Tailoring local electron density and molecular oxygen activation behavior via potassium/halogen co-tuned graphitic carbon nitride for enhanced photocatalytic activity.

Graphite carbon nitride (g-C3N4) is a promising photocatalyst,but its inadequate reactive sites, weak visible light responsiveness, and sluggish separation of photogenerated carriers hamperthe improvement of photodegradation efficiency. In this work, potassium (K) and halogen atoms co-modified g-C3N4 photocatalysts (CN-KX, X = F, Cl, Br, I) were constructed to adjust the electrical and band structure for enhanced generation of reactive oxygen species. Through an integration of theoretical calculation and experimental exploration, the doping sites of halogen atoms as well as the evolution of crystal, band, and electronic structures were investigated. The results show that a covalent bond is formed between the F atom and the C atom, substitution of the N atom occurs with a Cl atom, and doping of Br, I, or K atoms takes place at the interstitial site. CN-KX photocatalysts exhibits lower band gap, faster photogenerated electron migration, and enhanced photocatalytic activity. Specifically, the CN-KI photocatalyst exhibits the highest photodegradation efficiency because of its smaller interplanar spacing, formation of the midgap state, and adjustable local electron density. Equally, the doping of I atom not only provides a stable adsorption site for oxygen (O2) but also facilitates electron transfer, promoting the production of superoxide radicals (O2-) and contributing to the process of photodegradation.

Unveiling the lithium deintercalation mechanisms in spent lithium-ion batteries via sulfation roasting.

Recovery of valuable metals from spent lithium-ion batteries (LIBs) is of great importance for resource sustainability and environmental protection. This study introduced pyrite ore (FeS2) as an alternative additive to achieve the selective recovery of Li2CO3 from spent LiCoO2 (LCO) batteries. The mechanism study revealed that the sulfation reaction followed two pathways. During the initial stage (550 °C-800 °C), the decomposition and oxidation of FeS2 and the subsequent gas-solid reaction between the resulting SO2 and layered LCO play crucial roles. The sulfation of lithium occurred prior to cobalt, resulting in the disruption of layered structure of LCO and the transformation into tetragonal spinel. In the second stage (over 800 °C), the dominated reactions were the decomposition of orthorhombic cobalt sulfate and its combination with rhombohedral Fe2O3 to form CoFe2O4. The deintercalation of Li from LCO by the substitution of Fe and conversion of Co(III)/Fe(II) into Co3O4/CoFe2O4 were further confirmed by density functional theory (DFT) calculation results. This fundamental understanding of the sulfation reaction facilitated the future development of lithium extraction methods that utilized additives to substantially reduce energy consumption.

Process parameters and biological mechanism of efficient removal of Cd(II) ion from wastewater by a novel Bacillus subtilis TR1.

The safe treatment of heavy metals in wastewater is directly related to the human health and social development. In this paper, a new biological strain has been isolated from electroplating wastewater, which can effectively remove metal ions in wastewater. The results of 16 S rDNA sequencing analysis and NCBI GenBank database comparison show that the strain belongs to a novel Bacillus genus and names Bacillus subtilis TR1 with the accession number of OL441606. The removal rate of Cd(II) reaches to 85.68% with the conditions of pH = 7, C0Cd(II) = 20 mg L-1, t = 48 h, m = 0.1 g, and T = 35 °C. The biological removal mechanism of Cd(II) is in-depth studied by FTIR and XRD combined with third-generation sequencing. The results indicate that Bacillus subtilis TR1 removes Cd(II) mainly through two synergistic pathways, namely, extracellular chemisorption and intracellular bioaccumulation: 1) The groups carried on the surface of the strain, such as -COOH, -NH, -OH and C-H, have good chemisorption properties for Cd(II) and easily form cadmium containing chelation (-COO-Cd(II), -N-Cd(II), etc.) with these groups. The appearance of TR1 strain changes from cylindrical to spherical after Cd(II) adsorption, which is due to the biotoxicity of Cd(II); 2) Cd(II) exchanges on the surface of TR1 strain with K and Na ions released from the intracellular cytoplasm and enters the cytoplasm under the transfer of biological transport medium. This part of Cd(II) is converted into its own components by anabolic enzymes and accumulates in the cytoplasm. These data provide a new biological agent for the efficient treatment of heavy metal ions in wastewater and enrich relevant theoretical knowledge.

