Clay-polymer hybrid hydrogels in the vanguard of technological innovations for bioremediation, metal biorecovery, and diverse applications.

Polymeric hydrogels are among the most studied materials due to their exceptional properties for many applications. In addition to organic and inorganic-based hydrogels, "hybrid hydrogels" have been gaining significant relevance in recent years due to their enhanced mechanical properties and a broader range of functionalities while maintaining good biocompatibility. In this sense, the addition of micro- and nanoscale clay particles seems promising for improving the physical, chemical, and biological properties of hydrogels. Nanoclays can contribute to the physical cross-linking of polymers, enhancing their mechanical strength and their swelling and biocompatibility properties. Nowadays, they are being investigated for their potential use in a wide range of applications, including medicine, industry, and environmental decontamination. The use of microorganisms for the decontamination of environments impacted by toxic compounds, known as bioremediation, represents one of the most promising approaches to address global pollution. The immobilization of microorganisms in polymeric hydrogel matrices is an attractive procedure that can offer several advantages, such as improving the preservation of cellular integrity, and facilitating cell separation, recovery, and transport. Cell immobilization also facilitates the biorecovery of critical materials from wastes within the framework of the circular economy. The present work aims to present an up-to-date overview on the different "hybrid hydrogels" used to date for bioremediation of toxic metals and recovery of critical materials, among other applications, highlighting possible drawbacks and gaps in research. This will provide the latest trends and advancements in the field and contribute to search for effective bioremediation strategies and critical materials recovery technologies.

Microbial influence in Spanish bentonite slurry microcosms: Unveiling a-year long geochemical evolution and early-stage copper corrosion related to nuclear waste repositories.

The deep geological repository (DGR) concept consists of storing radioactive waste in metal canisters, surrounded by compacted bentonite, and placed deeply into a geological formation. Here, bentonite slurry microcosms with copper canisters, inoculated with bacterial consortium and amended with acetate, lactate and sulfate were set up to investigate their geochemical evolution over a year under anoxic conditions. The impact of microbial communities on the corrosion of the copper canisters in an early-stage (45 days) was also assessed. The amended bacterial consortium and electron donors/acceptor accelerated the microbial activity, while the heat-shocked process had a retarding effect. The microbial communities partially oxidize lactate to acetate, which is subsequently consumed when the lactate is depleted. Early-stage microbial communities showed that the bacterial consortium reduced microbial diversity with Pseudomonas and Stenotrophomonas dominating the community. However, sulfate-reducing bacteria such as Desulfocurvibacter, Anaerosolibacter, and Desulfosporosinus were enriched coupling oxidation of lactate/acetate with reduction of sulfates. The generated biogenic sulfides, which could mediate the conversion of copper oxides (possibly formed by trapped oxygen molecules on the bentonite or driven by the reduction of H2O) to copper sulfide (Cu2S), were identified by X-ray photoelectron spectroscopy (XPS). Overall, these findings shed light on the ideal geochemical conditions that would affect the stability of DGR barriers, emphasizing the impact of the SRB on the corrosion of the metal canisters, the gas generation, and the interaction with components of the bentonite.

Long-term tracking of the microbiology of uranium-amended water-saturated bentonite microcosms: A mechanistic characterization of U speciation.

Deep geological repositories (DGRs) stand out as one of the optimal options for managing high-level radioactive waste (HLW) such as uranium (U) in the near future. Here, we provide novel insights into microbial behavior in the DGR bentonite barrier, addressing potential worst-case scenarios such as waste leakage (e.g., U) and groundwater infiltration of electron rich donors in the bentonite. After a three-year anaerobic incubation, Illumina sequencing results revealed a bacterial diversity dominated by anaerobic and spore-forming microorganisms mainly from the phylum Firmicutes. Highly U tolerant and viable bacterial isolates from the genera Peribacillus, Bacillus, and some SRB such as Desulfovibrio and Desulfosporosinus, were enriched from U-amended bentonite. The results obtained by XPS and XRD showed that U was present as U(VI) and as U(IV) species. Regarding U(VI), we have identified biogenic U(VI) phosphates, U(UO2)·(PO4)2, located in the inner part of the bacterial cell membranes in addition to U(VI)-adsorbed to clays such as montmorillonite. Biogenic U(IV) species as uraninite may be produced as result of bacterial enzymatic U(VI) reduction. These findings suggest that under electron donor-rich water-saturation conditions, bentonite microbial community can control U speciation, immobilizing it, and thus enhancing future DGR safety if container rupture and waste leakage occurs.

