Experimental analysis and prediction of radionuclide solubility using machine learning models: Effects of organic complexing agents.

Radioactive wastes contain organic complexing agents that can form complexes with radionuclides and enhance the solubility of these radionuclides, increasing the mobility of radionuclides over great distances from a radioactive waste repository. In this study, four radionuclides (cobalt, strontium, iodine, and uranium) and three organic complexing agents (ethylenediaminetetraacetic acid, nitrilotriacetic acid, and iso-saccharic acid) were selected, and the solubility of these radionuclides was assessed under realistic environmental conditions such as different pHs (7, 9, 11, and 13), temperatures (10 °C, 20 °C, and 40 °C), and organic complexing agent concentrations (10-5-10-2 M). A total of 720 datasets were generated from solubility batch experiments. Four supervised machine learning models such as the Gaussian process regression (GPR), ensemble-boosted trees, artificial neural networks, and support vector machine were developed for predicting the radionuclide solubility. Each ML model was optimized using Bayesian optimization algorithm. The GPR evolved as a robust model that provided accurate predictions within the underlying solubility patterns by capturing the intricate relationships of the independent parameters of the dataset. At an uncertainty level of 95%, both the experimental results and GPR simulated estimations were closely correlated, confirming the suitability of the GPR model for future explorations.

Optimization of electrochemical regeneration of intercalated MXene for the adsorptive removal of ciprofloxacin: Prospective mechanism.

2D-Ti3C2Tx MXene nanosheets intercalated with sodium ions (SI-Ti3C2Tx) were synthesized and utilized in simultaneous adsorption and electrochemical regeneration with ciprofloxacin (CPX). The primary focus of this study is to investigate the long-term stability of SI-Ti3C2Tx MXene and to propose the underlying regeneration mechanisms. The successful synthesis of Ti3AlC2, Ti3C2Tx MXene, and SI-Ti3C2Tx MXene was confirmed using X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy. Electrochemical regeneration parameters such as charge passed, regeneration time, current density, and electrolyte composition were optimized with values of 787.5 C g-1, 7.5 min, 10 mA cm-2, and 2.5w/v% sodium chloride, respectively, enabling the complete regeneration of the SI-Ti3C2Tx MXene. In addition, the electrochemical regeneration significantly enhanced CPX removal from the SI-Ti3C2Tx MXene owing to partial amorphization, disorderliness, increased functional groups, delamination, and defect creation in the structure. Thus, the synthesized nano-adsorbent has proven helpful in practical water treatment with optimized electrochemical regeneration processes.

Sodium-alginate-laden MXene and MOF systems and their composite hydrogel beads for batch and fixed-bed adsorption of naproxen with electrochemical regeneration.

Sodium alginate (SA)-laden two-dimensional (2D) Ti3C2Tx MXene (MX) and MIL-101(Fe) (a type of metal-organic framework (MOF)) composites were prepared and used for the removal of naproxen (NPX), following the adsorption and electrochemical regeneration processes. The fixed-bed adsorption column studies were also conducted to study the process of removal of NPX by hydrogels. The number of interactions via which the MX-embedded SA (MX@SA) could adsorb NPX was higher than the number of pathways associated with NPX adsorption on the MIL-101(Fe)-embedded SA (MIL-101(Fe)@SA), and the MX and MIL-101(Fe) composite embedded SA (MX/MIL-101(Fe)@SA). The optimum parameters for the electrochemical regeneration process were determined: charge passed and current density values were 169.3 C g-1 and 10 mA cm-2, respectively, for MX@SA, and the charge passed and current density values were 16.7 C g-1 and 5 mA cm-2, respectively, for both MIL-101(Fe)@SA and MX/MIL-101(Fe)@SA. These parameters enabled excellent regeneration, consistent over multiple adsorption and electrochemical regeneration cycles. The mechanism for the regeneration of the materials was proposed that the regeneration of MX@SA and MIL-101(Fe)@SA involved the indirect electrooxidation process in the presence of OH radicals, and the regeneration of MX/MIL-101(Fe)@SA involved the indirect oxidation process in the presence of active chlorine species.

