) as a template. It was found that the reaction temperature and the amount of precursors influence the particle size, crystallinity and specific surface area of the CS/HAP nanorods, and consequently their U(VI) adsorption efficiency. Moreover, the synthesized CS/HAP-40 with smaller particle size, lower crystallinity, and larger specific surface area show a more efficient U(VI) removal compared with CS/HAP-55 and CS/HAP-55-AT. It has a maximum adsorption capacity of 294.12 mg·g-1 of the CS/HAP-40. Interestingly, the U(VI) removal mechanism of CS/HAP-40 in acidic (pH = 3) and alkaline (pH = 8) aqueous solutions was found to be different. As one of the main results, the U(VI) adsorption mechanisms at pH 8 could be surface complexation and ion exchange. On the contrary, three different mechanisms could be observed at pH 3: dissolution-precipitation to form chernikovite, surface complexation, and ion exchange.

Phytoremediation of uranium-contaminated soil by perennial ryegrass (Lolium perenne L.) enhanced with citric acid application.

Perennial ryegrass (Lolium perenne L.) was planted in uranium-contaminated soil mixtures supplemented with different amounts of citric acid to investigate the defense strategies of perennial ryegrass against U and the enhanced mechanism of citric acid on the remediation efficiency in the laboratory. The uranium content in the plant tissues showed that the roots were the predominant tissue for uranium accumulation. In both root and shoot cells, the majority of U was located in the cell wall fraction. Furthermore, antioxidant enzymes were also stimulated when exposed to U stress. These results suggested that perennial ryegrass had evolved defense strategies, such as U sequestration in root tissue, compartmentalization in the cell wall, and antioxidant enzyme systems, to minimize uranium stress. For an enhanced mechanism, the optimal concentration of citric acid was 5 mmol/kg, and the removal efficiency of U in the shoots and roots increased by 47.37% and 30.10%, respectively. The treatment with 5 mmol/kg citric acid had the highest contents of photosynthetic pigment and soluble protein, the highest activity of antioxidant enzymes, and the lowest content of MDA (malondialdehyde) and relative electrical conductivity. Moreover, the TEM (transmission electron microscope) results revealed that after 5 mmol/kg citric acid was added, the cell structure of plant branches partially returned to normal, the number of mitochondria increased, chloroplast surfaces seemed normal, and the cell wall became visible. The damage to the cell ultrastructure of perennial ryegrass was significantly alleviated by treatment with 5 mmol/kg citric acid. All the results above indicated that perennial ryegrass could accumulate uranium with elevated uranium tolerance and enrichment ability with 5 mmol/kg citric acid.

Preparation of aluminum sludge composite gel spheres and adsorption of U(IV) from aqueous solution.

A novel three-dimensional aluminum sludge/polyvinyl alcohol/sodium alginate(AS/PA/SA) gel spheres were designed and prepared for uranium(VI) adsorption, and it overcomes the shortcomings of poor recycling of powdery aluminum sludge adsorbent and poor stability of sodium alginate. Experiments show that the P-S-AS has a good pH range for removal of uranium (4-5). Fitting experimental data with pseudo-first-order kinetic model and pseudo-second-order kinetic model shows that the adsorption of U(VI) by P-S-AS is a chemical action. The fit of the Langmuir isotherm model and Freundlich isotherm model to the experimental data found that the P-S-AS adsorbed U(VI) to a single layer. Thermodynamic analysis shows that the adsorption occurs spontaneously, and an increase in temperature is favorable for the adsorption of uranium by the P-S-AS. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis of the P-S-AS before and after adsorption showed that the main adsorption mechanism was the complexation reaction between functional groups and U(VI), the bonding reaction between metal oxides and U(VI).

Investigation of a modified metal-organic framework UiO-66 with nanoscale zero-valent iron for removal of uranium (VI) from aqueous solution.

A novel composite material (nZVI/UiO-66) of nanoscale zero-valent iron (nZVI) with a functionalized metal-organic framework was synthesized by this study via a coprecipitation method, which was used for the efficient removal of U(VI) in the aqueous solution. The nZVI/UiO-66 had an excellent removal capacity of 404.86 mg g-1 with an initial U(VI) concentration of 80 mg L-1, 313 K and pH = 6. The transmission electron microscopy (TEM) revealed that nZVI particles were inhomogeneously distributed on the surface of UiO-66. The analysis by the X-ray diffraction (XRD) has further illustrated that the introduction of nZVI did not change the structure of UiO-66. The adsorption process closely followed the pseudo-second-order kinetic and the Freundlich isotherm model. The removal process of U(VI) by nZVI/UiO-66 was spontaneous and endothermic. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses have illustrated that the mechanism was mainly related to adsorption of U(VI) from UiO-66 and reduction of U(VI) by nZVI. The Zr-O bonds were shown to play a vital role in the uranium removal. nZVI/UiO-66 could be recycled. The uptake rate could be maintained at around 80% after 5 cycles of use. Therefore, these results manifested that the nZVI/UiO-66 is a promising sorbent for the efficient and selective removal of U(VI) in radioactive wastewaters.

