Shewanella oneidensis MR-1 dissimilatory reduction of ferrihydrite to highly enhance mineral transformation and reactive oxygen species production in redox-fluctuating environments.

Diverse paths generated by reactive oxygen species (ROS) can mediate contaminant transformation and fate in the soil/aquatic environments. However, the pathways for ROS production upon the oxygenation of redox-active ferrous iron minerals are underappreciated. Ferrihydrite (Fh) can be reduced to produce Fe(II) by Shewanella oneidensis MR-1, a representative strain of dissimilatory iron-reducing bacteria (DIRB). The microbial reaction formed a spent Fh product named mr-Fh that contained Fe(II). Material properties of mr-Fh were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Magnetite could be observed in all mr-Fh samples produced over 1-day incubation, which might greatly favor the Fe(II) oxygenation process to produce hydroxyl radical (•OH). The maximum amount of dissolved Fe(II) can reach 1.1 mM derived from added 1 g/L Fh together with glucose as a carbon source, much higher than the 0.5 mM generated in the case of the Luria-Bertani carbon source. This may confirm that MR-1 can effectively reduce Fh and produce biogenetic Fe(II). Furthermore, the oxygenation of Fe(II) on the mr-Fh surface can produce abundant ROS, wherein the maximum cumulative •OH content is raised to about 120 µM within 48 h at pH 5, but it is decreased to about 100 µM at pH 7 for the case of MR-1/Fh system after a 7-day incubation. Thus, MR-1-mediated Fh reduction is a critical link to enhance ROS production, and the •OH species is among them the predominant form. XPS analysis proves that a conservable amount of Fe(II) species is subject to adsorption onto mr-Fh. Here, MR-1-mediated ROS production is highly dependent on the redox activity of the form Fe(II), which should be the counterpart presented as the adsorbed Fe(II) on surfaces. Hence, our study provides new insights into understanding the mechanisms that can significantly govern ROS generation in the redox-oscillation environment.

Highly efficient adsorption of antibiotic ciprofloxacin hydrochloride from aqueous solution by diatomite-basic zinc chloride composites.

The antibiotic ciprofloxacin (CIP) is used to treat a variety of bacterial infections, yet it poses significant health risks to aquatic environments. While adsorption is a promising technique for CIP removal, current adsorption capacities remain limited. In this study, we introduce a diatomite and basic zinc chloride composite (ZnHC-Dt) prepared using a straightforward deposition method, with the ability to achieve highly efficient ciprofloxacin removal. ZnHC-Dt is characterized using field emission scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), and the Brunauer-Emmett-Teller method (BET). We also assess the zeta potential. The optimized ZnHC-Dt adsorbent, achieved at a mass ratio of 0.45 with ZnHC/(ZnHC+Dt), is adopted with a CIP adsorption capacity of 831.96 mg/g at 25 °C, broad pH adaptability (within 3.0-10.0), rapid adsorption rate (reaching equilibrium in 4 h), and stable performance under Na+ ionic strength. The CIP adsorption process follows pseudo-second-order kinetics and aligns well with the Langmuir adsorption model. The high adsorption capacity of ZnHC-Dt can be attributed to electrostatic attraction, hydrogen bonding, surface complexation, and available adsorption sites. During the desorption process, the CIP removal rate retains 65.33% effectiveness after five cycles. The results suggest that ZnHC-Dt holds significant potential for CIP removal in aqueous solutions.

Construction of an allophane-based molecularly imprinted polymer for the efficient removal of antibiotic from aqueous solution.

The widespread presence of ciprofloxacin (CIP) antibiotic in the water and soil poses substantial potential risks to the environment, threatening both human and animal health. In this study, we used nanoclay mineral allophane (Allo), ß-cyclodextrin (ß-CD) as a bifunctional monomer, and sodium alginate as a cross-linking agent, to prepare 3D porous Allo-ß-CD molecularly imprinted polymers (MIPs) for the efficient removal of CIP from aqueous solution. The prepared Allo-ß-CD MIP was characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and zeta potential measurements. The effects of initial concentration, time, pH level, and ion concentration on CIP removal dynamics were systematically studied. The adsorption kinetics and equilibrium data of CIP were well-fitted by the pseudo-second-order kinetic model and Langmuir isotherm models, respectively. The Allo-ß-CD MIP can efficiently remove CIP from an aqueous solution, with a maximal adsorption capacity of 635 mg/g. It also has impressive recyclability, and enhanced selectivity, and is widely adaptable to various environmental conditions. The adsorption mechanisms of the as-prepared adsorbent include H bonds, hydrophobic interactions, surface complexation, and n-π EDA interactions. Given the experimental evidence, as-prepared adsorbent is therefore a promising candidate for the effective removal of CIP from the aquatic environment.

