Nitrogen-doped carbon-coated Cu0 activates molecular oxygen for norfloxacin degradation over a wide pH range.

The Fenton-like activated molecular oxygen technology demonstrates significant potential in the treatment of refractory organic pollutants in wastewater, offering promising development prospects. We prepared a N-doped C-coated copper-based catalyst Cu0/NC3-600 through the pyrolysis of Mel-modified Cu-based metal-organic framework (MOF). The results indicate that the degradation of 20 mg/L norfloxacin (NOR) was achieved using 1.0 g/L Cu0/NC3-600 across a wide pH range, with a removal rate exceeding 95 % and total organic carbon (TOC) removals approaching 70 % after 60 min at pH 5-11. The nitrogen doping enhances the electronic structure of the carbon material, facilitating the adsorption of molecular oxygen. Additionally, the formed carbon layer effectively prevent copper leaching,contributing to increased stability to a certain extent. Subsequently, we propose the catalytic reaction mechanism for the Cu0/NC/air system. Under acidic conditions, Cu0/NC3-600 activates molecular oxygen to produce the •O2-, which serves as the primary active species for NOR degradation. While in alkaline conditions, the high-valent copper species Cu3+ is generated in conjunction with •O2-, both working simultaneously for NOR degradation. Furthermore, based on the LC-MS results, we deduced four possible degradation pathways. This work offers a novel perspective on expanding the pH range of copper-based catalysts with excellent ability to activate molecular oxygen for environmental water treatment.

Mineralization of Few-Layer Graphene Made It Bioavailable in Chlamydomonas reinhardtii.

Numerous studies have emphasized the toxicity of graphene-based nanomaterials to algae, however, the fundamental behavior and processes of graphene in biological hosts, including its transportation, metabolization, and bioavailability, are still not well understood. As photosynthetic organisms, algae are key contributors to carbon fixation and may play an important role in the fate of graphene. This study investigated the biological fate of 14C-labeled few-layer graphene (14C-FLG) in Chlamydomonas reinhardtii (C. reinhardtii). The results showed that 14C-FLG was taken up by C. reinhardtii and then translocated into its chloroplast. Metabolomic analysis revealed that 14C-FLG altered the metabolic profiles (including sugar metabolism, fatty acid, and tricarboxylic acid cycle) of C. reinhardtii, which promoted the photosynthesis of C. reinhardtii and then enhanced their growth. More importantly, the internalized 14C-FLG was metabolized into 14CO2, which was then used to participate in the metabolic processes required for life. Approximately 61.63%, 25.31%, and 13.06% of the total radioactivity (from 14CO2) was detected in carbohydrates, lipids, and proteins of algae, respectively. Overall, these results reveal the role of algae in the fate of graphene and highlight the potential of available graphene in bringing biological effects to algae, which helps to better assess the environmental risks of graphene.

Sparse Actuator Attack Detection and Identification: A Data-Driven Approach.

This article aims to investigate the data-driven attack detection and identification problem for cyber-physical systems under sparse actuator attacks, by developing tools from subspace identification and compressive sensing theories. First, two sparse actuator attack models (additive and multiplicative) are formulated and the definitions of I/O sequence and data models are presented. Then, the attack detector is designed by identifying the stable kernel representation of cyber-physical systems, followed by the security analysis of data-driven attack detection. Moreover, two sparse recovery-based attack identification policies are proposed, with respect to sparse additive and multiplicative actuator attack models. These attack identification policies are realized by the convex optimization methods. Furthermore, the identifiability conditions of the presented identification algorithms are analyzed to evaluate the vulnerability of cyber-physical systems. Finally, the proposed methods are verified by the simulations on a flight vehicle system.

Performance Optimization and Fault-Tolerance of Highly Dynamic Systems Via Q-Learning With an Incrementally Attached Controller Gain System.

High-performance and reliable control of systems that are highly dynamic and open-loop unstable is challenging but of considerable practical interest. Thus, this article investigates the performance optimization and fault tolerance of highly dynamic systems. First, an incremental control structure is proposed, where a controller gain system is attached to the predesigned controller, and by reconfiguring the controller gain system, the performance can be equivalently optimized as configuring the predesigned one. The incremental attachment of the controller gain system does not modify the existing control system, and it can be easily attached via various communication channels. Second, a structure integrating fault-tolerance strategy and hardware redundancy is proposed. Under this structure, command fusion and fault-tolerance strategies are developed where the control commands from different control units are optimally fused, and each control unit can be reconfigured w.r.t. the performance of the other ones. Furthermore, Q -learning algorithms are developed to realize the proposed structures and strategies in real-time model-freely. As such, varying operational conditions of the highly dynamic system can be tackled. Finally, the proposed structures and algorithms are validated case by case to show their effectiveness.

