The Bioaccumulation and Health Risk Assessment of Metals among Two Most Consumed Species of Angling Fish (Cyprinus carpio and Pseudohemiculter dispar) in Liuzhou (China): Winter Should Be Treated as a Suitable Season for Fish Angling.

Wild fish caught by anglers were validated to be commonly polluted by metals, but their contamination status could be varied with changing seasons. To determine the seasonal variation in metal pollution and health risks in these fish, this study took Liuzhou City as an example to investigate the concentrations of eight metals in two dominant angling fishes (Cyprinus carpio and Pseudohemiculter dispar) collected, respectively, in winter and summer. The obtained results suggested the mean concentrations of metals in fish are overall lower in winter. Only Cr, Zn, and Cd in some fish were beyond the thresholds in summer. The significant correlations between fish length and weight and most metals suggested the biological dilution effect could exert its influence in winter. The similar distribution of metals in winter suggested that metal bioaccumulation should be manipulated by living habitats, while the inconsistent distribution of metals in summer may be related to the variation in feeding behavior. The metal pollution index (Pi) values were all below 0.2 in winter, which suggested no metal contamination in fish, but most fish were found to be mostly contaminated by Cr and Cd in summer, which was confirmed by their Pi > 0.2. The fish could be consumed freely in winter due to the total target hazard quotient (TTHQ) below 1, while the consumption of fish was not entirely safe in summer, particularly for children, due to TTHQ values that were generally beyond 1. Given the higher weekly recommended consumption of fish in winter, winter should be treated as a suitable season for fish angling.

The Accumulation and Transformation of Heavy Metals in Sediments of Liujiang River Basin in Southern China and Their Threatening on Water Security.

Heavy metal (HM) pollution in sediments is tightly related to the security of water quality in rivers, but the accumulation and conversion of HMs are poorly researched, so that a field study was conducted as an example in the Liujiang River Basin. Seven HMs were analyzed to determine between the overlying water and sediments. Moreover, the regulation of HMs speciation and environmental factors in their accumulation and conversion were identified. The obtained results suggested the HM concentrations in water are far below the primary standard of water quality, but in sediments, the contents of Cd and Zn are significantly higher than their corresponding baseline of soil. Only Cd and Pb are dominantly in non-residual form (carbonate-bound fraction and reducible fraction, respectively). The non-significant correlations suggested pH and Eh may be hard to influence HMs in water, while the significant correlations highlighted the regulations of Eh, organic matter and mean grain size on the accumulation of metals in sediments. The opposite correlations between EC, TDS, pH and Cd confirmed the emission of acid wastewater contributed to the accumulation of Cd in sediment. The conversion of metals between water and sediments were found to be significant only in specific forms of Cd, As, Cu, Zn and Pb, suggesting the conversion of HMs in sediments should be largely regulated by their specific forms. The very high risk disclosed by the higher values of Eri and RI are only found upstream, while the higher risk of Cd should be treated as a critical environmental threat.

Directing photocatalytic pathway to exceedingly high antibacterial activity in water by functionalizing holey ultrathin nanosheets of graphitic carbon nitride.

Metal-free polymeric carbon nitride (C3N4) photocatalysts offer attractive technological advantages over the conventional transition metal oxides or sulfides -based photocatalysts in water disinfection, but their antimicrobial activities are limited by their rapid charge carrier recombination and low specific surface areas. By controlling photocatalytic pathways, we obtained in amino-rich holey ultrathin g-C3N4 nanosheets (AHUCN) a highly efficient inactivation rate against E-coli, which is the highest among the monolithic g-C3N4 and exceeds the antibacterial performance of the most of the previously reported g-C3N4-based photocatalysts. Both the experiments and theoretical calculations demonstrated that the high photocatalytic disinfection performance of AHUCN was derived from the synergistic advantages of their unique holey ultrathin structure and the amino - rich surface in controlling the charge separation and transfer, and most importantly in increasing the photo-production of the dominant antibacterial species, H2O2. From the analysis of the reactive oxygen species and rotating disk electrode (RDE) measurements, it was found that the presence of abundant surface amino groups enabled the switch of the oxygen-reduction pathway from the two-step single-electron indirect reduction on holey ultrathin g-C3N4 nanosheets (HUCN) to the one-step two-electron direct reduction on AHUCN. The switch of the H2O2 production pathway not only facilitated the separation of photogenerated electron-hole pairs but also promoted the generation of reactive oxygen species, greatly enhancing photocatalytic disinfection efficiency.