The interaction of ZnO nanoparticles, Cr(VI), and microorganisms triggers a novel ROS scavenging strategy to inhibit microbial Cr(VI) reduction.

Cr(VI) contaminated water usually contains other contaminants like engineered nanomaterials (ENMs). During the process of microbial treatment, the inevitable interaction of Cr(VI), ENMs, and microorganisms probably determines the efficiency of Cr(VI) biotransformation, however, the corresponding information remains elusive. This study investigated the interaction of ZnO nanoparticles (NPs), Cr(VI), and Pannonibacter phragmitetus BB (hereafter BB), which changed the process of microbial Cr(VI) reduction. ZnO NPs inhibited Cr(VI) reduction, but had no effect on bacterial viability. In particular, Cr(VI) induced BB to produce organic acids and to drive Zn2+ dissolution from ZnO NPs inside and outside of cells. The dissolved Zn2+ not only promoted Cr(VI) reduction to Cr(V)/Cr(IV) by strengthening sugar metabolism and inducing increase in NAD(P)H production, but also hindered Cr(V)/Cr(IV) transformation to Cr(III) through down-regulating Cr(VI) reductase genes. A novel bacterial driven ROS scavenging mechanism leading to the inhibition of Cr(VI) reduction was elucidated. Specifically, the accumulated Cr(VI) and Cr(V)/Cr(IV) formed a redox dynamic equilibrium, which triggered the disproportionation of superoxide radicals mimicking superoxide dismutase through the flip-flop of Cr(VI) and Cr(V)/Cr(IV) in bacterial cells. This study provided a realistic insight into design the applicability of biological remediation technology for Cr(VI) contaminant and evaluating environmental risks of ENMs.

Response of Trametes hirsuta to hexavalent chromium promotes laccase-mediated decolorization of reactive black 5.

The recalcitrant azo dyes combined with heavy metals constitute a major challenge for the bioremediation of industrial effluents. This study aimed to investigate the effect and mechanism of action of a white-rot fungus Trametes hirsuta TH315 on the simultaneous removal of hexavalent chromium [Cr(VI)] and azo dye (Reactive Black 5, RB5). Here, this study discovered that toxic Cr(VI) (1 mM) greatly promoted RB5 decolorization (from 57.15% to 83.65%) by white-rot fungus Trametes hirsuta with high Cr(VI)-reducing ability (>96%), resulting in the simultaneous removal of co-contaminants. On the basis of transcriptomic and biochemical analysis, our study revealed that the oxidative stress in co-contaminants mainly caused by Cr(VI), and a number of dehydrogenases and oxidases showed up-regulation in response to Cr(VI) stress. It was noteworthy that the oxidative stress caused by Cr(VI) in co-contaminants can both significantly induce glutathione S-transferase and laccase expression. Glutathione S-transferase potentially involved in antioxidation against Cr(VI) stress. Laccase was found to play a key role in RB5 decolorization by T. hirsuta. These results suggested that the simultaneous removal of co-contaminants by T. hirsuta could be achieved with Cr(VI) exposure. Overall, the elucidation of the molecular basis in details will help to advance the general knowledge about the fungus by facing harsh environments, and put forward a further possible application of fungi on environmental remediation.

Response of Cupriavidus basilensis B-8 to CuO nanoparticles enhances Cr(VI) reduction.

