Unconventional structural evolution of an oxide surface in water unveiled by in situ sum-frequency spectroscopy.

Oxide-water interfaces host a wide range of important reactions in nature and modern industrial applications; however, accurate knowledge about these interfaces is still lacking at the molecular level owing to difficulties in accessing buried oxide surfaces. Here we report an experimental scheme enabling in situ sum-frequency vibrational spectroscopy of oxide surfaces in liquid water. Application to the silica-water interface revealed the emergence of unexpected surface reaction pathways with water. With ab initio molecular dynamics and metadynamics simulations, we uncovered a surface reconstruction, triggered by deprotonation of surface hydroxylated groups, that led to unconventional five-coordinated silicon species. The results help demystify the multimodal chemistry of aqueous silica discovered decades ago, bringing in fresh information that modifies the current understanding. Our study will provide new opportunities for future in-depth physical and chemical characterizations of other oxide-water interfaces.

Impact of microplastics on plant physiology: A meta-analysis of dose, particle size, and crop type interactions in agricultural ecosystems.

The increasing prevalence of plastic pollution has led to widespread environmental concerns, particularly with microplastics (MPs) that persist in various ecosystems. As MPs accumulate in terrestrial environments, their potential impact on plant health and agricultural productivity has become a growing area of focus. This study presents a comprehensive meta-analysis evaluating the effects of MPs on plant physiological and biochemical parameters, synthesizing data from 37 studies comprising 2886 observations. Our findings indicate that MPs significantly decrease plant biomass by 13 % (95 % CI: 7-19 %) and chlorophyll content by 28 % (95 % CI: 23-34 %), impairing crop growth and quality. Notably, higher doses and smaller MP particle sizes exert more pronounced inhibitory effects, particularly on root activity and biomass, while larger MPs predominantly damage plant roots. Furthermore, MPs were found to significantly increase oxidative stress in plants, evidenced by a 20 % rise in oxidative damage (95 % CI: 15-25 %) and a 14 % increase in antioxidant capacity (95 % CI: 8-19 %). This study highlights intricate interactions between MP type, particle size, dose, and plant species, with particle size having a greater impact than dose. This study emphasizes the importance of accounting for crop diversity and environmental factors to fully elucidate the potential risks posed by MP pollution to agricultural ecosystems.

Phytotoxicity of 6PPD and its uptake by Myriophyllum verticillatum: Oxidative stress and metabolic processes.

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), a widely utilized antioxidant in automobile tires and rubber goods, is frequently detected in aquatic ecosystems and poses a potential threat to aquatic organisms. However, research on the impact of 6PPD on aquatic plants is still scarce. Here, we investigated the bioaccumulation of 6PPD in Myriophyllum verticillatum (M. verticillatum) (watermilfoil), and its impacts on biochemical characteristics and metabolomics. 6PPD (10,100 mg/L) significantly inhibited the growth and photosynthetic pigment content of M. verticillatum. After 14 days of exposure to 100 µg/L 6PPD, accumulation levels of 6PPD and its metabolite 6PPDQ in M. verticillatum reached 0.52 mg/kg and 0.09 mg/kg, respectively. Moreover, 6PPD significantly induced the activities of superoxide dismutase (SOD), peroxidase (POD), catalase (CAT) enzymes and glutathione (GSH), reducing the levels of reactive oxygen species (ROS) and malondialdehyde (MDA), thereby mitigating oxidative damage in M. verticillatum. Furthermore, metabolic pathway analysis revealed that 6PPD has remarkable effects on amino acid and sugar metabolism. This study provides data support for understanding the toxic effects of 6PPD on aquatic plants and evaluating its potential risks.

Microplastics regulate soil microbial activities: Evidence from catalase, dehydrogenase, and fluorescein diacetate hydrolase.