Photovoltage response of (XZn)Fe2O4-BiFeO3 (X=Mg, Mn or Ni) interfaces for highly selective Cr3+, Cd2+, Co2+ and Pb2+ ions detection.

High-photostability fluorescent (XZn)Fe2O4 (X=Mg, Mn or Ni) embedded in BiFeO3 spinel-perovskite nanocomposites were successfully fabricated via a novel bio-induced phase transfer method using shewanella oneidensis MR-1. These nanocomposites have the near-infrared fluorescence response (XZn or Fe)-O-O-(Bi) interfaces (785/832nm), and the (XZn)Fe2O4/BiFeO3 lattices with high/low potentials (572.15-808.77meV/206.43-548.1meV). Our results suggest that heavy metal ion (Cr3+, Cd2+, Co2+ and Pb2+) d↓ orbitals hybridize with the paired-spin X-Zn-Fe d↓-d↓-d↑↓ orbitals to decrease the average polarization angles (-29.78 to 44.71°), qualitatively enhancing the photovoltage response selective potentials (39.57-487.84meV). The fluorescent kinetic analysis shows that both first-order and second-order equilibrium adsorption isotherms are in line and meet the Langmuir and Freundlich modes. Highly selective fluorescence detection of Co2+, Cr3+ and Cd2+ can be achieved using Fe3O4-BiFeO3 (Langmuir mode), (MgZn)Fe2O4-BiFeO3 and (MnZn)Fe2O4-BiFeO3 (Freundlich mode), respectively. Where the corresponding max adsorption capacities (qmax) are 1.5-1.94, 35.65 and 43.7 multiple, respectively, being more competitive than that of other heavy metal ions. The present bio-synthesized method might be relevant for high-photostability fluorescent spinel-perovskite nanocomposites, for design of heavy metal ion sensors.

Enhanced Photovoltage Response of Hematite-X-Ferrite Interfaces (X = Cr, Mn, Co, or Ni).

High-fluorescent p-X-ferrites (XFe2O4; XFO; X = Fe, Cr, Mn, Co, or Ni) embedded in n-hematite (Fe2O3) surfaces were successfully fabricated via a facile bio-approach using Shewanella oneidensis MR-1. The results revealed that the X ions with high/low work functions modify the unpaired spin Fe2+-O2- orbitals in the XFe2O4 lattices to become localized paired spin orbitals at the bottom of conduction band, separating the photovoltage response signals (73.36~455.16/-72.63~-32.43 meV). These (Fe2O3)-O-O-(XFe2O4) interfacial coupling behaviors at two fluorescence emission peaks (785/795 nm) are explained via calculating electron-hole effective masses (Fe2O3-FeFe2O4 17.23 × 10-31 kg; Fe2O3-CoFe2O4 3.93 × 10-31 kg; Fe2O3-NiFe2O4 11.59 × 10-31 kg; Fe2O3-CrFe2O4 -4.2 × 10-31 kg; Fe2O3-MnFe2O4 -11.73 × 10-31 kg). Such a system could open up a new idea in the design of photovoltage response biosensors.

Mechanism of Fluorescence Enhancement of Biosynthesized XFe2O4-BiFeO3 (X = Cr, Mn, Co, or Ni) Membranes.