Microbial characteristic and bacterial community assessment of sediment sludge upon uranium exposure.

The microbial characteristics and bacterial communities of sediment sludge upon different concentrations of exposure to uranium were investigated by high solution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and high-throughput sequencing. After exposure to initial uranium concentrations of 10-50 µM for 24 h in synthetic wastewater, the removal efficiencies of uranium reached 80.7%-96.5%. The spherical and short rod bacteria were dominant in the sludge exposed to uranium. HRTEM-EDS and XPS analyses indicated that reduction and adsorption were the main mechanisms for uranium removal. Short-term exposure to low concentrations of uranium resulted in a decrease in bacterial richness but an increase in diversity. A dramatic change in the composition and abundances of the bacterial community were present in the sediment sludge exposed to uranium. The highest removal efficiency was identified in the sediment sludge exposed to 30 µM uranium, and the dominant bacteria included Acinetobacter (44.9%), Klebsiella (20.0%), Proteiniclasticum (6.7%), Enterobacteriaceae (6.6%), Desulfovibrio (4.4%), Porphyromonadaceae (4.1%), Comamonas (2.4%) and Sedimentibacter (2.3%). By comparison to the inoculum sediment sludge, exposure to uranium caused a substantial difference in the majority of bacterial abundance.

Influence of Leifsonia sp. on U(VI) removal efficiency and the Fe-U precipitates by zero-valent iron.

Zero-valent iron (ZVI) has been widely applied to the remediation of uranium (U)-contaminated water. Notably, indigenous bacteria may possess potential positive or unfavorable influence on the mechanism and stability of Fe-U precipitates. However, the focus of the researches in this field has mainly been on physical and/or chemical aspects. In this study, batch experiments were conducted to explore the effects of an indigenous bacterium (Leifsonia sp.) on Fe-U precipitates and the corresponding removal efficiency by ZVI under different environmental factors. The results showed that the removal rate and capacity of U(VI) was significantly inhibited and decreased by ZVI when the pH increased to near-neutral level (pH = 6~8). However, in the ZVI + Leifsonia sp. coexistence system, the U(VI) removal efficiency were maintained at high levels (over 90%) within the experimental scope (pH = 3~8). This revealed that Leifsonia sp. had a synergistic effect on U(VI) remove by ZVI. According to scanning electron microscope and energy dispersive X-ray detector (SEM-EDX) analysis, dense scaly uranium-phosphate precipitation was observed on ZVI + Leifsonia sp. surface. The X-photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analysis indicated that Leifsonia sp. facilitated the generation of U(VI)-phosphates precipitates. The X-ray diffraction (XRD) analyses further revealed that new substances, such as (Fe(II)Fe(III)2(PO4)2(OH)2), Fe(II)(UO2)2(PO4)2·8H2O, Fe(II)Fe(III)5(PO4)4(OH)2·4H2O, etc., were produced in the coexisting system of ZVI and Leifsonia sp. This study provides new insights on the feasibility and validity of site application of ZVI to U(VI)-contaminated subsurface water in situ. Graphical abstract.

Analysis of uranium removal capacity of anaerobic granular sludge bacterial communities under different initial pH conditions.

The bacterial community of an anaerobic granular sludge associated with uranium depletion was investigated following its exposure to uranium under different initial pH conditions (pH 4.5, 5.5, and 6.5). The highest uranium removal efficiency (98.1%) was obtained for the sample with an initial pH of 6.5, which also supported the highest bacterial community richness and diversity. Venn diagrams visualized the decrease in the number of genera present in both the inoculum and the uranium-exposed biomass as the initial pH decreased from 6.5 to 4.5. Compared with the inoculum, a significant increase in the abundances of the phyla Chloroflexi and Proteobacteria was observed following uranium exposure. At initial pH conditions of 6.5 to 4.5, the proportions of the taxa Anaerolineaceae, Chryseobacterium, Acinetobacter, Pseudomonas, and Sulfurovum increased significantly, likely contributing to the observed uranium removal. Uranium exposure induced a greater level of dynamic diversification of bacterial abundances than did the initial pH difference.

Uranium adsorption and subsequent re-oxidation under aerobic conditions by Leifsonia sp. - Coated biochar as green trapping agent.

