Spatiotemporal distribution and inter-media transfer of polycyclic aromatic hydrocarbons in Shanghai, China: Historical patterns and future trends.

Polycyclic Aromatic Hydrocarbons (PAHs) represent pervasive pollutants, posing health risks in urban environments. It is essential to comprehend the spatiotemporal distributions, composition profiles, and inter-media transfer processes of PAHs in various environmental compartments, influenced by both natural changes and anthropogenic activities. This study integrates historical and future spatiotemporally changing environmental parameters, including climate data, GDP, population data, land-use types, and hydrological variables, into the Multimedia Urban Model (MUM). This integration enables the simulation of spatiotemporal distributions and inter-media transfer fluxes of PAHs among six different media from the 2010s to the 2100s under two distinct Shared Socio-economic Pathways (SSP) scenarios in the megacity of Shanghai, China. The MUM model, featuring diverse gridded parameters, effectively captures PAH concentrations and movement across environmental compartments. Results indicate a decreasing trend in PAHs concentrations in the 2100s compared to the 2010s, with PAH concentrations in water, sediment, vegetation, and organic film covering impermeable surfaces under the SSP3-7.0 scenario higher than those of the SSP1-2.6 scenario. Low molecular weight PAHs dominate in the sediment, water, and air, whereas high molecular weight PAHs prevail in the organic film, vegetation, and soil. Sediment and soil serve as the predominant sinks for PAHs. The primary transport processes for PAH movement include air-film, air-soil, film-water, soil-air, and water-air. Almost all transfer fluxes exhibit a declining trend in future periods except for the air-film transport pathway. The principal input and removal routes for PAHs in Shanghai involve the advection of air and water. The study provides essential insights into the environmental behavior of PAHs and informs targeted pollution control in Shanghai. Additionally, it serves as a technical reference for similar pollution prediction research.

A Proline-Based Artificial Enzyme That Favors Aldol Condensation Enables Facile Synthesis of Aliphatic Ketones via Tandem Catalysis.

A proline-based artificial enzyme is prepared by grafting the l-proline moieties onto the surface of bovine serum albumin (BSA) protein through atom transfer radical polymerization (ATRP). The artificial enzyme, the BSA-PolyProline conjugate, prefers to catalyze the formation of unsaturated ketones rather than ß-hydroxy ketones in the reaction between acetone and aldehydes, which is difficult to achieve in free-proline catalysis. The altered reaction selectivity is ascribed to the locally concentrated l-proline moieties surrounding the BSA molecule, indicating a microenvironmental effect-induced switching of the reaction mechanism. Taking advantage of this selectivity, we used this artificial enzyme in conjunction with a natural enzyme, old yellow enzyme 1 (OYE1), to demonstrate a simple synthesis of different aliphatic ketones from acetone and aldehydes via tandem catalysis.

Environmental fate and health risks of polycyclic aromatic hydrocarbons in the Yangtze River Delta Urban Agglomeration during the 21st century.

Understanding the spatiotemporal distribution and behavior of Polycyclic Aromatic Hydrocarbons (PAHs) in the context of climate change and human activities is essential for effective environmental management and public health protection. This study utilized an integrated simulation system that combines land-use, hydrological, and multimedia fugacity models to predict the concentrations, transportation, and degradation of 16 priority-controlled PAHs across six environmental compartments (air, water, soil, sediment, vegetation, and impermeable surfaces) within one of the world's prominent urban agglomerations, the Yangtze River Delta Urban Agglomeration (YRDUA), under future Shared Socio-economic Pathways (SSP)-Representative Concentration Pathways (RCP) scenarios. Incremental lifetime carcinogenic risk for adults and children exposed to PAHs were also evaluated. The results show a declining trend in PAHs concentrations and associated health risks during the 21st century. Land use types, hydrological characteristics, population, and GDP, have significant correlations with the fate of PAHs. The primary removal for PAHs is determined to be driven by advection through air and water. PAHs covering on impermeable surfaces pose a relatively higher health risk compared to those in other environmental media. This study offers valuable insights into PAHs pollution in the YRDUA, aiming to ensure public health safety, with the potential for application in other urban areas.

Smart enzyme catalysts capable of self-separation by sensing the reaction extent.

