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.

Long-term groundwater storage variations estimated in the Songhua River Basin by using GRACE products, land surface models, and in-situ observations.

Influences of climatic change and anthropogenic activities on the terrestrial water storage (TWS) change are significant in the mid- and high-latitude areas. Since 2002, the Gravity Recovery and Climate Experiment (GRACE) satellite mission has provided quantitative measurements of TWS changes with unprecedented accuracy at global, regional and basin scales. In this study, the noise level of various GRACE-derived TWS anomalies (TWSA) data were evaluated by using a generalized three-cornered hat (GTCH) method. A time-dependent weights approach was adopted to obtain a combined TWSA series over the Songhua River Basin (SRB) from 2003 to 2013. Monthly TWSA data during the past decades (1982-2002) were reconstructed by using an artificial neural network (ANN) approach with the good performance evaluated by the correlation coefficient of 0.89 and the Nash-Sutcliff efficiency of 0.79 over the study region. In-situ groundwater level measurements were used for validation of the groundwater storage (GWS) changes (estimated by using GRACE-derived TWS changes in association with the other simulated components of water storage changes from land surface models (LSMs)). The primary driving factors of spatiotemporal variations of GWS, as well as their inter-/intra-annually varying characteristics, were explored. The present study revealed that the variations of GWS featured a "downward fluctuations" (1982-1994), "stable upward" (1998-2008) and "decreasing dramatically" (2009-2013) period, respectively, over the SRB. In general, GWS had varied in a steady decline trend at a decreasing rate of 1.04 ±â€¯0.59 mm year-1 from 1982 to 1994. With the enhanced climatic and anthropogenic influences over the region since 2000, several severe fluctuations characterized the GWS variations with occurrences of spring droughts and flooding over the region, which suggested significant effects of global changes posed on GWS variations of the region.

A multimedia fugacity model to estimate the fate and transport of polycyclic aromatic hydrocarbons (PAHs) in a largely urbanized area, Shanghai, China.

Increasing PAHs pollution is creating more complex urban pollution system. However, the availability of sufficient monitoring activities for PAHs in multicompartment and corresponding multi-interface migration processes is still not well understood. In this study, a Level III steady state fugacity model was validated to evaluate the detailed local variations, and mass fluxes of PAHs in various environmental compartments (i.e., air, soil, sediment, water, vegetation and organic film). This model was applied to a region of Shanghai in 2012 based on a large number of measured data and brings model predictions in 2020. The model results indicate that most of the simulated concentrations agreed with the observed values within one order of magnitude with a tendency of underestimation for vegetation. Direct emission is the main input pathway of PAHs entering the atmosphere, whereas advection is the main outward flow from Shanghai. Organic film was achieved the highest concentration of PAHs compared to other compartments up to 58.17 g/m3. The soil and sediment served as the greatest sinks of PAHs and have the longest retention time (2421.95-78642.09 h). Importantly, a decreasing trend of PAHs was observed in multimedia from 2012 to 2020 and the transfer flux from the air to vegetation to soil was the dominant pathways of BaP intermedia circulation processes. A sensitivity analysis showed that temperature was the most influential parameter, especially for Phe. A Monte Carlo simulation emphasized heavier PAHs were overpredicted in film and sediment, but lighter PAHs in air and water were generally underestimated.

Binding of tea catechins to rice bran protein isolate: Interaction and protective effect during in vitro digestion.

Rice bran protein isolate (RBPI) was prepared from defatted rice bran and used to deliver tea catechins. RBPI had the high adsorption selectivity for tea catechins over caffeine. The adsorption characteristics of tea catechins onto RBPI were determined over a range of time (0-300min), concentration (0.25-3.5gL-1) and temperatures (5°C, 20°C and 35°C). The adsorption kinetic data of EGCg and total catechins (TC) onto RBPI showed excellent fitness with the pseudo-second-order model, indicating that chemisorption is the dominating process. Langmuir and Freundlich models adequately described the isothermal adsorption of tea catechins onto RBPI, and the maximum adsorption of EGCg and TC were achieved at 5°C. SDS-PAGE profiles indicated that globulin and albumin were the major soluble proteins in RBPI to bind tea catechins. Fourier transforms infrared spectroscopy analysis showed that the protein secondary structures of RBPI were altered upon interaction with catechins, with a great increase in random coil and ß-antiparallel, a minor increase in α-helix and a reduction in large loop and turn. Binding tea catechins to RBPI respectively increased the recovery% of EGCg and TC from 10.5% and 17.7% to 29.5% and 31.6% after in vitro intestinal digestion. Thus, RBPI is a promising food matrix for delivering tea catechins to gastrointestinal tract.