Soil microbiomes drive many soil processes and maintain the ecological functions of terrestrial ecosystems. Microplastics (MPs, size < 5 mm) are pervasive emerging contaminants worldwide. However, how MPs affect soil microbial activity has not been well elucidated. This review article first highlights the effects of MPs on overall soil microbial activities represented by three soil enzymes, i.e., catalase, dehydrogenase, and fluorescein diacetate hydrolase (FDAse), and explores the underlying mechanisms and influencing factors. Abundant evidence confirms that MPs can change soil microbial activities. However, existing results vary greatly from inhibition to promotion and non-significance, depending on polymer type, degradability, dose, size, shape, additive, and aging degree of the target MPs, soil physicochemical and biological properties, and exposure conditions, such as exposure time, temperature, and agricultural practices (e.g., planting, fertilization, soil amendment, and pesticide application). MPs can directly affect microbial activities by acting as carbon sources, releasing additives and pollutants, and shaping microbial communities via plastisphere effects. Smaller MPs (e.g., nanoplastics, 1 to < 1000 nm) can also damage microbial cells through penetration. Indirectly, MPs can change soil attributes, fertility, the toxicity of co-existing pollutants, and the performance of soil fauna and plants, thus regulating soil microbiomes and their activities. In conclusion, MPs can regulate soil microbial activities and consequently pose cascading consequences for ecosystem functioning.

Earthworms Enhance Crop Resistance to Insects Under Microplastic Stress by Mobilizing Physical and Chemical Defenses.

To assess the ecological risk of microplastics (MPs) in agricultural systems, it is critical to simultaneously focus on MP-mediated single-organism response and different trophic-level organism interaction. Herein, we placed earthworms in soils contaminated with different concentrations (0.02% and 0.2% w/w) of polyethylene (PE) and polypropylene (PP) MPs to investigate the effect of earthworms on tomato against Helicoverpa armigera (H. armigera) under MPs stress. We found that earthworms alleviated the inhibitory effects of MPs stress on tomato growth and disrupted H. armigera growth. Compared to individual MPs exposure, earthworm incorporation significantly increased the silicon and lignin content in herbivore-damaged tomato leaves by 19.1% and 57.6%, respectively. Metabolites involved in chemical defense (chlorogenic acid) and phytohormones (jasmonic acid) were also activated by earthworm incorporation. Furthermore, earthworms effectively reduced oxidative damage induced by H. armigera via promoting antioxidant metabolism. Overall, our results suggest that utilizing earthworms to regulate above- and below-ground interactions could be a promising strategy for promoting green agriculture.

Orientation-dependent electronic structure in interfacial superconductors LaAlO3/KTaO3.

Emergent superconductivity at the LaAlO3/KTaO3 interfaces exhibits a mysterious dependence on the KTaO3 crystallographic orientations. Here by soft X-ray angle-resolved photoemission spectroscopy, we directly resolve the electronic structure of the LaAlO3/KTaO3 interfacial superconductors and the non-superconducting counterpart. We find that the mobile electrons that contribute to the interfacial superconductivity show strong k⊥ dispersion. Comparing the superconducting and non-superconducting interfaces, the quasi-three-dimensional electron gas with over 5.5 nm spatial distribution ubiquitously exists and shows similar orbital occupations. The signature of electron-phonon coupling is observed and intriguingly dependent on the interfacial orientations. Remarkably, the stronger electron-phonon coupling signature correlates with the higher superconducting transition temperature. Our observations help scrutinize the theories on the orientation-dependent superconductivity and offer a plausible and straightforward explanation. The interfacial orientation effect that can modify the electron-phonon coupling strength over several nanometers sheds light on the applications of oxide interfaces in general.

Comparative toxic effect of tire wear particle-derived compounds 6PPD and 6PPD-quinone to Chlorella vulgaris.

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), a widely used antioxidant in rubber products, and its corresponding ozone photolysis product N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-Q), have raised public concerns due to their environmental toxicity. However, there is an existing knowledge gap on the toxicity of 6PPD and 6PPD-Q to aquatic plants. A model aquatic plant, Chlorella vulgaris (C. vulgaris), was subjected to 6PPD and 6PPD-Q at concentrations of 50, 100, 200, and 400 µg/L to investigate their effects on plant growth, photosynthetic, antioxidant system, and metabolic behavior. The results showed that 6PPD-Q enhanced the photosynthetic efficiency of C. vulgaris, promoting growth of C. vulgaris at low concentrations (50, 100, and 200 µg/L) while inhibiting growth at high concentration (400 µg/L). 6PPD-Q induced more oxidative stress than 6PPD, disrupting cell permeability and mitochondrial membrane potential stability. C. vulgaris responded to contaminant-induced oxidative stress by altering antioxidant enzyme activities and active substance levels. Metabolomics further identified fatty acids as the most significantly altered metabolites following exposure to both contaminants. In conclusion, this study compares the toxicity of 6PPD and 6PPD-Q to C. vulgaris, with 6PPD-Q demonstrating higher toxicity. This study provides valuable insight into the risk assessment of tire wear particles (TWPs) derived chemicals in aquatic habitats and plants.