Ferrites-bismuth ferrite is an intriguing option for medical diagnostic imaging device due to its magnetoelectric and enhanced near-infrared fluorescent properties. However, the embedded XFO nanoparticles are randomly located on the BFO membranes, making implementation in devices difficult. To overcome this, we present a facile bio-approach to produce XFe2O4-BiFeO3 (XFO-BFO) (X = Cr, Mn, Co, or Ni) membranes using Shewanella oneidensis MR-1. The perovskite BFO enhances the fluorescence intensity (at 660 and 832 nm) and surface potential difference (-469 ~ 385 meV and -80 ~ 525 meV) of the embedded spinel XFO. This mechanism is attributed to the interfacial coupling of the X-Fe (e- or h+) and O-O (h+) interfaces. Such a system could open up new ideas in the design of environmentally friendly fluorescent membranes.

Computational Study of the Cation-Modified GSH Peptide Interactions With Perovskite-Type BFO-(111) Membranes Under Aqueous Conditions.

We elucidated a number of facets regarding glutathione (GSH)-bismuth ferrite (BiFeO3, BFO) interactions and reactivity that have previously remained unexplored on a molecular level. In this approach, the cation-modified reduced GSH (or oxidised glutathione (GS·)) formed on the (111)-oriented BiFeO3 membrane (namely BFO-(111)) can serve as an efficient quencher, and the luminescence mechanism is explained in aqueous conditions. Notably, we suggest the use of Fe(2+)↓ ion as an electron donor and K(+) ion as an electron acceptor to exert a "gluing" effect on the glutamic acid (Glu) and glycine (Gly) side chains, producing an exposed sulfhydryl (-SH) configuration. This method may enable the rational design of a convenient platform for biosensors.

DFT and two-dimensional correlation analysis methods for evaluating the Pu(3+)-Pu(4+) electronic transition of plutonium-doped zircon.

Understanding how plutonium (Pu) doping affects the crystalline zircon structure is very important for risk management. However, so far, there have been only a very limited number of reports of the quantitative simulation of the effects of the Pu charge and concentration on the phase transition. In this study, we used density functional theory (DFT), virtual crystal approximation (VCA), and two-dimensional correlation analysis (2D-CA) techniques to calculate the origins of the structural and electronic transitions of Zr1-cPucSiO4 over a wide range of Pu doping concentrations (c=0-10mol%). The calculations indicated that the low-angular-momentum Pu-fxy-shell electron excites an inner-shell O-2s(2) orbital to create an oxygen defect (VO-s) below c=2.8mol%. This oxygen defect then captures a low-angular-momentum Zr-5p(6)5s(2) electron to form an sp hybrid orbital, which exhibits a stable phase structure. When c>2.8mol%, each accumulated VO-p defect captures a high-angular-momentum Zr-4dz electron and two Si-pz electrons to create delocalized Si(4+)→Si(2+) charge disproportionation. Therefore, we suggest that the optimal amount of Pu cannot exceed 7.5mol% because of the formation of a mixture of ZrO8 polyhedral and SiO4 tetrahedral phases with the orientation (10-1). This study offers new perspective on the development of highly stable zircon-based solid solution materials.

First principles simulation of temperature dependent electronic transition of FM-AFM phase BFO.

Understanding how temperature affects the electronic transitions of BFO is important for design of BiFeO3 (BFO)-based temperature-sensitive device. Hitherto, however, there have been only very limited reports of the quantitative simulation. Here, we used density functional theory (DFT) and two-dimensional correlation analysis (2D-CA) techniques to calculate the systematic variations in electronic transitions of BFO crystal, over a range of temperature (50~1500 K). The results suggest that the heat accumulation accelerates the O-2p(4) orbital splitting, inducing the Fe(3+)-3d(5) → Fe(2+)-3d(5)d(0) charge disproportionation. The origin is observed as the temperature-dependent electron transfer process changes from threefold degeneracy to twofold degeneracy. Additionally, the crystallographic orientation (111) can be used to control the 2p-hole-induced electronic transition as O → unoccupied Fe(3+)-3d(5), in comparison to the O → Bi-6p(3) + Fe(3+)-3d(5)d(0) on the orientations (001) and (101). This study offers new perspective on the improvement of BFO-based temperature-sensitive device.