A smart biocatalyst should dissolve homogeneously for catalysis and recover spontaneously at the end of the reaction. In this study, we present a strategy for preparing self-precipitating enzyme catalysts by exploiting reaction-induced pH decreases, which connect the reaction extent to the catalyst aggregation state. Using poly(methacrylic acid)-functionalized gold nanoparticles as carriers, we construct smart catalysts with three model systems, including the glucose oxidase (GOx)-catalase (CAT) cascade, the alcohol dehydrogenase (ADH)-glucose dehydrogenase (GDH) cascade, and a combination of two lipases. All smart catalysts can self-separate with a nearly 100% recovery efficiency when a certain conversion threshold is reached. The threshold can be adjusted depending on the reaction demand and buffer capacity. By monitoring the optical signals caused by the dissolution/precipitation of smart catalysts, we propose a prototypic automation system that may enable unsupervised batch/fed-batch bioprocessing.

Analog soil organo-ferrihydrite composites as suitable amendments for cadmium and arsenic stabilization in co-contaminated soils.

Remediation of CdAs co-contaminated soils has long been considered a difficult problem to solve, as Cd and As have distinctly different metallic characters. Amending contaminated soils with traditional single passivation materials may not always work well in the stabilization of both Cd and As. Here, we reported that analog soil organo-ferrihydrite composites made with either living or non-living organics (bacterial cells or humic acid) could achieve stabilization of both Cd and As in contaminated soils. BCR and Wenzel sequential extractions showed that organo-ferrihydrite, particularly at 1 wt% loading, shifted liable Cd and As to more stable phases. Organo-ferrihydrite amendments significantly (p < 0.05) increased soil urease, alkaline phosphatase and catalase enzyme activities. With organo-ferrihydrite amendments, the bioavailable fraction of Cd decreased to 35.3 % compared with the control (65.1 %), while the bioavailable As declined from 29.4 % to 12.4%. Soil pH, microbial community abundance and diversity were almost unaffected by organo-ferrihydrite. Ferrihydrite and organo fractions both contributed to direct Cd-binding, while the organo fraction probably maintained the Fe-bound As via lowering ferrihydrite phase transformation. Compared to pure ferrihydrite, organo-ferrihydrite composites performed better not only in reducing liable Cd and As, but also in maintaining soil quality and ecosystem functions. This study demonstrates the applications of organo-ferrihydrite composites in eco-friendly remediation of CdAs contaminated soils, and provides a new direction in selecting appropriate soil amendments.

Impact of preparation method on nickel speciation and methane dry reforming performance of Ni/SiO2 catalysts.

The methane dry reforming reaction can simultaneously convert two greenhouse gases (CH4 and CO2), which has significantly environmental and economic benefits. Nickel-based catalysts have been widely used in methane dry reforming in past decade due to their low cost and high activity. However, the sintering and coke deposition of catalysts severely limit their industrial applications. In this paper, three Ni/SiO2 catalysts prepared by different methods were systematically studied, and the samples obtained by the ammonia evaporation method exhibited excellent catalytic performance. The characterization results such as H2-TPR, XPS and TEM confirmed that the excellent performance was mainly attributed to the catalyst with smaller Ni particles, stronger metal-support interactions, and abundant Ni-O-Si units on the catalyst surface. The anti-sintering/-coking properties of the catalyst were significantly improved. However, the Ni/SiO2-IM catalyst prepared by impregnation method had uneven distribution of nickel species and large particles, and weak metal-support interactions, showing poor catalytic performance in methane dry reforming. Since the nickel species were encapsulated by the SiO4 tetrahedral network, the Ni/SiO2-SG catalyst prepared by sol-gel method could not expose more effective active sites even if the nickel species were uniformly dispersed, resulting in poor dry reforming performance. This study provides guidance for the preparation of novel anti-sintering/-coking nickel-based catalysts.

Amplified oxidative stress therapy by a degradable copper phosphate nanozyme coated by the in situ polymerization of PEGDA.

The elimination of reactive oxygen species (ROS) caused by glutathione (GSH) is a fundamental concern in the oxidative stress therapy (OST) of tumors. This is the first report of copper phosphate nanospheres coated by poly (ethylene glycol) diacrylate (Cu3(PO4)2@PEGDA) which act as nanozymes to amplify the anti-tumor effects of OST. Cu3(PO4)2@PEGDA not only catalyzes the generation of ˙OH from H2O2 but also consumes GSH, which is counterproductive to the role of ˙OH. Moreover, the photothermal properties of Cu3(PO4)2@PEGDA further enhances the outcome of the OST when exposed to an 808 nm laser. Another novelty lies in that a new PEGylation strategy of peroxidase-like nanozymes is proposed, in which the Cu3(PO4)2 cores work as internal heaters and radical generators, which are necessary to initiate the radical polymerization of PEGDA. An elaborate core-shell nanostructure is obtained since the polymerization prefers to take place in the vicinity of the cores, overcoming the drawbacks of traditional PEGylation methods which include invalid polymerization far away from the cores and easy core-shell disassembly during applications.