Enhanced biodegradation of perfluorooctanoic acid in a dual biocatalyzed microbial electrosynthesis system.

The toxic perfluorooctanoic acid (PFOA) is widely spread in terrestrial and aquatic habitats owing to its resistance to conventional degradation processes. Advanced techniques to degrade PFOA requires drastic conditions with high energy cost. In this study, we investigated PFOA biodegradation in a simple dual biocatalyzed microbial electrosynthesis system (MES). Different PFOA loadings (1, 5, and 10 ppm) were tested and a biodegradation of 91% was observed within 120 h. Propionate production improved and short-carbon-chain PFOA intermediates were detected, which confirmed PFOA biodegradation. However, the current density decreased, indicating an inhibitory effect of PFOA. High-throughput biofilm analysis revealed that PFOA regulated the microbial flora. Microbial community analysis showed enrichment of the more resilient and PFOA adaptive microbes, including Methanosarcina and Petrimonas. Our study promotes the potential use of dual biocatalyzed MES system as an environment-friendly and inexpensive method to remediate PFOA and provides a new direction for bioremediation research.

Enhanced bio-electrochemical performance of microbially catalysed anode and cathode in a microbial electrosynthesis system.

Most bio-electrochemical systems (BESs) use biotic/abiotic electrode combinations, with platinum-based abiotic electrodes being the most common. However, the non-renewability, cost, and poisonous nature of such electrode systems based on noble metals are major bottlenecks in BES commercialisation. Microbial electrosynthesis (MES), which is a sustainable energy platform that simultaneously treats wastewater and produces chemical commodities, also faces the same problem. In this study, a dual bio-catalysed MES system with a biotic anode and cathode (MES-D) was tested and compared with a biotic cathode/abiotic anode system (MES-S). Different bio-electrochemical tests revealed improved BES performance in MES-D, with a 3.9-fold improvement in current density compared to that of MES-S. Volatile fatty acid (VFA) generation also increased 3.2-, 4.1-, and 1.8-fold in MES-D compared with that in MES-S for acetate, propionate, and butyrate, respectively. The improved performance of MES-D could be attributed to the microbial metabolism at the bioanode, which generated additional electrons, as well as accumulative VFA production by both the bioanode and biocathode chambers. Microbial community analysis revealed the enrichment of electroactive bacteria such as Proteobacteria (60%), Bacteroidetes (67%), and Firmicutes + Proteobacteria + Bacteroidetes (75%) on the MES-S cathode and MES-D cathode and anode, respectively. These results signify the potential of combined bioanode/biocathode BESs such as MES for application in improving energy and chemical commodity production.

Microalgae-Based Biohybrid Microrobot for Accelerated Diabetic Wound Healing.

A variety of wound healing platforms have been proposed to alleviate the hypoxic condition and/or to modulate the immune responses for the treatment of chronic wounds in diabetes. However, these platforms with the passive diffusion of therapeutic agents through the blood clot result in the relatively low delivery efficiency into the deep wound site. Here, a microalgae-based biohybrid microrobot for accelerated diabetic wound healing is developed. The biohybrid microrobot autonomously moves at velocity of 33.3 µm s-1 and generates oxygen for the alleviation of hypoxic condition. In addition, the microrobot efficiently bound with inflammatory chemokines of interleukin-8 (IL-8) and monocyte chemoattractant protein-1 (MCP-1) for modulating the immune responses. The enhanced penetration of microrobot is corroborated by measuring fibrin clots in biomimetic wound using microfluidic devices and the enhanced retention of microrobot is confirmed in the real wounded mouse skin tissue. After deposition on the chronic wound in diabetic mice without wound dressing, the wounds treated with microrobots are completely healed after 9 days with the significant decrease of inflammatory cytokines below 31% of the control level and the upregulated angiogenesis above 20 times of CD31+ cells. These results confirm the feasibility of microrobots as a next-generation platform for diabetic wound healing.

