Chelating Effect of Siderophore Desferrioxamine-B on Uranyl Biomineralization Mediated by Shewanella putrefaciens.

In contaminated water and soil, little is known about the role and mechanism of the biometabolic molecule siderophore desferrioxamine-B (DFO) in the biogeochemical cycle of uranium due to complicated coordination and reaction networks. Here, a joint experimental and quantum chemical investigation is carried out to probe the biomineralization of uranyl (UO22+, referred to as U(VI) hereafter) induced by Shewanella putrefaciens (abbreviated as S. putrefaciens) in the presence of DFO and Fe3+ ion. The results show that the production of mineralized solids {hydrogen-uranium mica [H2(UO2)2(PO4)2·8H2O]} via S. putrefaciens binding with UO22+ is inhibited by DFO, which can both chelate preferentially UO22+ to form a U(VI)-DFO complex in solution and seize it from U(VI)-biominerals upon solvation. However, with Fe3+ ion introduced, the strong specificity of DFO binding with Fe3+ causes re-emergence of biomineralization of UO22+ {bassetite [Fe(UO2)2(PO4)2·8(H2O)]} by S. putrefaciens, owing to competitive complexation between Fe3+ and UO22+ for DFO. As DFO possesses three hydroxamic functional groups, it forms hexadentate coordination with Fe3+ and UO22+ ions via these functional groups. The stability of the Fe3+-DFO complex is much higher than that of U(VI)-DFO, resulting in some DFO-released UO22+ to be remobilized by S. putrefaciens. Our finding not only adds to the understanding of the fate of toxic U(VI)-containing substances in the environment and biogeochemical cycles in the future but also suggests the promising potential of utilizing functionalized DFO ligands for uranium processing.

MD-DFT Calculations on Dissociative Absorption Configurations of FOX-7 on (001)- and (101)-Oriented Crystalline Parylene Protective Membranes.

Crystalline poly-para-xylylene (parylene) has the potential for use as a protective membrane to delay the nucleation of explosives by separating the explosives and their decomposition products to decrease the explosive sensitivity. Here, molecular dynamics (MD) and density functional theory (DFT) techniques were used to calculate the dissociative adsorption configurations of 1,1-diamino-2,2-dinitroethylene (FOX-7) on (001)- and (101)-oriented crystalline parylene membranes. Based on the results of the calculations, this work demonstrates that the -NO2-π electrostatic interactions are the dominant passivation mechanism of FOX-7 on these oriented surfaces. FOX-7 can dissociatively adsorb on oriented parylene membranes due to the interactions between the LUMO of the toluene (or methyl) groups on parylene and the HOMO of the -NO2 (or -NH2) groups on FOX-7. The formation of a new intermolecular H-bond with the ONO group leads to FOX-7 decomposition via intramolecular C-NO2 bond fission and nitro-to-nitrite rearrangement. The most likely adsorption configurations are described in terms of the decomposition products, surface active groups of parylene, binding behaviors, and N charge transfer. Importantly, the (001)-oriented parylene AF8 membrane is promising for use as a protective membrane to passivate the high-energy -NO2 bonds during the dissociative adsorption of FOX-7. This study offers a new perspective on the development of protective membranes for explosives.

hsa_circ_0008500 regulates Benzo(a)pyrene-loaded gypsum-induced inflammation and apoptosis in human bronchial epithelial cells via activation of Ahr/C-myc pathways.

Polycyclic aromatic hydrocarbons (PAHs) are major organic pollutants attached to fine particulate matter in the atmosphere. They induce lung inflammation, asthma, and other lung diseases. Exploring the toxic mechanism of PAHs on lung epithelial cells may provide a theoretical basis for the prevention and treatment of respiratory diseases induced by PAHs. In our study, 16 human bronchial epithelial (16HBE) cells were exposed to different concentrations of gypsum dust, Benzo(a)pyrene (BaP), and BaP-loaded gypsum dust for 24 hours. Gypsum dust loaded with BaP significantly increased the cytotoxicity of 16HBE cells, enhanced the production of lactate dehydrogenase (LDH), interleukin-6 (IL-6) and interleukin-8 (IL-8), induced cell apoptosis, and upregulate the expression of hsa_circ_0008500 (circ_0008500). The mechanism was studied with a BaP-loaded gypsum dust concentration of 1.25 mg/mL. StemRegenin 1 (SR1) pretreat significantly reduced the release of LDH, IL-6, and IL-8 and decreased the protein levels of Ahr、XAP2, C-myc, and p53. Second-generation sequencing indicated that circ_0008500 was highly expressed after 16HBE induced by BaP-loaded gypsum dust. Functional experiments confirmed that circ_0008500 promoted the inflammation and apoptosis of 16HBE cells induced by BaP-loaded gypsum dust by regulating the Ahr signaling pathway. Our study showed that fine particulate matter adsorption of BaP significantly increased the toxic effect of BaP on cells. By activating the Ahr/C-myc pathway, circ_0008500 promoted inflammation and apoptosis of 16HBE cells induced by BaP-loaded gypsum dust.