Environmental concentrations of 6PPD and 6PPD-Q cause oxidative damage and alter metabolism in Eichhornia crassipes.

N-(1,3-dimethylbutyl)-N '-phenyl-p-phenylenediamine (6PPD) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-Q) are ubiquitous in the environment and can cause toxicity to aquatic animals. However, research on the toxicological effects of 6PPD and 6PPD-Q on aquatic plants remains limited. The present study investigated the physiological, biochemical, and metabolic responses of the floating aquatic plant Eichhornia crassipes (E. crassipes) to environmentally relevant concentrations (0.1, 1, and 10 µg·L-1) of 6PPD and 6PPD-Q. We found that 6PPD and 6PPD-Q elicited minimal effects on plant growth, but 6PPD induced a concentration-dependent decrease in the content of photosynthetic pigments. Low doses (0.1 µg·L-1 and 1 µg·L-1) of 6PPD-Q significantly elevated Reactive Oxygen Species (ROS) content in E. crassipes roots, indicating oxidative damage. Furthermore, 6PPD-Q induced a more pronounced osmotic stress compared to 6PPD. Metabolic analyses revealed that carbohydrates were significantly altered under 6PPD and 6PPD-Q treatments. The findings of this study enhance the understanding of the environmental risks posed by 6PPD and 6PPD-Q to plants and reveal the potential mechanisms of phytotoxicity.

Biodegradable Microplastic-Driven Change in Soil pH Affects Soybean Rhizosphere Microbial N Transformation Processes.

The potential impacts of biodegradable and nonbiodegradable microplastics (MPs) on rhizosphere microbial nitrogen (N) transformation processes remain ambiguous. Here, we systematically investigated how biodegradable (polybutylene succinate, PBS) MPs and nonbiodegradable (polyethylene, PE) MPs affect microbial N processes by determining rhizosphere soil indicators of typical Glycine max (soybean)-soil (i.e., red and brown soils) systems. Our results show that MPs altered soil pH and dissolved organic carbon in MP/soil type-dependent manners. Notably, soybean growth displayed greater sensitivity to 1% (w/w) PBS MP exposure in red soil than that in brown soil since 1% PBS acidified the red soil and impeded nutrient uptake by plants. In the rhizosphere, 1% PBS negatively impacted microbial community composition and diversity, weakened microbial N processes (mainly denitrification and ammonification), and disrupted rhizosphere metabolism. Overall, it is suggested that biodegradable MPs, compared to nonbiodegradable MPs, can more significantly influence the ecological function of the plant-soil system.

Burden of gout among different WHO regions, 1990-2019: estimates from the global burden of disease study.

The global incidence of gout has increased rapidly, likely secondary to the increase in the prevalence of conditions that predispose to gout, such as obesity. Depending on the population studied, the prevalence of gout ranges from less than 1 to 6.8%. Thus, gout can be a significant burden on healthcare systems. The objective of this study is to observe the trends in the incidence, prevalence, and disability-adjusted life years (DALYs) of gout between 1990 and 2019 globally and in the European Union (EU) 15+ nations. We extracted data from the Global Burden of Disease Study database based on the International Classification of Diseases (ICD) versions 10 and 9. Incidence, prevalence, and disability-adjusted life years (DALYs) were extracted for individual EU15+ countries and globally in males and females between 1990 and 2019. Joinpoint regression analysis was used to describe trends. Between 1990 and 2019, gout prevalence, incidence, and DALYs increased in both males (+ 21.42%, + 16.87%, + 21.49%, respectively) and females (+ 21.06%, + 18.75%, + 20.66%, respectively) globally. The United States of America had the highest increase in prevalence (males: + 90.6%; females + 47.1%), incidence (males: + 63.73%; females: + 39.11%) and DALYs (males: + 90.43%; females: + 42.75%). Incidence, prevalence, and DALYs from gout are increasing worldwide and in most of the EU15+ countries for males and females. Studies have reported the association of gout with comorbidities such as metabolic syndrome, diabetes mellitus, and cardiovascular disease. Health policies and resource allocation are required to increase awareness and modify risk factors globally.