Distribution characteristics of and personal exposure with polycyclic aromatic hydrocarbons and particulate matter in indoor and outdoor air of rural households in Northern China.

Gaseous and particulate polycyclic aromatic hydrocarbons (PAHs) and size-segregated particulate matter (PM) in indoor air and outdoor air, along with personal exposure, were monitored in rural households of Northern China. The daily average concentrations of 28 species were 1310 ±â€¯811, 738 ±â€¯321, 465 ±â€¯247, and 655 ±â€¯250 ng/m3 in kitchen air, bedroom air, and outdoor air, and for personal exposure, respectively. PAHs tended to occur in the particulate phase with increasing molecular weight. Absorption by particulate organic carbon was dominant in the gas-particle partitioning process. The daily averaged concentrations of PM2.5 and PM1.0 were 104 ±â€¯39.5 and 88.4 ±â€¯39.3 µg/m3 in kitchen air, 79.0 ±â€¯63.2 and 65.7 ±â€¯57.5 µg/m3 in bedroom air, 52.9 ±â€¯16.5 and 41.5 ±â€¯12.5 µg/m3 in outdoor air, and 71.7 ±â€¯30.8 and 61.5 ±â€¯28.4 µg/m3 for personal exposure, respectively. The non-priority components contributed 5.5 ±â€¯2.8% to the total PAHs, while their fraction of carcinogenic risk reached 85.6 ±â€¯6.9%. The mean cancer risk posed to rural residents via inhalation exposure to PAHs exceeded the current acceptable threshold of 1.0 × 10-6 and the national average estimated in China. The personal exposure levels of PAHs and PM in households using clean energy were lower than those in households using traditional biomass by 30.0%, 29.4%, and 38.5% for PAH28, PM2.5, and PM1.0, respectively. However, the cancer risk of personal inhalation exposure to PAH28 from using liquid petroleum gas (LPG) was higher than that from using firewood, implying the adoption of LPG may not effectively reduce the cancer risk despite the decreasing exposure levels of PAH28 and PM with respect to the use of firewood. Cooking individuals suffered higher exposure levels of PAH28 and PM1.0 compared with non-cooking individuals, and the cancer risk of personal inhalation exposure to PAH28 for cooking individuals was 1.7 times that for non-cooking individuals. Cooking was a critical factor that affected the personal exposure levels of the local male and female residents.

Occurrence, source, and risk assessment of atmospheric parent polycyclic aromatic hydrocarbons in the coastal cities of the Bohai and Yellow Seas, China.

Parent polycyclic aromatic hydrocarbons (PPAHs) in the ambient air of the coastal cities near the Bohai and Yellow Seas were measured over a full year. The range and geometric average of total PPAH29 (29 species) were 5.16-1.22 × 103 and 118 ng/m3, respectively, with 77 ±â€¯14% in a gaseous phase. The 16 priority components accounted for 90 ±â€¯4% of the total mass concentration. The incremental life cancer risk (ILCR) via inhalation exposure to the PPAHs (3.17 × 10-4) was underestimated by 80%, as only the priority PPAHs were considered. The air concentrations of PPAHs in the Bohai Sea area were generally higher (p < 0.01) than those in the Yellow Sea area. A significant increase (p < 0.01) in the levels of PPAHs and large fractions of high molecular weight (HMW) components were observed in winter. Absorption by particulate organic carbon dominated in gas-particle partitioning of the PPAHs, and the seasonal variations in gas-particle partitioning of the low and moderate molecular weight compounds were more noticeable relative to the HMW species. In summer, significantly higher concentrations of PPAHs were found in the daytime than during nighttime, while the opposite case occurred in winter (p < 0.05). The positive matrix factorization (PMF) results indicated greater contributions of coal and biomass combustion to the PPAH emissions in the coastal cities of the Bohai Sea area compared with the Yellow Sea area. The burning of coal and biomass served as the main source of PPAHs in winter, while traffic exhaust was the dominant source in other seasons. The potential source contribution function (PSCF) revealed the important impacts of the external inputs on the local PPAHs via air mass transport. The contributions of the resolved emission sources to the ILCR were clearly different from those of the mass concentrations, indicating the necessity for source-oriented risk assessments.

Characteristics and human inhalation exposure of ionic per- and polyfluoroalkyl substances (PFASs) in PM10 of cities around the Bohai Sea: Diurnal variation and effects of heating activity.