Intensive adsorption of tetracycline by cobalt oxide quantum dots-loaded mineral carbon.

Spent bleaching earth (SBE), a waste by-product produced from the bleaching step of edible oil by montmorillonite clays (bleaching earth), causes serious public health and environmental problems. Accordingly, in this study, SBE was pyrolyzed to yield mineral carbon materials (SBE@C) and cobalt oxide (Co3O4) was loaded to improve the active site of those materials. Due to the carrier function of SBE@C, ultra-fine Co3O4 quantum dots (QDs) (2-6 nm) were homogeneously and robustly immobilized onto SBE@C. The obtained adsorbent exhibited high regeneration performance and an outstanding adsorption capacity (253.36 mg/g). It can be attributed to the surface complexation of cobalt with TC being the dominant process contributing to adsorption behavior. Further, Co3O4 QDs-SBE@C still maintained adequate sorption capacity at a broad range of pH values and in the presence of co-occurring ions. These results suggested the significant application potential of SBE and demonstrated the efficiency of using Co3O4 QDs-SBE@C for wastewater remediation.

Direct Atomic-Scale Insight into the Precipitation Formation at the Lanthanum Hydroxide Nanoparticle/Solution Interface.

Understanding precipitation formation at lanthanum hydroxide (La(OH)3) nanoparticle-solution interfaces plays a crucial role in catalysis, adsorption, and electrochemical energy storage applications. Liquid-phase transmission electron microscopy enables powerful visualization with high resolution. However, direct atomic-scale imaging of the interfacial metal (hydro)oxide nanostructure in solutions has been a major challenge due to their beam-driven dissolution. Combining focused ion beam and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, we present an atomic-scale study of precipitation formation at La(OH)3 nanoparticle interfaces after reaction with phosphate. The structure transformation is observed to occur at high- and low-crystalline La(OH)3 nanoparticle surfaces. Low-crystalline La(OH)3 mostly transformed and high-crystalline ones partly converted to LaPO4 precipitations on the outer surface. The long-term structure evolution shows the low transformation of high-crystalline La(OH)3 nanoparticles to LaPO4 precipitation. Because precipitation at solid-solution interfaces is common in nature and industry, these results could provide valuable references for their atomic-scale observation.

Mechanistic insights into the interfacial adsorption behaviors of Cr(VI) on ferrihydrite: Effects of pH and naturally coexisting anions in the environment.

Interfacial interaction of hexavalent chromium (Cr[VI]) with ferrihydrite (Fh) plays a key role in the behavior of Cr(VI) in the environment. In this study, H2PO4-, SO42-, NO3-, Cl-, and HCO3- were chosen as coexisting anions to explore their inhibition of the capacity of Fh to adsorb Cr(VI). We employed X-ray diffraction, scanning electron microscopy, attenuated total reflection Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy to thoroughly characterize Fh reaction products before and after adsorption of Cr(VI). The results clearly revealed that pH has a marked effect on the extent of Cr(VI) adsorption onto Fh, and this process is also highly dependent on the types of anions present. H2PO4- exhibited the most evident inhibition of Cr(VI) adsorption, even at low concentrations. Similarly, the inhibition of Cr(VI) adsorption by HCO3- increased markedly with increasing pH. In contrast, SO42- only slightly competed with Cr(VI) for reactive Fh surface sites. The anions Cl- and NO3- exhibited almost no inhibitory effect on Cr(VI) adsorption. The differential order of adsorptive affinity of all six anions for Fh was as follows: H2PO4- > HCO3- > SO42- ≈ HCrO4- > NO3- ≈ Cl-. Based on these results, we further provide mechanistic insights into the complexities of Cr(VI) adsorption/desorption behaviors on Fh surfaces. Using Fh as a geosorbent, these interfacial properties could be exploited to mediate the immobilization and release of chromate from and/or into contaminated environments such as aquifers.