Ferrihydrite-organo composites are a suitable analog for predicting Cd(II)-As(V) coexistence behaviors at the soil solid-liquid interfaces.

Organomineral assemblages are building units of soil micro-aggregates and exert their essential roles in immobilizing toxic elements. Currently, our knowledge of the adsorption and partitioning behaviors of coexisting Cd-As onto organomineral composites is limited. Herein, we carefully studied Cd-As cosorption onto ferrihydrite organomineral composites made with either living or non-living organics, i.e., bacteria (Delftia sp.) or humic acid (HA), using batch adsorption and various spectroscopies. Batch results show that As(V) only enhances Cd(II) sorption on pure Fh at pH < 6 but cannot promote Cd(II) sorption to Fh-organo composites. However, Cd(II) noticeably promotes As(V) sorption at pH>~5-6. Synchrotron micro X-ray fluorescence indicates that Cd(II) adsorbs predominately to the bacterial fraction (Cd versus P, r = 0.924), whereas As(V) binds mainly to the Fh fraction (As versus Fe, r = 0.844) of the Fh-bacteria composite. On Fh-HA composite, however, Cd(II) and As(V) are both primarily sorbed by the Fh fraction (Cd/As versus P, r > 0.8), based on the scanning transmission electron microscopy-energy disperse spectroscopy analyses. Elemental distribution characterization also manifests the co-localization of Cd(II) and As(V) within the organomineral composite, particular in Fh-HA composite (Cd versus As, r = 0.8), which is further identified as the Fh-As-Cd ternary complex based on the observations (higher frequencies at ~753-761 cm-1) of attenuated total reflection Fourier-transform infrared spectroscopy. Moreover, this ternary interaction is more pronounced in Fh-HA than in Fh-bacteria. In summary, our results suggest that Cd-As coadsorption behaviors on Fh-organo composites are different from those on pure minerals, and the presence of bacteria/HA can significantly affect metal (loid)s speciation, distribution, and ternary interaction. Therefore organomineral composites are a more suitable analog than pure mineral phases to predict the mobility and fate of Cd-As in natural environments.

Effective Antibacterial Activity of Degradable Copper-Doped Phosphate-Based Glass Nanozymes.

Copper-containing antimicrobials are highly valuable in the field of medical disinfectants owing to their well-known high antimicrobial efficacy. Artificially synthesized nanozymes which can increase the level of reactive oxygen species (ROS) in the bacterial system have become research hotspots. Herein, we describe the design and fabrication of degradable Cu-doped phosphate-based glass (Cu-PBG) nanozyme, which can achieve excellent antibacterial effects against Gram-positive and Gram-negative bacteria. The antibacterial mechanism is based on the generation of ROS storm and the release of copper. It behaves like a peroxidase in wounds which are acidic and exerts lethal oxidative stress on bacteria via catalyzing the decomposition of H2O2 into hydroxyl radicals (•OH). Quite different from any other reported nanozymes, the Cu-PBG is intrinsically degradable due to its phosphate glass nature. It gradually degrades and releases copper ions in a physiological environment, which further enhances the inhibition efficiency. Satisfactory antibacterial effects are verified both in vitro and in vivo. Being biodegradable, the prepared Cu-PBG exhibits excellent in vivo biocompatibility and does not cause any adverse effects caused by its long-time residence time in living organisms. Collectively, these results indicate that the Cu-PBG nanozyme could be used as an efficient copper-containing antimicrobial with great potential for clinical translation.

Large left paraduodenal hernia with intestinal ischemia: a case report and literature review.

A left paraduodenal hernia is a rare type of internal hernia but the most common type of peritoneal recess hernia. Preoperative diagnosis of a left paraduodenal hernia is difficult because of its nonspecific clinical manifestations, and it is often confused with other causes of acute abdomen. Diagnosis is therefore often delayed, resulting in serious clinical outcomes. We herein report a case of a large paraduodenal hernia with small intestinal obstruction and ischemia without abdominal pain. The patient was successfully discharged after emergency hernia repair. This case reveals the importance of diagnosing a left paraduodenal hernia with or without abdominal pain, especially in patients with no history of abdominal surgery.