Meta-analysis of impacts of microplastics on plant heavy metal(loid) accumulation.

The co-occurrence of microplastics (MPs) and heavy metal(loid)s (HMs) has attracted growing scientific interest because of their wide distribution and environmental toxicity. Nevertheless, the interactions between MPs and HMs in soil-plant systems remain unclear. We conducted a meta-analysis with 3226 observations from 87 independent studies to quantify the impact of MPs addition on the plant biomass and HMS accumulation. Co-occurrence of MPs and HMs (except for As) induced synergistic toxicity to plant growth. MPs promoted their uptake in the shoot by 11.0% for Cd, 30.0% for Pb, and 47.1% for Cu, respectively. In contrast, MPs caused a significant decrease (22.6%, 17.9-26.9%) in the shoot As accumulation. The type and dose of MPs were correlated with the accumulation of HMs. MPs increased available concentrations of Cd, Pb, and Cu, but decreased available As concentration in soils. Meanwhile, MPs addition significantly lowered soil pH. These findings may provide explanations for MPs-mediated effects on influencing the accumulation of HMs in plants. Using a machine learning approach, we revealed that soil pH and total HMs concentration are the major contributors affecting their accumulation in shoot. Overall, our study indicated that MPs may increase the environmental risks of HMs in agroecosystems, especially metal cations.

S defect-rich MoS2 aerogel with hierarchical porous structure: Efficient photocatalysis and convenient reuse for removal of organic dyes.

To avoid the difficulty of separating solids from liquids when reusing powder photocatalysts, 3D stereoscopic photocatalysts were constructed. In this study, three-dimensional S defect-rich MoS2 hierarchical aerogel was prepared by chemical cross-linking of functional ultrathin 2D MoS2. Its phase, micro-morphology and structure were characterized, and it was used in the study of photocatalytic degradation of organic pollutants. Of the samples tested, MS@CA-3 (i.e., defect-rich 3D MoS2 aerogel with a loading of 30 mg of defect-rich MoS2) exhibited the best photocatalytic activity due to its suitable load, good light transmission, and a degradation rate of up to 91.0% after 3 h. In addition, MS@CA-3 aerogel offers high recyclability and structural stability, and the degradation rate of the organic pollutant methylene blue decreases only 9.8% after more than ten cycles of photocatalytic degradation. It combines the high catalytic performance of S defect-rich 2D MoS2 and the convenient reusability of hierarchical porous aerogel. This study provides valuable data and a reference for the practical promotion and application of photocatalytic technology in the field of environmental remediation.

Sources and human health risks associated with potentially toxic elements (PTEs) in urban dust: A global perspective.

Long-term exposure to urban dust containing potentially toxic elements (PTEs) poses detrimental impacts on human health. However, studies estimating human health risks in urban dusts from a global perspective are scarce. We evaluated data for twelve PTEs in urban dusts across 59 countries from 463 published articles, including their concentrations, input sources, and probabilistic risks to human health. We found that 34.1 and 60.3% of those investigated urban dusts have been heavily contaminated with As and Cd, respectively. The input of PTEs was significantly correlated with economic structure due to emissions of industrial activities and traffic emissions being the major sources. Based on the Monte Carlo simulation, we found that the mean hazard index below the safe threshold (1.0) could still cause non-negligible risks to human health. Arsenic and Cr were the major PTEs threatening human health, and relatively high risk levels were observed in cities in China, Korea, Chile, Malaysia, and Australia. Importantly, our analysis suggested that PTEs threaten the health of approximately 92 million adults and 280 million children worldwide. Overall, our study provides important foundational understanding and guidance for policy decision-making to reduce the potential risks associated with PTE exposure and to promote sustainable development of urban economies.

Secondary inorganic aerosols and aerosol acidity at different PM2.5 pollution levels during winter haze episodes in the Sichuan Basin, China.

Wintertime fine particle (PM2.5) pollution remains to be perplexing air quality problems in many parts of China. In this study, PM2.5 compositions and aerosol acidity at different pollution levels at an urban cite in the southwest China's Sichuan Basin were investigated during a sustained winter haze episode. Organic matter was the most abundant component of PM2.5, followed by nitrate, sulfate and ammonium. Shares of organic aerosol in PM2.5 mass decreased with the elevated PM2.5 levels, while the enhancements of sulfate and secondary organic aerosol were much less than that of nitrate and ammonium during heavy pollution with increased ratios of nitrate to sulfate, implying a significant role of nitrate in the haze formation. Results also suggest the nighttime chemistry might contribute substantially to the formation of nitrate under severe pollutions. The daily average aerosol pH showed a decreasing trend with the elevated levels of PM2.5, and this increased aerosl acidity was mainly due to the fast rising secondary inorganic aerosol (SIA) concentration, with the increase in hydronium ion concentration in air (Hair+) surpassing the dilution effect of elevated aerosol liquid water content (LWC). Thermodynamic model calculations revealed that the air environment was NH3-rich with total NHx (NH3 + NH4+) greater than required NHx, and the aerosol pH exponentially declined with the decreasing excess NHx (p < 0.01). This study demonstrated that under air stagnation and NH3-rich environment during winter, the raised relative humidity (RH) would lead to an increase in LWC and thereby facilitate the aqueous chemistry processes with the neutralization capacity of NH3 to form sulfate and nitrate, which would further increase the LWC and lower the pH. This self-amplifying SIA formation might be crucial to the severe PM2.5 pollution and haze events during winter, and therefore cutting both NOx and NH3 emissions would benefit stopping the self-amplification.