Converting Chrysotile Nanotubes into Magnesium Oxide and Hydroxide Using Lanthanum Oxycarbonate Hybridization and Alkaline Treatment for Efficient Phosphate Adsorption.

Magnesium oxide and hydroxide nanomaterials comprise a class of promising advanced functional metal nanomaterials whose use in environmental and material applications is increasing. Several strategies to synthesize these nanomaterials have been described but are unsustainable and uneconomic. This work reports on a processing strategy that turns natural magnesium-rich chrysotile into magnesium oxide and hydroxide nanoparticles via nanoparticle hybridization and an alkaline process while enabling La-based nanoparticles to coat the chrysotile nanotube surfaces. The adsorbent's resulting hybrid nanostructure had an outstanding capacity for phosphate uptake (135.2 mg P g-1) and enhanced regeneration performance. Furthermore, the adsorbent featured wide applicability with respect to the coexistence of competitive anions and a broad range of pH conditions, and its high-performance phosphate removal from sewage effluent was also demonstrated. Spectroscopic and microscopic analyses revealed the scavenging ability of phosphate by the La-based and Mg-based nanoparticles and the multiple capture mechanisms involved, including surface complexation and ion exchange. This proposed approach expands chrysotile's potential use as a magnesium-rich nanomaterial and harbors great promise for the removal of pollutants in a variety of real-world settings.

Transfer Printing of Perovskite Whispering Gallery Mode Laser Cavities by Thermal Release Tape.

The outstanding optoelectrical properties and high-quality factor of whispering gallery mode perovskite nanocavities make it attractive for applications in small lasers. However, efforts to make lasers with better performance have been hampered by the lack of efficient methods for the synthesis and transfer of perovskite nanocavities on desired substrate at quality required for applications. Here, we report transfer printing of perovskite nanocavities grown by chemical vapor deposition from mica substrate onto SiO2 substrate. Transferred perovskite nanocavity has an RMS roughness of ~ 1.2 nm and no thermal degradation in thermal release process. We further use femtosecond laser to excite a transferred perovskite nanocavity and measures its quality factor as high as 2580 and a lasing threshold of 27.89 µJ/cm2 which is almost unchanged as compared with pristine perovskite nanocavities. This method represents a significant step toward the realization of perovskite nanolasers with smaller sizes and better heat management as well as application in optoelectronic devices.

Coupling Natural Halloysite Nanotubes and Bimetallic Pt-Au Alloy Nanoparticles for Highly Efficient and Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

The aerobic oxidation of 5-hydroxymethylfurfural (HMF), a key platform compound derived from biomass, to 2,5-furandicarboxylic acid (FDCA) is a highly important reaction in the production of green and sustainable chemicals. Here, we developed a highly efficient and stable halloysite-supported Pt-Au alloy catalyst for the selective oxidation of HMF to FDCA. The catalyst was synthesized through the organosilane functionalization of halloysite nanotubes, followed by the in situ formation and dispersion of Pt-Au alloy nanoparticles on the internal and external surfaces of nanotubes. The composition, morphology, and structure of the prepared catalyst were characterized. The catalyst with the optimal composition of Pt/Au molar ratio of 1/4 and metal loading of 1.5 wt % exhibited outstanding catalytic activity for the oxidation of HMF to FDCA using O2 as an oxidant with 100% conversion of HMF and 99% selectivity of FDCA. This excellent catalytic performance is mainly attributed to the high dispersion and alloying effects of bimetallic nanoparticles, which promoted the activation of reactants or intermediates and further improved FDCA selectivity. Furthermore, the halloysite-supported Pt/Au bimetallic catalyst showed high stability and reusability. This study provides a promising strategy by combining clay mineral halloysite and bimetallic alloys for developing efficient catalysts with high FDCA selectivity and stability for the oxidation of HMF to FDCA.

Highly regenerative and efficient adsorption of phosphate by restructuring natural palygorskite clay via alkaline activation and co-calcination.