Insights into the Impact of Physicochemical and Microbiological Parameters on the Safety Performance of Deep Geological Repositories.

Currently, the production of radioactive waste from nuclear industries is increasing, leading to the development of reliable containment strategies. The deep geological repository (DGR) concept has emerged as a suitable storage solution, involving the underground emplacement of nuclear waste within stable geological formations. Bentonite clay, known for its exceptional properties, serves as a critical artificial barrier in the DGR system. Recent studies have suggested the stability of bentonite within DGR relevant conditions, indicating its potential to enhance the long-term safety performance of the repository. On the other hand, due to its high resistance to corrosion, copper is one of the most studied reference materials for canisters. This review provides a comprehensive perspective on the influence of nuclear waste conditions on the characteristics and properties of DGR engineered barriers. This paper outlines how evolving physico-chemical parameters (e.g., temperature, radiation) in a nuclear repository may impact these barriers over the lifespan of a repository and emphasizes the significance of understanding the impact of microbial processes, especially in the event of radionuclide leakage (e.g., U, Se) or canister corrosion. Therefore, this review aims to address the long-term safety of future DGRs, which is critical given the complexity of such future systems.

Microbial responses to elevated temperature: Evaluating bentonite mineralogy and copper canister corrosion within the long-term stability of deep geological repositories of nuclear waste.

Deep Geological Repositories (DGRs) consist of radioactive waste contained in corrosion-resistant canisters, surrounded by compacted bentonite clay, and buried few hundred meters in a stable geological formation. The effects of bentonite microbial communities on the long-term stability of the repository should be assessed. This study explores the impact of harsh conditions (60 °C, highly-compacted bentonite, low water activity), and acetate:lactate:sulfate addition, on the evolution of microbial communities, and their effect on the bentonite mineralogy, and corrosion of copper material under anoxic conditions. No bentonite illitization was observed in the treatments, confirming its mineralogical stability as an effective barrier for future DGR. Anoxic incubation at 60 °C reduced the microbial diversity, with Pseudomonas as the dominant genus. Culture-dependent methods showed survival and viability at 60 °C of moderate-thermophilic aerobic bacterial isolates (e.g., Aeribacillus). Despite the low presence of sulfate-reducing bacteria in the bentonite blocks, we proved their survival at 30 °C but not at 60 °C. Copper disk's surface remained visually unaltered. However, in the acetate:lactate:sulfate-treated samples, sulfide/sulfate signals were detected, along with microbial-related compounds. These findings offer new insights into the impact of high temperatures (60 °C) on the biogeochemical processes at the compacted bentonite/Cu canister interface post-repository closure.

Biostimulation of indigenous microbes for uranium bioremediation in former U mine water: multidisciplinary approach assessment.

Characterizing uranium (U) mine water is necessary to understand and design an effective bioremediation strategy. In this study, water samples from two former U-mines in East Germany were analysed. The U and sulphate (SO42-) concentrations of Schlema-Alberoda mine water (U: 1 mg/L; SO42-: 335 mg/L) were 2 and 3 order of magnitude higher than those of the Pöhla sample (U: 0.01 mg/L; SO42-: 0.5 mg/L). U and SO42- seemed to influence the microbial diversity of the two water samples. Microbial diversity analysis identified U(VI)-reducing bacteria (e.g. Desulfurivibrio) and wood-degrading fungi (e.g. Cadophora) providing as electron donors for the growth of U-reducers. U-bioreduction experiments were performed to screen electron donors (glycerol, vanillic acid, and gluconic acid) for Schlema-Alberoda U-mine water bioremediation purpose. Thermodynamic speciation calculations show that under experimental conditions, U(VI) is not coordinated to the amended electron donors. Glycerol was the best-studied electron donor as it effectively removed 99% of soluble U, 95% of Fe, and 58% of SO42- from the mine water, probably by biostimulation of indigenous microbes. Vanillic acid removed 90% of U, and no U removal occurred using gluconic acid.