Electrocatalytic oxidation of antidiabetic drug metformin adsorbed on intercalated MXene.

Two-dimensional (2D) Ti3C2Tx transition metal carbide (MXene) nanosheets intercalated with sodium ions (SI-Ti3C2Tx MXene) were used in the adsorption and electrochemical regeneration process for removal of the antidiabetic drug metformin (MF) as a model emerging pollutant. After MF adsorption, SI-Ti3C2Tx MXene oxidized the MF on its surface through its electrocatalytic activity at very low current density and cell potential. For complete oxidation the optimum parameters were 0.525 C g-1, 0.005 mA cm-2, and pH 6 in absence of NaCl or 26.25 C g-1 and 0.5 mA cm-2 in the presence of 2.5 w/v% NaCl. The overall regeneration of SI-Ti3C2Tx is governed by a combined mechanism, i.e., desorption followed by degradation. The degradation mechanism, such as direct electron transfer or indirect oxidation, depends on the applied operating conditions. Thus, the investigation suggests that these 2D sheets are good nanoadsorbents as well as good electrocatalysts and proves their usefulness in practical water-treatment applications.

Buckwheat hull-derived biochar immobilized in alginate beads for the adsorptive removal of cobalt from aqueous solutions.

Buckwheat hull-derived biochar (BHBC) beads were synthesized by immobilizing biochar powder with alginate. Due to their cation-exchange ability, abundant functional groups, microporous structure, and large surface area, BHBC beads were successfully applied for the removal of cobalt from aqueous solution. The adsorption behavior followed pseudo-second-order kinetics and the Langmuir isotherm model showed a better fit to adsorption data than the Freundlich or Temkin isotherm models. The maximum adsorption capacity of BHBC beads was 24.0 mg/g at pH 5, 35 °C, and an initial cobalt concentration of 1.0 g/L, which was higher than those of previously reported natural resource-based adsorbents. In a fixed-bed column study, the effects of operating parameters such as flow rate, bed height, and bed diameter were investigated. Both the Thomas and Yoon-Nelson models were applied to the experimental data to predict the breakthrough curves using nonlinear regression. Overall, BHBC beads can be used as an efficient adsorbent for removal of radioactive cobalt from aqueous solution.

Development of a three-dimensional macroporous sponge biocathode coated with carbon nanotube-MXene composite for high-performance microbial electrosynthesis systems.

Microbial electrosynthesis (MES) is a renewable energy platform capable of reducing the carbon footprint by converting carbon dioxide/bicarbonate to useful chemical commodities. However, the development of feasible electrode structures, inefficient current densities, and the production of unfavorable electrosynthesis products remain a major challenge. To this end, a three-dimensional (3D) macroporous sponge coated with a carbon nanotube/MXene composite (CNT-MXene@Sponge) was evaluated as an MES cathode. The macroporous scaffold, together with intrinsic electrical conductivity, enhanced the charge transfer efficiency and selective microbial enrichment characteristics of the CNT-MXene@Sponge cathode resulted in an average current density of -324 mA m-2, which was substantially higher than that of the uncoated (-100 mA m-2), CNT (-141 mA m-2), and MXene (-214 mA m-2) coated sponge electrode. The uniform 3D structure and abundant active sites of the coated material facilitated mass diffusion and microbial growth, which produced 1.5 orders of magnitude higher butyrate than the uncoated sponge. The high-throughput sequencing results showed the selective enrichment of electrogenic and butyrate-producing phylum, Firmicutes. These results suggest that the MES performance could be enhanced using the collective features of large-pore network structure, such as better conductivity, improved capacitance, and selective microbial enrichment.

Enhanced photocatalytic degradation of bisphenol A by magnetically separable bismuth oxyiodide magnetite nanocomposites under solar light irradiation.