Efficient purification of low-level uranium-containing wastewater by polyamine/amidoxime synergistically reinforced fiber.

The removal and recovery of uranium [U(VI)] from organic containing wastewater has been a challenging in radioactive wastewater purification. Here, we designed a polyamine/amidoxime polyacrylonitrile fiber (PAN-AO-A) with high removal efficiency, excellent selectivity, excellent organic resistance and low cost by combining the anti-organic properties of amidoxime polyacrylonitrile fiber (PAN-AO-A) with the high adsorption capacity of polyamine polyacrylonitrile fiber, which is used to extract U(VI) from low-level uranium-containing wastewater with high ammonia nitrogen and organic content. PAN-AO-A adsorbent with high grafting rate (86.52%), high adsorption capacity (qe = 618.8 mg g-1), and strong resistance to organics and impurity interference is achieved. The adsorption rate of U(VI) in both real organic and laundry wastewater containing uranium is as high as 99.7%, and the partition coefficients (Kd) are 7.61 × 105 mL g-1 and 9.16 × 106 mL g-1, respectively. The saturated adsorption capacity of PAN-AO-A in the continuous system solution can reach up to 505.5 mg g-1, and the concentration of U(VI) in the effluent is as low as 1 µg L-1. XPS analysis and Density functional theory (DFT) studies the coordination form between U(VI) and PAN-AO-A, where the most stable structure is η2-AO(UO2)(CO3)2. The -NH-/-NH2 and -C(NH2)N-OH groups of PAN-AO-A exhibit a synergistic complex effect in the U(VI) adsorption process. PAN-AO-A is a material with profound influence and limitless potential that can be used for wastewater containing U(VI) and organic matter.

Unveiling biochar potential to promote safe crop production in toxic metal(loid) contaminated soil: A meta-analysis.

Biochar application emerges as a promising and sustainable solution for the remediation of soils contaminated with potentially toxic metal (loid)s (PTMs), yet its potential to reduce PTM accumulation in crops remains to be fully elucidated. In our study, a hierarchical meta-analysis based on 276 research articles was conducted to quantify the effects of biochar application on crop growth and PTM accumulation. Meanwhile, a machine learning approach was developed to identify the major contributing features. Our findings revealed that biochar application significantly enhanced crop growth, and reduced PTM concentrations in crop tissues, showing a decrease trend of grains (36.1%, 33.6-38.6%) > shoots (31.1%, 29.3-32.8%) > roots (27.5%, 25.7-29.2%). Furthermore, biochar modifications were found to amplify its remediation potential in PTM-contaminated soils. Biochar application was observed to provide favorable conditions for reducing PTM uptake by crops, primarily through decreasing available PTM concentrations and improving overall soil quality. Employing machine learning techniques, we identified biochar properties, such as surface area and C content as a key factor in decreasing PTM bioavailability in soil-crop systems. Furthermore, our study indicated that biochar application could reduce probabilistic health risks associated with of the presence of PTMs in crop grains, thereby contributing to human health protection. These findings highlighted the essential role of biochar in remediating PTM-contaminated lands and offered guidelines for enhancing safe crop production.

Uranium speciation and distribution on the surface of Shewanella putrefaciens in the presence of inorganic phosphate and zero-valent iron under anaerobic conditions.

Shewanella putrefaciens (S. putrefaciens) is one of the main microorganisms in soil bioreactors, which mainly immobilizes uranium through reduction and mineralization processes. However, the effects of elements such as phosphorus and ZVI, which may be present in the actual environment, on the mineralization and reduction processes are still not clearly understood and the environment is mostly in the absence of oxygen. In this study, we ensure that all experiments are performed in an anaerobic glove box, and we elucidate through a combination of macroscopic experimental findings and microscopic characterization that the presence of inorganic phosphates enhances the mineralization of uranyl ions on the surface of S. putrefaciens, while zero-valent iron (ZVI) facilitates the immobilization of uranium by promoting the reduction of uranium by S. putrefaciens. Interestingly, when inorganic phosphates and ZVI co-exist, both the mineralization and reduction of uranium on the bacterial surface are simultaneously enhanced. However, these two substances exhibit a certain degree of antagonism in terms of uranium immobilization by S. putrefaciens. Furthermore, it is found that the influence of pH on the mineralization and reduction of uranyl ions is far more significant than that of inorganic phosphates and ZVI. This study contributes to a better understanding of the environmental fate of uranium in real-world settings and provides valuable theoretical support for the bioremediation and risk assessment of uranium contamination.