Herein, we present a new strategy to create a highly regenerative and efficient phosphate adsorbent based on activating natural palygorskite structures. Both the regeneration via alkaline activation and synthesis via co-calcination restructured the palygorskite and created adsorptive metal oxides. The phosphate adsorbent exhibits excellent regeneration performance with high removal capacity.

The health concern of polychlorinated biphenyls (PCBs) in a notorious e-waste recycling site.

Polychlorinated biphenyls (PCBs) remain a relatively high level in e-waste recycling regions 3 decades after ban on use. Illegal recycling activities cunningly moved under the environmental law enforcement. Here, we analyzed PCBs in soils and plants from Guiyu, China (one of the world's largest recycling areas) to understand the relationship between PCBs pollution and the transition of recycling activities (locations and techniques). High concentrations of PCBs were found in soil and plant samples from emerging recycling sites, up to 234 ng g-1 and 236 ng g-1 (dry weight), respectively. The recycling activities, specifically the open burning process, would obviously aggravate the PCB pollution levels in its environment. The calculated values of estimated daily intake and hazard ratios of PCBs in dietary routes showed that health risks should be taken seriously.

Novel mutations of COL4A3, COL4A4, and COL4A5 genes in Chinese patients with Alport Syndrome using next generation sequence technique.

BACKGROUND: Alport syndrome (AS) is an inherited progressive renal disease caused by mutations in COL4A3, COL4A4, and COL4A5 genes. The large sizes of these genes and the absence of mutation hot spots have complicated mutational analysis by routine PCR-based approaches. In recent years, the development of next-generation sequencing (NGS) has made possible the time- and cost-effective and accurate analysis of the three genes in a single step. METHODS: Here, we analyze COL4A3, COL4A4, and COL4A5 simultaneously in 29 AS patients using NGS. Candidate mutations were validated by classic Sanger sequencing and Real-time PCR. RESULTS: Twenty two new mutations and 10 known mutations were detected. Of those novel mutations, 18, 3, and 1 mutations were detected in COL4A5, COL4A4, and COL4A3, respectively. Twenty six patients showed X-linked inheritance, one showed autosomal recessive inheritance and two showed digenic inheritance (DI). CONCLUSION: A comparison of the clinical manifestations caused by different types of mutations in COL4A5 suggested that large fragment mutations are relatively more severe than the other missense mutations and AS by some mutations may show inter- and intra-familial phenotypic variability. It is important to consider these transmission patterns in the clinical evaluation according to the results of genetic testing, especially for DI. Twenty two new mutations can expand the genotypic spectrum of AS.

Activation of natural halloysite nanotubes by introducing lanthanum oxycarbonate nanoparticles via co-calcination for outstanding phosphate removal.

Halloysite nanotubes were activated via co-calcination of halloysite and the precursors of lanthanum oxycarbonate (LO), generating reactive alumina nanoparticles and uniformly anchoring LO nanoparticles to halloysite surfaces. The resulting LO-alumina combination exhibits record-high phosphate adsorption capacity as well as excellence in adsorption selectivity and sewage phosphate removal.

Activating 2D nano-kaolinite using hybrid nanoparticles for enhanced phosphate capture.

A synergistic host-guest coupling is exploited to disorder nano-kaolinite unit layers to form Al2O3 nanoparticles, which act as activated adsorptive sites; meanwhile, the coupling enables La-based nanoparticles to anchor homogenously on the nano-kaolinite surfaces, fully utilizing their adsorption ability. The activated hybrid nanostructures exhibit an excellent phosphate adsorption capacity.

Biosurfactant rhamnolipid enhanced modification of corn stalk and its application for sorption of phenanthrene.

The application of modified agricultural wastes for removing polycyclic aromatic hydrocarbons (PAHs) from water is gaining a growing interest. However, most modified methods using synthetic chemicals may cause secondary pollution. To overcome this limitation, in this study, a rhamnolipid modified corn stalk (RL-CS) for the removal of phenanthrene (PHE) from aqueous solution was prepared using a rhamnolipid-enhanced acid modification method. RL-CS with higher surface area and lower polarity exhibited higher PHE removal efficiency than that of raw corn stalk (RCS). The adsorption kinetics of RL-CS fitted well with pseudo-second-order kinetics (R2 > 0.999). Sorption coefficients and carbon-normalized sorption coefficient of RL-CS were 4.68 and 2.86 times higher than that of RCS. Sorption process of RL-CS was nonlinear. Meanwhile, the sorption was an exothermic process and could occur spontaneously. The present study demonstrated that biosurfactant-modified biosorbent RL-CS may be of great potential for the removal of low concentrations of PAHs from the contaminated waters.