Effects of deep coal mining on groundwater hydrodynamic and hydrochemical processes in a multi-aquifer system: Insights from a long-term study of mining areas in ecologically fragile western China.

The groundwater hydrodynamic and hydrochemical process of the multi-aquifer system will experience complicated and serious influence under deep coal mining disturbance. There is relatively little research that has integrated hydrodynamic and hydrochemical properties of groundwater to investigate the spatiotemporal distribution characteristics and evolution patterns of hydrogeochemistry and hydrodynamic information in deep multi-aquifer systems. The study of the groundwater hydrodynamic and hydrochemical spatiotemporal coupling response of multi-aquifer systems under the deep and special thick coal seam mining-motivated effect in ecologically fragile western mining areas is of great significance for the safe mining of coal resources and ecological environment protection. In this research, the hydrochemical analysis data composed of 218 groundwater samples from Tangjiahui coalfield, Northwest China with 1526 measurements and a 6-year (2016-2021) sampling period were collected for studying the hydrogeochemical spatiotemporal evolution process and governing mechanism of the multi-aquifer system using hierarchical cluster analysis, ion-ratio method, saturation index and multidimensional statistical analysis. Additionally, wavelet analysis and cross-wavelet coherence analysis were implemented to quantitatively recognize the spatiotemporal variation characteristics of hydrodynamic information and analyze the coherence relationships between time series. The results demonstrate that the hydrochemical characteristics exhibit significant spatial differences, while the temporal variation of hydrochemical characteristics in the Permian Shanxi Formation fractured sandstone aquifer (PSFFA), mine water (MW), and Ordovician karst limestone aquifer (OKA) is not significant. The water-rock interaction is the predominant control mechanism for the spatial evolution of hydrogeochemistry in the research area. Moreover, the large-scale mining of deep coal seams controls the type and degree of water-rock interactions by damaging the structure of aquifers and altering the hydrodynamic conditions of groundwater. The period from 2016 to 2021 exhibits multi-time scale characteristics in time series of precipitation, mine water discharge, and the water level of PSFFA and OKA. The mine water discharge has a positive correlation with the water level of PSFFA and OKA, whereas the significant period of precipitation and the water level of PSFFA coherence is not obvious. The research findings not only provide in-depth insights to protect the groundwater resources in water-shortage mining areas but also promote the secure mining of deep coal resources.

Does a "Western Lifestyle" Confer a Higher Burden of Colorectal Cancer? A Comparison of EU15+ Countries versus Global Trends between 1990 and 2019.

The incidence of colorectal cancer (CRC) in the U.S. is declining in adults 50 years and older; however, recent studies suggest an increasing disease burden among adults under age 50. This study aims to compare the incidence, mortality, and mortality-to-incidence ratios (MIRs) of CRC in EU15+ countries to determine if similar age-stratified occurrences are observed across these countries with similar "Western lifestyle"-related risk factors. Incidence and mortality rates for CRC between 1990 and 2019 were extracted using the Global Burden of Disease database. The data were age-stratified into groups between ages 25-49, 50-69, and greater than 69 years. We observed that the incidence of CRC increased globally for all age groups, with the highest increase observed for males (75.9%) and females (27.7%) aged 25-49. A similar trend was observed in 15 of the 19 EU15+ countries for males and 16 of the 19 EU15+ countries for females aged 25-49. Global mortality rates decreased for all age groups in females but increased for males in all age groups. This raises concerns regarding potentially modifiable risk factors contributing to increased CRC development and underscores the importance of implementing standardized screening at an earlier stage to ensure adequate detection in the younger population.

Nonlinear optical signatures of topological Dirac fermion.