Bismuth oxyiodide/magnetite (BiOI/Fe3O4) nanocomposites were synthesized by a hydrothermal reaction. The synthesized BiOI/Fe3O4 was used to remove bisphenol A (BPA) from an aqueous solution under simulated solar light. The molar ratio of Bi to Fe in BiOI/Fe3O4 significantly affected BPA degradation, with the optimal BiOI/Fe3O4 (2:1) ratio in the composites. Optimum operating conditions such as a catalyst dosage of 1.0 g/L, an initial BPA concentration of 10 mg/L, and pH 7 gave a complete degradation of completely removed BPA within 30 min. The primary reactive oxygen species were verified as superoxide radicals and holes in oxidative species experiments. The magnetic BiOI/Fe3O4 could be easily collected from an aqueous solution by an external magnet, and its reusability was successfully demonstrated through recycling experiments. Furthermore, the derivatives in BiOI/Fe3O4 photocatalytic reactions were investigated, and a possible BPA degradation pathway was proposed. These results show that BiOI/Fe3O4 nanocomposites have great potential for BPA removal from water and wastewater treatment systems.

Cell disruption and astaxanthin extraction from Haematococcus pluvialis: Recent advances.

The green microalga Haematococcus pluvialis is an excellent source of astaxanthin, a powerful antioxidant widely used in cosmetics, aquaculture, health foods, and pharmaceuticals. This review explores recent developments in cell disruption and astaxanthin extraction techniques applied using H. pluvialis as a model species for large-scale algal biorefinery. Notably, this alga develops a unique cyst-like cell with a rigid three-layered cell wall during astaxanthin accumulation (∼4% of dry weight) under stress. The thick (∼2 µm), acetolysis-resistant cell wall forms the strongest barrier to astaxanthin extraction. Various physical, chemical, and biological cell disruption methods were discussed and compared based on theoretical mechanisms, biomass status (wet, dry, and live), cell-disruption efficacy, astaxanthin extractability, cost, scalability, synergistic combinations, and impact on the stress-sensitive astaxanthin content. The challenges and future prospects of the downstream processes for the sustainable and economic development of advanced H. pluvialis biorefineries are also outlined.

MXsorption of mercury: Exceptional reductive behavior of titanium carbide/carbonitride MXenes.

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have drawn considerable attention for application in the field of environmental remediation. In this study, we report the simultaneous reductive-adsorption behavior of Ti3CNTx for toxic metal ion Hg2+ ion in the aqueous phase. 2D Ti3CNTx and Ti3C2Tx MXene nanosheets were synthesized by exfoliation of Ti3AlCN and Ti3AlC2 MAX phases, respectively. Various characteristics analysis confirmed the successful fabrication of MAX phases and their exfoliation into MXenes. The fabricated MXene nanosheets were used to investigate their Hg2+ removal, Hg2+ intercalation, and surface interaction mechanism efficiencies. Both MXenes were found to adsorb and reduce a large amount of Hg2+. Analytical techniques such as X-ray powder diffraction, field emission transmission electron microscopy, zeta-potential analyses, and X-ray photoelectron spectroscopy were used to investigate the material characteristics and structural changes after uptake of Hg2+. The quantitative investigation confirmed the interaction of bimetal and hydroxyl groups with Hg2+ using electrostatic interactions and adsorption-coupled reduction. In addition, both MXenes exhibited extraordinary Hg ion removal capabilities in terms of fast kinetics with an excellent distribution coefficient (KdHg) up to 1.36 × 10+9. Based on batch adsorption results, Ti3C2Tx and Ti3CNTx exhibited removal capacities of 5473.13 and 4606.04 mg/g, respectively, for Hg2+, which are higher than those of previous Hg adsorbents.

MXene-coated biochar as potential biocathode for improved microbial electrosynthesis system.