It has generally been assumed that the immobilization of U(VI) via polyphosphate accumulating microorganisms may present a sink for uranium, but the potential mechanisms of the process and the stability of precipitated uranium under aerobic conditions remain elusive. This study seeks to explore the mechanism, capacity, and stability of uranium precipitation under aerobic conditions by a purified indigenous bacteria isolated from acidic tailings (pH 6.5) in China. The results show that over the treatment ranges investigated, maximum removal of U(VI) from aqueous solution was 99.82% when the initial concentration of U(VI) was 42 µM, pH was 3.5, and the temperature was with 30 °C much higher than that of other reported microorganisms. The adsorption mechanism was elucidated via the use of SEM-EDS, XPS and FTIR. SEM-EDS showed two peaks of uranium on the surface. A plausible explanation for this, supported by FTIR, is that uranium precipitated on the biosorbent surfaces. XPS measurements indicated that the uranium product is most likely a mixture of 13% U(VI) and 87% U(IV). Notably, the reoxidation experiment found that the uranium precipitates were stable in the presence of Ca2+ and Mg2+, however, U(IV) is oxidized to U(VI) in the presence of NO3- and Na+ ions, resulting in rapid dissolution. It implies that the synthesized Leifsonia sp. coated biochar could be utilized as a green and effective biosorbent. However, it may not a good choice for in-situ remediation due to the subsequent re-oxidation under aerobic conditions. These observations can be of some guiding significance to the application of the bioremediation technology in surface environments.

Assessment of Bacterial Community Composition of Anaerobic Granular Sludge in Response to Short-Term Uranium Exposure.

The effect of 10-50 µM uranium (U(VI)) on the bacterial community of anaerobic granular sludge was investigated by 24-h exposure tests, after which the bacterial community was analyzed by high-throughput sequencing. The specific U(VI) reducing activity of the anaerobic granular sludge ranged between 3.1 to 19.7 µM U(VI) g-1(VSS) h-1, independently of the initial U(VI) concentration. Alpha diversity revealed that microbial richness and diversity was the highest for anaerobic granular sludge upon 10 µM uranium exposure. Compared with the original biomass, the phylum of Euryarchaeota was significantly affected, whereas the Bacteroidetes, Firmicutes, and Synergistetes phyla were only slightly affected. However, the abundance of Chloroflexi and Proteobacteria phyla clearly increased after 24 h uranium exposure. Based on the genus level analysis, significant differences appeared in the bacterial abundance after uranium exposure. The proportions of Pseudomonas, Acinetobacter, Parabacteroides, Brevundimonas, Sulfurovum, and Trichococcus increased significantly, while the abundance of Paludibacter and Erysipelotrichaceae incertae sedis decreased dramatically. This study shows a dynamic diversification of the bacterial composition as a response to a short time (24 h) U(VI) exposure (10-50 µM).

Biosorption of uranium (VI) by immobilized Aspergillus fumigatus beads.

Biosorption of uranium (VI) ions by immobilized Aspergillus fumigatus beads was investigated in a batch system. The influences of solution pH, biosorbent dose, U (VI) concentration, and contact time on U (VI) biosorption were studied. The results indicated that the adsorption capacity was strongly affected by the solution pH, the biosorbent dose and initial U (VI) concentration. Optimum biosorption was observed at pH 5.0, biosrobent dose (w/v) 2.5%, initial U (VI) concentration 60 mg L(-1). Biosorption equilibrium was established in 120 min. The adsorption process conformed to the Freunlich and Temkin isothermal adsorption models. The dynamic adsorption model conformed to pseudo-second order model.

[Efficiency and mechanism on reduction of U(VI) by sulfate reducing bacteria].

Under anaerobic conditions, the characteristics of sulfate reducing bacteria (SRB) were applied to reduce U(VI) under different temperature, pH values, U(VI) concentrations and coexisting ions. The results showed that the optimum reduction condition was the temperature 35 degrees C, pH 7.0 and U(VI) concentration 25 mg x L(-1). The maximum reduction capacity of SRB was 179.1 mg x g(-1). Mo(VI) or Ca2+ did not affect SRB on the reduction process of U(VI) under the concentration less than 5 g x L(-1), but they strongly inhibited the process under the concentration more than 20 g x L(-1). The main inhibition of Mo (VI) was physiological inhibition and the inhibition of Ca2+ was competitive inhibition through the stable complex formation, Ca-UO2-CO3. The results also showed that lag phase did not appear on the concentration of Ca2+ less than 5 g x L(-1), but the lag phase of 24 hours appeared on the concentration of Ca2+ more than 20 g x L(-1).

Study on biosorption kinetics and thermodynamics of uranium by Citrobacter freudii.

Biosorption has been developed as an effective and economic method to treat wastewater containing low concentrations of metal pollutants. In this study, a bacterium, Citrobacter freudii, was used as a biosorbent to adsorb uranium ions. The thermodynamics and kinetics of this adsorption, as well as its mechanism, were investigated. The results indicated that the biosorption rate could be better described by a pseudo 2nd-order model than a pseudo 1st-order model. The adsorption of U (VI) proceeded very rapidly in the first 30min and subsequently slowed down continuously for a long period. The biosorption isotherm of uranium by C. freudii could be described well by the Langmuir or Freundlich isotherm, and the latter was better. The thermodynamics parameters, DeltaH degrees , DeltaG degrees , and DeltaS degrees were calculated according to the results of the experiment, which showed this biosorption as being endothermic and spontaneous. The authors investigated the active sites of bacteria for biosorption and the results proved that carboxyl in the cell wall played an important role in biosorption.