Dirac fermion in topological materials exhibits intriguing nonlinear optical responses. However, their direct correlation with the linearly dispersed band remains elusive experimentally. Here, we take topological semimetal ZrSiS as a paradigm, unveiling three unique nonlinear optical signatures of Dirac fermion. These signatures include strong quadrupolar response, quantum interference effect, and exponential divergent four-wave mixing (FWM), all of which are described by the prominent third-order nonlinear optical susceptibility. Resonantly enhanced by linear bands, quadrupolar second harmonic generation in centrosymmetric bulk overwhelms the electric-dipole contribution at the surface with inherent inversion symmetry breaking. Furthermore, owing to the interference between multiple resonant transition pathways within linear bands, difference-frequency FWM is several orders of magnitude stronger than sum-frequency FWM and third harmonic generation. The difference-frequency FWM further displays an inverse-square divergence toward degenerate excitation, whose scaling law perfectly matches with the long-sought behavior of Dirac fermion. These signatures lay the solid foundation toward the practical applications of topological materials in nonlinear optoelectronics and photonics.

Cu-optimized long-range interaction between Co nanoparticles and Co single atoms: Improved Fenton-like reaction activity.

The interplay between multi-atom assembly configurations and single atoms (SAs) has been gaining attention in research. However, the effect of long-term range interactions between SAs and multi-atom assemblies on the orbital filling characteristics has yet to be investigated. In this context, we introduced copper (Cu) doping to strengthen the interaction between cobalt (Co) nanoparticles (NPs) and Co SAs by promoting the spontaneous formation of Co-Cu alloy NPs that tends toward aggregation owing to its negative cohesive energy (-0.06454), instead of forming Cu SAs. The incorporation of Cu within the Co-Cu alloy NPs, compared to the pure Co NPs, significantly expedites the kinetics of peroxymonosulfate (PMS) oxidation processes on Co SAs. Unlike Co NPs, Co-Cu NPs facilitate electron rearrangement in the d orbitals (especially dz2 and dxz) near the Fermi level in Co SAs, thereby optimizing the dz2-O (PMS) and dxz-O (SO5-) orbital interaction. Eventually, the Co-Cu alloy NPs embedded in nitrogen-doped carbon (CC@CNC) catalysts rapidly eliminated 80.67% of 20 mg L-1 carbamazepine (CBZ) within 5 min. This performance significantly surpasses that of catalysts consisting solely of Co NPs in a similar matrix (C@CNC), which achieved a 58.99% reduction in 5 min. The quasi in situ characterization suggested that PMS acts as an electron donor and will transfer electrons to Co SAs, generating 1O2 for contaminant abatement. This study offers valuable insights into the mechanisms by which composite active sites formed through multi-atom assembly interact at the atomic orbital level to achieve high-efficiency PMS-based advanced oxidation processes at the atomic orbital level.

Earthworms improve the rhizosphere micro-environment to mitigate the toxicity of microplastics to tomato (Solanum lycopersicum).

Microplastics (MPs) are widespread in agricultural soil, potentially threatening soil environmental quality and plant growth. However, toxicological research on MPs has mainly been limited to individual components (such as plants, microbes, and animals), without considering their interactions. Here, we examined earthworm-mediated effects on tomato growth and the rhizosphere micro-environment under MPs contamination. Earthworms (Eisenia fetida) mitigated the growth-inhibiting effect of MPs on tomato plant. Particularly, when exposed to environmentally relevant concentrations (ERC, 0.02% w/w) of MPs, the addition of earthworms significantly (p < 0.05) increased shoot and root dry weight by 12-13% and 13-14%, respectively. MPs significantly reduced (p < 0.05) soil ammonium (NH4+-N) (0.55-0.69 mg/kg), nitrate nitrogen (NO3--N) (7.02-8.65 mg/kg) contents, and N cycle related enzyme activities (33.47-42.39 µg/h/g) by 37.7-50.9%, 22.6-37.2%, and 34.2-48.0%, respectively, while earthworms significantly enhanced (p < 0.05) inorganic N mineralization and bioavailability. Furthermore, earthworms increased bacterial network complexity, thereby enhancing the robustness of the bacterial system to resist soil MPs stress. Meanwhile, partial least squares modelling showed that earthworms significantly influenced (p < 0.01) soil nutrients, which in turn significantly affected (p < 0.01) plant growth. Therefore, the comprehensive consideration of soil ecological composition is important for assessing MPs ecological risk.