Microbial electrosynthesis (MES) holds tremendous large scale energy storage potential. By promoting the bioconversion of carbon dioxide (bicarbonate) into useful chemical commodities, this technique utilizes renewable energy and reduces carbon footprint. However, expensive electrode materials, low current densities, and multiple electrosynthesis products are major challenges to this field. To this end, this study examines a multilayered and conductive MXene structure that was coated on a cost-effective biochar substrate and tested as a MES cathode. These results show this coating yielded improved electrical conductivity, increased charge transfer efficiency, and selective microbial enrichment characteristics, resulting in a 2.3-fold increase in cathodic current production in comparison to the uncoated biochar. Moreover, an increase in active sites improved mass transfer and microbial growth, producing 1.7-fold increase in butyrate in comparison to the uncoated control. Considering that electrode attached microbial communities play a major role in final products, microbial community analyses was completed, suggesting that selective microbial enrichment was promoted as Firmicutes (66%), Proteobacteria (13%), and Bacteroidetes (12%) (i.e., exoelectrogenic and butyrate producing phyla) which were dominant in the MXene-coated biochar biofilm. These results show that biochar modification is an effective technique for achieving selective products through MES.

MnCo2O4 coated carbon felt anode for enhanced microbial fuel cell performance.

A highly efficient anode is very crucial for an improved microbial fuel cell (MFC) performance. In this study, a binder-free manganese cobalt oxide (MnCo2O4@CF) anode was synthesized using a conventional carbon felt (CF) by a facile hydrothermal method. A large electrochemically active and rough electrode surface area of MnCo2O4@CF anode improved the substrate fluxes and microbial adhesion/growth. Furthermore, the electrochemical tests on the synthesized anode confirmed the superior bioelectrochemical activity, reduced ion transfer resistance, and excellent capacitance. This resulted in an improved power density (945 mW/m2), which was 3.8 times higher than that of CF anode. The variable valence state, high stability and biocompatibility of MnCo2O4@CF resulted in continuous current density performance for five MFC cycles. High-throughput biofilm analysis revealed the enrichment of electricity producing phylum of Proteobacteria and Bacteroidetes (∼90.0%), which signified that the modified MnCo2O4 anode accelerated the enrichment of electro-active microbes.

Nickel ferrite/MXene-coated carbon felt anodes for enhanced microbial fuel cell performance.

In recent years, the modification of electrode materials for enhancing the power generation of microbial fuel cells (MFCs) has attracted considerable attention. In this study, a conventional carbon felt (CF) electrode was modified by NiFe2O4 (NiFe2O4@CF), MXene (MXene@CF), and NiFe2O4-MXene (NiFe2O4-MXene@CF) using facile dip-and-dry and hydrothermal methods. In these modified CF electrodes, the electrochemical performance considerably improved, while the highest power density (1385 mW/m2), which was 5.6, 2.8, and 1.4 times higher than those of CF, NiFe2O4@CF, and MXene@CF anodes, respectively, was achieved using NiFe2O4-MXene@CF. Furthermore, electrochemical impedance spectroscopy and cyclic voltammetry results confirmed the superior bioelectrochemical activity of a NiFe2O4-MXene@CF anode in a MFC. The improved performance could be attributed to the low charge transfer resistance, high conductivity and number of catalytically active sites of the NiFe2O4-MXene@CF anode. Microbial community analysis demonstrated the relative abundance of electroactive bacteria on a NiFe2O4-MXene@CF anodic biofilm rather than CF, MXene@CF, and NiFe2O4@CF anodes. Therefore, these results suggest that combining the favorable properties of composite materials such as NiFe2O4-MXene@CF anodes can open up new directions for fabricating novel electrodes for renewable energy-related applications.

Investigating the role of anodic potential in the biodegradation of carbamazepine in bioelectrochemical systems.