Atmospheric PM10 (particulate matter with aerodynamic diameter <10 µm) samples were collected in the cities along the Bohai Sea Rim during heating and non-heating periods, and ionic per- and polyfluoroalkyl species (PFASs) in the PM10 were measured. The total concentration of ionic PFASs ranged from 21.8 to 87.0 pg/m3, and the mean concentration of ionic PFASs during the day (42.6 pg/m3) was slightly higher than that at night (35.1 pg/m3). Generally, diurnal variations in the levels of ionic PFASs were consistent with those in the PM10 concentrations. Perfluorooctanoic acid (PFOA, 23.5-33.7%), perfluoropentanoic acid (PFPeA, 28.3-39.9%) and perfluorobutyric acid (PFBA, 17.1-20.1%) accounted for the dominant compositional contributions. Significant positive correlations (p < 0.05) between the main components of PFASs and O3 implied that oxidative degradation (O3 served as the main oxidant) in the period of non-heating may affect the short-chain PFASs. The clustering analysis of a 72-h backward trajectory indicated that cross-provincial transport contributed to ionic PFASs at the sampling sites. Compared with ingestion via daily diet, the inhalation of PM10 exhibited an insignificant contribution to the estimated average daily intakes (ADIs) of PFASs by different age groups. In addition, the calculated hazard ratios (HRs) for the non-cancer respiratory risk, based on the air concentrations of PFOA and perfluorooctane sulfonate (PFOS), also manifested lower non-cancer risk through inhalation exposure. CAPSULE: The effects of heating and non-heating activity and diurnal variation on the concentrations of PFASs, dominated by PFOA, PFPeA, and PFBA in PM10, were determined, and atmospheric trans-provincial input served as an important source.

Characteristics and oxidative potential of atmospheric PM2.5 in Beijing: Source apportionment and seasonal variation.

PM2.5 (particulate matter with the aerodynamic diameter Dp < 2.5 µm) was hypothesized to generate reactive oxygen species (ROS) and induce oxidative stress associated with inflammation and cardiovascular diseases. In the current study, PM2.5 concentrations, water-soluble ions and elements, carbonaceous components and ROS activity characterized by the dithiothreitol (DTT) assay were determined for the PM2.5 samples collected in Beijing, China, over a whole year. Source apportionments of PM2.5 and DTT activity were also performed. The mean ±â€¯standard deviation of PM2.5, DTTm (mass-normalized DTT activity) and DTTv (volume-normalized DTT activity) were 113.8 ±â€¯62.7 µg·m-3, 0.13 ±â€¯0.10 nmol·µg-1·min-1 and 12.26 ±â€¯6.82 nmol·m-3·min-1, respectively. The seasonal averages of DTTm and DTTv exhibited peak values during the local summer. Organic carbon (OC), NO3-, SO42-, NH4+ and elemental carbon (EC) were the dominant components in the constituents tested. Higher concentrations of carbonaceous components occurred in autumn and winter compared with spring and summer. Based on the positive matrix factorization model (PMF), the simulation results of source apportionment for PM2.5 in Beijing, obtained using the annual data, identified the main categories as follows: dust, coal combustion, secondary sulfate and industrial emissions, vehicle emissions and secondary nitrates. Most detected constituents exhibited significantly positive correlations with DTTv (p < 0.01). The results corresponding to multiple linear regression (MLR) between DTTv activity and source contribution to PM2.5 manifested the sensitivity sequence of DTTv activity for the resolved sources as vehicle emissions > secondary sulfate and industrial emissions > coal combustion > dust. CAPSULE: Based on a descending sequence of relative contribution, the diagnostic sources of DTTv activity in PM2.5 from Beijing included primarily vehicle emissions, secondary sulfates and industrial emissions, coal combustion, and dust.

Characteristics of perfluoroalkyl acids in atmospheric PM10 from the coastal cities of the Bohai and Yellow Seas, Northern China.