CuO nanoparticles (NPs) released into aqueous environments induce metal toxicity, which generally exerts negative effects on various organisms and leads to great challenge for wastewater biotreatment. In this study, a promotion effect of CuO NPs on biological process was first found. Cr(VI) reduction by Cupriavidus basilensis B-8 (hereafter B-8) was enhanced in the presence of CuO NPs. The efficiency of Cr(VI) bioreduction was much higher with B-8 and CuO NPs (approximately 100%) than with B-8 (approximately 37.6%) and CuO NPs (39.9-44.7%) alone, indicating a stimulatory effect of CuO NPs on Cr(VI) reduction by B-8. Our material analyses revealed different response mechanisms of B-8 to Cr(VI), with and without CuO NPs. The addition of CuO NPs influenced the interaction of Cr(VI) with the N-, P-, S-, and C-related functional groups of B-8. Transcriptomic analysis indicated that multiple mechanisms, including Cr(VI) uptake and reactive oxygen species detoxification, were induced by Cr(VI). Many genes involved in various metabolic processes were significantly upregulated by the addition of CuO NPs. To a certain extent, the pressure of DNA repairment by B-8 induced by Cr(VI) was also alleviated by the presence of CuO NPs. They contributed to facilitate B-8 growth and enhance Cr(VI) reduction, even with 50 mg/L Cr(VI). This study not only elaborated the mechanisms of bacterial Cr(VI) reduction when enhanced by CuO NPs, but also provided a novel perspective for wastewater biotreatment.

Multi-omics response of Pannonibacter phragmitetus BB to hexavalent chromium.

The release of hexavalent chromium [Cr(VI)] into water bodies poses a major threat to the environment and human health. However, studies of the biological response to Cr(VI) are limited. In this study, a toxic bacterial mechanism of Cr(VI) was investigated using Pannonibacter phragmitetus BB (hereafter BB), which was isolated from chromate slag. The maximum Cr(VI) concentrations with respect to the resistance and reduction by BB are 4000 mg L-1 and 2500 mg L-1, respectively. In the BB genome, more genes responsible for Cr(VI) resistance and reduction are observed compared with other P. phragmitetus strains. A total of 361 proteins were upregulated to respond to Cr(VI) exposure, including enzymes for Cr(VI) uptake, intracellular reduction, ROS detoxification, DNA repair, and Cr(VI) efflux and proteins associated with novel mechanisms involving extracellular reduction mediated by electron transfer, quorum sensing, and chemotaxis. Based on metabolomic analysis, 174 metabolites were identified. Most of the upregulated metabolites are involved in amino acid, glucose, lipid, and energy metabolisms. The results show that Cr(VI) induces metabolite production, while metabolites promote Cr(VI) reduction. Overall, multi-enzyme expression and metabolite production by BB contribute to its high ability to resist/reduce Cr(VI). This study provides details supporting the theory of Cr(VI) reduction and a theoretical basis for the efficient bioremoval of Cr(VI) from the environment.

Spotted Fever Group Rickettsiae in Inner Mongolia, China, 2015-2016.

We found Rickettsia raoultii infection in 6/261 brucellosis-negative patients with fever of unknown origin in brucellosis-endemic Inner Mongolia, China. We further identified Hyalomma asiaticum ticks associated with R. raoultii, H. marginatum ticks associated with R. aeschlimannii, and Dermacentor nuttalli ticks associated with both rickettsiae species in the autonomous region.

Discerning three novel chromate reduce and transport genes of highly efficient Pannonibacter phragmitetus BB: From genome to gene and protein.