Anode potential is a critical factor in the biodegradation of organics in bioelectrochemical systems (BESs), but research on these systems with complex recalcitrant co-substrates at set anode potentials is scarce. In this study, carbamazepine (CBZ) biodegradation in a BES was examined over a wide range of set anode potentials (-200 to +600 mV vs Ag/AgCl). Current generation and current densities were improved with the increase in positive anode potentials. However, at a negative potential (-200 mV), current generation was higher as compared to that for +000 and +200 mV. The highest CBZ degradation (84%) and TOC removal efficiency (70%) were achieved at +400 mV. At +600 mV, a decrease in CBZ degradation was observed, which can be attributed to a low number of active bacteria and a poor ability to adapt to high voltage. This study signified that BESs operated at optimum anode potentials could be used for enhancing the biodegradation of complex and recalcitrant contaminants in the environment.

Exfoliation of Titanium Aluminum Carbide (211 MAX Phase) to Form Nanofibers and Two-Dimensional Nanosheets and Their Application in Aqueous-Phase Cadmium Sequestration.

A green approach was adopted to exfoliate a Ti2AlC MAX phase. The exfoliated nanostructures (Alk-Ti2Cfibr and Alk-Ti2Csheet) with exceptional mechanical, thermal, and water stabilites, as well as abundant oxygenated active binding sites, were synthesized via a controlled hydrothermal treatment in an alkaline environment. The successful synthesis of nanofibers and sheetlike nanostructures was inferred with scanning electron microscopy and X-ray diffraction analyses. Field emission scanning electron microscopy, field-emission transmission electron microscopy, Raman spectroscopy, Brunauer-Emmett-Teller surface area, ζ-potential analyses, and X-ray photoelectron spectroscopy were utilized to investigate the material's characteristics and its structural changes after metal ion adsorption. Heavy metal ion adsorption of the synthesized nanostructures was assessed in batch tests based on Cd2+ ion sequestration; the maximum adsorption capacity for Cd2+ was 325.89 mg/g, which is among the highest values reported for similar materials such as graphene oxide and its derivatives. The detailed quantitative investigation confirmed the interaction of hydroxyl groups with Cd2+ ions by electrostatic interactions, adsorption-coupled oxidation, and complex formation. Owing to their unique structure, high porosity, large specific surface area, and oxygenated functional groups, Alk-Ti2Csheet nanosheets were highly time-efficient for Cd2+ removal. Moreover, Alk-Ti2Cfibr and Alk-Ti2Csheet nanostructures were tested for simulated groundwater, showing that synthesized nanostructures were capable for removing Cd2+ ions at the ppb level. The results obtained from this study suggested that nanostructures synthesized using this route could provide a new approach to prepare and exfoliate additional MAX phases for the removal of heavy metal ions and other pollutants in the environment.

Rapid and Automated Quantification of Microalgal Lipids on a Spinning Disc.

We have developed a fully integrated centrifugal microfluidic device for rapid on-site quantification of lipids from microalgal samples. The fully automated serial process involving cell sedimentation and lysis, liquid-liquid extraction, and colorimetric detection of lipid contents was accomplished within 13 min using a lab-on-a-disc. The presented organic solvent-tolerable (for n-hexane, ethanol) microfluidic disc was newly fabricated by combining thermal fusion bonding and carbon dot-based valving techniques. It is expected that this novel platform will possibly contribute toward sustainable biofuel applications by providing a practical solution for on-site monitoring of lipid accumulation in microalgal samples, thus providing imperative contribution toward energy and environmental purposes of centrifugal microfluidic technology.

Digital Microfluidic Approach for Efficient Electroporation with High Productivity: Transgene Expression of Microalgae without Cell Wall Removal.

A unique digital microfluidic electroporation (EP) system successfully demonstrates higher transgene expression than that of conventional techniques, in addition to reliable productivity and feasible integrated processes. By systematic investigations into the effects of the droplet EP conditions for a wild-type microalgae, 1 order of magnitude higher transgene expression is accomplished without cell wall removal over the conventional bulk EP system. In addition, the newly proposed droplet EP method by a droplet contact charging phenomena shows a great potential for the integration of EP processes and on-chip cell culture providing easy controllability of each process. Finally, the implications of the accomplishments and future directions for development of the proposed technology are discussed.