Robust bistatic ghost imaging with no physical synchronization.

Ghost imaging (GI) requires each echo from the object being correctly matched with the corresponding illuminiation pattern. We proposed a way for such matching with no physical synchronization towards bistatic configuration. The illumination is dually encoded in spatial and time domain. With aperiodic waveform and progressive correlation, the echoes can be correctly located and images can be obtained. In the experiments, our scheme is verified under different levels of signal to noise ratios, as well as different intensity of crosstalk. Ghost imaging with two transmitters and one receiver is also demonstrated. With our method, it is also possible to improve the imaging speed with multiple sources.

Thromboprophylaxis for outpatients with COVID-19: a Systematic Review and Meta-analysis.

Patients with COVID-19 develop an increased risk of thromboembolism. Thromboprophylaxis is recommended for hospitalized COVID-19 patients, but the role of thromboprophylaxis in outpatients with COVID-19 is less well defined. We conducted a systematic review and meta-analysis to evaluate the safety and efficacy of thromboprophylaxis among outpatients with COVID-19. We searched PubMed, Embase, Cochrane Central Register of Controlled Trials, Web of Science, and Scopus from inception to August 2023. The outcomes of interest were venous thromboembolic events including deep venous thrombosis and pulmonary embolism, all-cause mortality, cardiovascular events, hospitalization, major bleeding events, and non-major bleeding events. We included 6 trials comprising 3352 patients. Patients who received thromboprophylaxis had an approximately 70% reduction in venous thromboembolism (RR, 0.28 [95% CI, 0.08 to 0.93]) compared to patients who did not receive thromboprophylaxis. The risk of mortality (RR, 0.79 [95% CI, 0.35 to 1.77]), cardiovascular events (RR, 0.91 [95% CI, 0.30 to 2.73]), and hospitalization (RR, 1.09 [95% CI, 0.81 to 1.47]) were similar between the two groups. Patients who received thromboprophylaxis had a higher risk of non-major bleeding (RR, 3.48 [95% CI, 1.72 to 7.05) compared to patients who did not receive thromboprophylaxis. Thromboprophylaxis reduced the risk of venous thromboembolism but not mortality, cardiovascular events, or hospitalization among outpatients with COVID-19.

Contrast-enhanced phase-resolved second harmonic generation microscopy.

The characterization of inverted structures (crystallographic, ferroelectric, or magnetic domains) is crucial in the development and application of novel multi-state devices. However, determining these inverted structures needs a sensitive probe capable of revealing their phase correlation. Here a contrast-enhanced phase-resolved second harmonic generation (SHG) microscopy is presented, which utilizes a phase-tunable Soleil-Babinet compensator and the interference between the SHG fields from the inverted structures and a homogeneous reference. By this means, such inverted structures are correlated through the π-phase difference of SHG, and the phase difference is ultimately converted into the intensity contrast. As a demonstration, we have applied this microscopy in two scenarios to determine the inverted crystallographic domains in two-dimensional van der Waals material MoS2. Our method is particularly suitable for applying in vacuum and cryogenic environments while providing optical diffraction-limited resolution and arbitrarily adjustable contrast. Without loss of generality, this contrast-enhanced phase-resolved SHG microscopy can also be used to resolve other non-centrosymmetric inverted structures, e.g. ferroelectric, magnetic, or multiferroic phases.

Determinants of consumer intention to adopt a self-service technology strategy for last-mile delivery in Guangzhou, China.

Self-service technology (SST) is a logistic innovation in e-commerce that enhances last-mile delivery efficiency in supply chain management. By combining Innovation Diffusion Theory with Resource Matching Theory, we proposed a comprehensive framework to explain the relationships between beliefs, attitude, and intention in Guanzhou, China. The findings revealed that attitude played a crucial role in influencing consumer intention to adopt SST and that attitude has direct and indirect effects. Additionally, consumer perceptions of compatibility, relative advantage, reliability, and complexity indirectly affected their adoption intention through attitude. These factors had positive and negative effects. The results highlighted the importance of attitudes as immediate predictors of intention, as consumer attitudes (favorable and unfavorable) were shaped by their perceptions. We conclude by recommending strategies to promote positive attitudes toward SST and enhance safety, efficiency, and the overall user experience.