Here, Pannonibacter phragmitetus BB was investigated at genomic, genetic and protein levels to explore molecular mechanisms of chromium biotransformation, respectively. The results of Miseq sequencing uncovered that a high-qualified bacterial genome draft was achieved with 5.07 Mb in length. Three novel genes involved in chromate reduce and transport, named nitR, chrA1 and chrA2, were identified by alignment, annotation and phylogenetic tree analyses, which encode a chromate reductase (NitR) and two chromate transporters (ChrA1 and ChrA2). Reverse transcription real-time polymerase chain reaction (RT-qPCR) analyses showed that the relative quantitative transcription of the three genes as the maximum reduction rate of Cr(VI) were significantly up-regulated with the increasing initial Cr(VI) concentrations. However, at the maximum cell growth points nitR was in a low transcription level, while the transcription of chrA1 and chrA2 were hold at a relatively high level and decreased with the increasing initial Cr(VI) concentrations. The ex-situ chromate reducing activity of NitR was revealed a Vmax of 34.46 µmol/min/mg enzyme and Km of 14.55 µmol/L, suggesting feasibility of the reaction with Cr(VI) as substrate. The multiple alignment demonstrates that NitR is potentially a nicotinamide adenine dinucleotide phosphate (NADPH) dependent flavin mononucleotide (FMN) reductase of Class I chromate reductases. Our results will prompt a large-scaled bioremediation on the contaminated soils and water by Pannonibacter phragmitetus BB, taking advantage of uncovering its molecular mechanisms of chromium biotransformation.

Case of Human Infection with Anaplasma phagocytophilum in Inner Mongolia, China.

Anaplasma phagocytophilum is an obligate intracellular bacterium that causes febrile illness in humans and livestock. A 49-year-old woman was suffering from feverish symptoms, fatigue, arthralgia, general body pain, and anorexia for 2 weeks. Later, she visited the Bayannur Centers for Disease Control and Prevention Hospital in Inner Mongolia, China. Molecular-based diagnostic analysis of the patient's blood revealed that A. phagocytophilum p44 DNA was positive, but Brucella omp31, spotted fever group Rickettsia gltA, Orientia tsutsugamushi 16S rDNA, and Ehrlichia p28 were negative. The amino acid sequences of 9 A. phagocytophilum p44 clones obtained from the patient shared 44-100% similarity among them and were closely related to those of previously identified p44 clones from Canis familiaris (accession no. KJV64194) and from Ixodes persulcatus tick (no. BAN28309). Serological tests using the patient's serum showed that immunoglobulin M (IgM) and IgG titers to A. phagocytophilum antigens were 160 and 20, respectively, determined using indirect immunofluorescence assay, and the reaction to recombinant P44 proteins (rP44-1, rP44-18ES, and/or rP44-47) was confirmed using Western blot analysis. Thus, the results obtained in this study strongly suggest that the patient was infected with A. phagocytophilum. To our knowledge, this is the first case of human anaplasmosis infection in the Inner Mongolia Autonomous Region.

Removal of Cr(VI) by magnetic Fe/C crosslinked nanoparticle for water purification: rapid contaminant removal property and mechanism of action.

In this study, a novel method based on the magnetic Fe/C crosslinked nanoparticles (MNZVI/CNTs-OH) is reported for the effective removal of Cr(VI) in aqueous solutions. Parameters that influence the effectiveness of the nanoparticles, such as pH, temperature, reaction time, and particle dosage, was analyzed. It was found that MNZVI/CNTs-OH particles exhibit significantly higher activity toward Cr(VI) removal than bare NZVI, carbon nanotubes (CNTs), and other synthetic nanomaterials. Under optimized conditions, the removal efficiency of Cr(VI) by MNZVI/CNTs-OH is up to 98% with an initial contaminant concentration of 50 mg/L, and chromium content in the residue up to 48 mg/g. Physical characterizations, including Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and TG-TD measurements, provide insights into the working mechanism of Cr(VI) purification. Our findings suggest that immobilization of MNZVI onto carbon nanotubes increase the covalent bond property, while crosslinked nanoparticles (NPs) provide the electron transfer passage from the NZVI surface and improves the dispersity of the MNZVI, thus enhancing the performance. These results demonstrate the potential of the MNZVI/CNTs-OH nanoparticles for the rapid and efficient treatment of Cr(VI)-containing wastewater.