Cosolubilization synergism occurrence in codesorption of PAH mixtures during surfactant-enhanced remediation of contaminated soil.

Surfactant-enhanced remediation (SER) has been widely applied in decontaminating PAH-polluted soil. Most researches focus on evaluating washing efficiency without considering pollutants' mutual interaction. This study aims to investigate cosolubilization effect between phenanthrene (Phe) and pyrene (Pyr) in nonionic surfactant Triton X-100 (TX100) solution on their codesorption performance from soil. Cosolubilization experiment showed that, when cosolubilized, solubility of Phe and Pyr in TX100 increased by 15.38% and 18.19%, respectively, as quantified by the deviation ratio of molar solubilization ratio in single and binary solute solubilization systems. The synergism may be due to the enlarged micelle volume caused by PAHs solubilized in the shell region of the micelle. The cosolubilization effect was further observed in the soil washing process. The strengthened TX100 solubilization capacity towards Phe and Pyr could increase the two PAHs' codesorption efficiency from soil, accompanied by synergistic extent of 6-15%. However, synergism in codesorption was weaker than that observed in the cosolubilization system, which may be related to surfactant loss to soil and PAH partition into soil organic matter and the sorbed surfactants. The improved remediation performance during codesorption of mixed PAHs implies the significance of combining PAHs' mutual interaction into evaluating SER, which may reduce the surfactant washing concentration and save remediation cost.

Electrokinetic-Enhanced Remediation of Phenanthrene-Contaminated Soil Combined with Sphingomonas sp. GY2B and Biosurfactant.

Electrokinetic-microbial remediation (EMR) has emerged as a promising option for the removal of polycyclic aromatic hydrocarbons (PAHs) from contaminated soils. The aim of this study was to enhance degradation of phenanthrene (Phe)-contaminated soils using EMR combined with biosurfactants. The electrokinetic (EK) remediation, combined with Phe-degrading Sphingomonas sp. GY2B, and biosurfactant obtained by fermentation of Pseudomonas sp. MZ01, degraded Phe in the soil with an efficiency of up to 65.1 % at the anode, 49.9 % at the cathode after 5 days of the treatment. The presence of biosurfactants, electricity, and a neutral electrolyte stimulated the growth of the degrading bacteria as shown by a rapid increase in microbial biomass with time. The electrical conductivity and pH changed little during the course of the treatment, which benefitted the growth of microorganisms and the remediation of Phe-contaminated soil. The EMR system with the addition of biosurfactant had the highest Phe removal, demonstrating the biosurfactant may enhance the bioavailability of Phe and the interaction with the microorganism. This study suggests that the EMR combined with biosurfactants can be used to enhance in situ bioremediation of PAH-contaminated soils.

Synthesis of tetrakis (hydroxymethyl) phosphonium chloride by high-concentration phosphine in industrial off-gas.

With increasing consumption of phosphate rock and acceleration of global phosphate production, the shortage of phosphate resources is increasing with the development and utilization of phosphate. China's Ministry of Land and Resources has classified phosphate as a mineral that cannot meet China's growing demand for phosphate rock in 2010. The phosphorus chemical industry is one of the important economic pillars for Yunnan province. Yellow phosphorus production in enterprises has led to a significant increase in the amount of phosphorus sludge. This paper focuses on phosphine generation in the process of phosphoric sludge utilization, where the flame retardant tetrakis (hydroxymethyl) phosphonium chloride (THPC) is synthesized by high concentrations of phosphine. The optimum conditions are determined at a space velocity of 150 h(-1), a reaction temperature of 60 °C, 0.75 g of catalyst, and a ratio of raw materials of 4:1. Because of the catalytic oxidation of copper chloride (CuCl2), the synthesis of THPC was accelerated significantly. In conclusion, THPC can be efficiently synthesized under optimal conditions and with CuCl2 as a catalyst.