[Morphological and cytohistological observations of seed germination and protocorm development of Bletilla striata].

In order to investigate the mechanism of growth for Bletilla striata, which could be applied for rapid propagation, morphological and cytohistological of seed germination and protocorm development in vitro culture were observed using paraffin section techniques. In this study, we have found that the development of B. striata goes through four stages： embryo, protocorm, rhizome and pseudobulb. The end away from embryo suspensor is able to differentiate green buds after the seed of B. striata swelling, growing point. At the same time, the other end of embryo grows many white villous roots, with the green bud differentiating into cotyledon, the embryo breaking through seed coat and being protocorm. The shoot apical meristem of protocorm consists of tunica, corpus and leaf primordium, whose developmental flowing tunica-corpus theory. After more vascular bundle appeared from the leaf primordium, B. striata grows into the stage of rhizome. While in the stage of rhizome, the root primordium of tissue culture seedlings are differentia initially that derived from rhizome vascular bundle, belonging to internal origin. Subsequently, the pseudobulb forms by the inner meristem growing into mature parenchymatous tissue and the rhizome enlargement gradually.

Boron and Nitrogen Codoped Carbon Layers of LiFePO4 Improve the High-Rate Electrochemical Performance for Lithium Ion Batteries.

An evolutionary composite of LiFePO4 with nitrogen and boron codoped carbon layers was prepared by processing hydrothermal-synthesized LiFePO4. This novel codoping method is successfully applied to LiFePO4 for commercial use, and it achieved excellent electrochemical performance. The electrochemical performance can be improved through single nitrogen doping (LiFePO4/C-N) or boron doping (LiFePO4/C-B). When modifying the LiFePO4/C-B with nitrogen (to synthesis LiFePO4/C-B+N) the undesired nonconducting N-B configurations (190.1 and 397.9 eV) are generated. This decreases the electronic conductivity from 2.56×10(-2) to 1.30×10(-2) S cm(-1) resulting in weak electrochemical performance. Nevertheless, using the opposite order to decorate LiFePO4/C-N with boron (to obtain LiFePO4/C-N+B) not only eliminates the nonconducting N-B impurity, but also promotes the conductive C-N (398.3, 400.3, and 401.1 eV) and C-B (189.5 eV) configurations-this markedly improves the electronic conductivity to 1.36×10(-1) S cm(-1). Meanwhile the positive doping strategy leads to synergistic electrochemical activity distinctly compared with single N- or B-doped materials (even much better than their sum capacity at 20 C). Moreover, due to the electron and hole-type carriers donated by nitrogen and boron atoms, the N+B codoped carbon coating tremendously enhances the electrochemical property: at the rate of 20 C, the codoped sample can elevate the discharge capacity of LFP/C from 101.1 mAh g(-1) to 121.6 mAh g(-1), and the codoped product based on commercial LiFePO4/C shows a discharge capacity of 78.4 mAh g(-1) rather than 48.1 mAh g(-1). Nevertheless, the B+N codoped sample decreases the discharge capacity of LFP/C from 101.1 mAh g(-1) to 95.4 mAh g(-1), while the commercial LFP/C changes from 48.1 mAh g(-1) to 40.6 mAh g(-1).

Assessment of water quality and identification of polluted risky regions based on field observations & GIS in the Honghe River watershed, China.

Water quality assessment at the watershed scale requires not only an investigation of water pollution and the recognition of main pollution factors, but also the identification of polluted risky regions resulted in polluted surrounding river sections. To realize this objective, we collected water samplings from 67 sampling sites in the Honghe River watershed of China with Grid GIS method to analyze six parameters including dissolved oxygen (DO), ammonia nitrogen (NH3-N), nitrate nitrogen (NO3-N), nitrite nitrogen (NO2-N), total nitrogen (TN) and total phosphorus (TP). Single factor pollution index and comprehensive pollution index were adopted to explore main water pollutants and evaluate water quality pollution level. Based on two evaluate methods, Geo-statistical analysis and Geographical Information System (GIS) were used to visualize the spatial pollution characteristics and identifying potential polluted risky regions. The results indicated that the general water quality in the watershed has been exposed to various pollutants, in which TP, NO2-N and TN were the main pollutants and seriously exceeded the standard of Category III. The zones of TP, TN, DO, NO2-N and NH3-N pollution covered 99.07%, 62.22%, 59.72%, 37.34% and 13.82% of the watershed respectively, and they were from medium to serious polluted. 83.27% of the watershed in total was polluted by comprehensive pollutants. These conclusions may provide useful and effective information for watershed water pollution control and management.