The concentration distributions, compositional profiles and seasonal variations of 17 perfluoroalkyl acids (PFAAs) in PM10 (particles with aerodynamic diameters < 10 µm) were determined in seven coastal cities of the Bohai and Yellow Seas. The detection rates of perfluorooctanoic acid (PFOA) and short-chain components (perfluoroalkyl carboxylic acids (PFCAs) with ≤7 carbon atoms and perfluoroalkane sulfonic acids (PFSAs) with ≤5 carbon atoms) were much higher than those of other long-chain PFAA species. The annual average concentration of total PFAAs in PM10 ranged from 23.6 pg/m3 to 94.5 pg/m3 for the sampling cities. The monthly mean concentrations of PFAAs in PM10 in some sampling cities reached a peak value in winter, while no significant seasonal differences presented in other cities. High concentrations of PFAAs in the northern cities generally occurred during the local heating period (from November to March). Generally, the dominant components of PFAAs were PFOA and perfluorobutyric acid (PFBA). Some significantly positive correlations (p < 0.01) between the 10 dominant components were revealed in the sampling cities, which implied similar sources and fate behaviors. Based on the simulated 72-hr backward trajectory tracking of air masses, the clustering results demonstrated the sampling cities were affected mainly by the atmospheric transport in sequence from the northwest, the southwest and the open seas, and many transport trajectories of air masses passed by the local fluorine chemical manufacturers in Liaoning, Shandong, Jiangsu, and Hubei Provinces. The estimated average daily intake (ADI) corresponding to the residents in different age groups indicated insignificant contributions to PFOA and perfluorooctane sulfonate (PFOS) exposures by inhalation of PM10 compared to ingestion by daily diet, while the higher ADI of PFOA than the reported levels for adults should be a concern. The calculated hazard ratios (HR) exhibited low noncancer risks by inhalation exposure to PFOA and PFOS in PM10.

Oxidative potential of ambient PM2.5 in the coastal cities of the Bohai Sea, northern China: Seasonal variation and source apportionment.

Emissions of air pollutants from primary and secondary sources in China are considerably higher than those in developed countries, and exposure to air pollution is main risk of public health. Identifying specific particulate matter (PM) compositions and sources are essential for policy makers to propose effective control measures for pollutant emissions. Ambient PM2.5 samples covered a whole year were collected from three coastal cities of the Bohai Sea. Oxidative potential (OP) was selected as the indicator to characterize associated PM compositions and sources most responsible for adverse impacts on human health. Positive matrix factorization (PMF) and multiple linear regression (MLR) were employed to estimate correlations of PM2.5 sources with OP. The volume- and mass-based dithiothreitol (DTTv and DTTm) activities of PM2.5 were significantly higher in local winter or autumn (p < 0.01). Spatial and seasonal variations in DTTv and DTTm were much larger than mass concentrations of PM2.5, indicated specific chemical components are responsible for PM2.5 derived OP. Strong correlations (r > 0.700, p < 0.01) were found between DTT activity and water-soluble organic carbon (WSOC) and some transition metals. Using PMF, source fractions of PM2.5 were resolved as secondary source, traffic source, biomass burning, sea spray and urban dust, industry, coal combustion, and mineral dust. Further quantified by MLR, coal combustion, biomass burning, secondary sources, industry, and traffic source were dominant contributors to the water-soluble DTTv activity. Our results also suggested large differences in seasonal contributions of different sources to DTTv variability. A higher contribution of DTTv was derived from coal combustion during the local heating period. Secondary sources exhibited a greater fraction of DTTv in summer, when there was stronger solar radiation. Traffic sources exhibited a prevailing contribution in summer, and industry contributed larger proportions in spring and winter. Future abatement priority of air pollution should reduce the sources contributing to OP of PM2.5.

[Recent Distribution and Sources of Polycyclic Aromatic Hydrocarbons in Surface Soils from Yangtze River Delta].

A total of 243 surface soil samples collected from 11 cities in the Yangtze River Delta region were analyzed for the concentrations, spatial distribution, component profiles and emission sources of 29 PAH species. The analytical results indicated the total concentrations of PAHs in Yangtze River Delta fell in the range from 21. 0 ng x g(-1) to 3 578.5 ng x g(-1) with an arithmetic mean and standard deviation of 310.6 ng x g(-1) and 459.1 ng x g(-1), respectively. Our data showed spatial distribution of PAHs concentrations varied greatly in the region. In addition, the contents of PAHs were positively correlated with the total organic carbon fractions in topsoil. The sites with the highest levels of PAHs in the 11 cities studied were located in Suzhou with 759.0 ng x g(-1) +/- 132.9 ng x g(-1) ollowed by the areas of Wuxi and Shanghai, with the total PAHs concentrations of 565. 3 ng x g(-1) +/- 705.5 ng x g(-1) and 349.4 ng g(-1) 220. 1 ng-g(-1) respectively. The profiles of different components pointed to a predominant role of the species with 2-4 rings, and especially for the low molecular weight components with 2-3 rings. A preliminary identification on emission sources of local PAHs was performed by the specific ratios of isomeric species and principal component analysis (PCA). The results designated industrial coal and biomass combustion as the main mixed emission sources of PAHs in surface soils from Yangtze River Delta, and tail gas from transport as another major source in some areas.