Variation of Chemical Microenvironment of Pores in Hydrazone-Linked Covalent Organic Frameworks for Photosynthesis of H2O2.

Photocatalytic synthesis of H2O2 is an advantageous and ecologically sustainable alternative to the conventional anthraquinone process. However, achieving high conversion efficiency without sacrificial agents remains a challenge. In this study, two covalent organic frameworks (COF-O and COF-C) were prepared with identical skeletal structures but with their pore walls anchored to different alkyl chains. They were used to investigate the effect of the chemical microenvironment of pores on photocatalytic H2O2 production. Experimental results reveal a change of hydrophilicity in COF-O, leading to suppressed charge recombination, diminished charge transfer resistance, and accelerated interfacial electron transfer. An apparent quantum yield as high as 10.3% (λ = 420 nm) can be achieved with H2O and O2 through oxygen reduction reaction. This is among the highest ever reported for polymer photocatalysts. This study may provide a novel avenue for optimizing photocatalytic activity and selectivity in H2O2 generation.

Charge redistribution of a spatially differentiated ferroelectric Bi4Ti3O12 single crystal for photocatalytic overall water splitting.

Artificial photosynthesis is a promising approach to produce clean fuels via renewable solar energy. However, it is practically constrained by two issues of slow photogenerated carrier migration and rapid electron/hole recombination. It is also a challenge to achieve a 2:1 ratio of H2 and O2 for overall water splitting. Here we report a rational design of spatially differentiated two-dimensional Bi4Ti3O12 nanosheets to enhance overall water splitting. Such a spatially differentiated structure overcomes the limitation of charge transfer across different crystal planes in a single crystal semiconductor. The experimental results show a redistribution of charge within a crystal plane. The resulting photocatalyst produces 40.3 µmol h-1 of hydrogen and 20.1 µmol h-1 of oxygen at a near stoichiometric ratio of 2:1 and a solar-to-hydrogen efficiency of 0.1% under simulated solar light.

Ecological risk assessment of microplastics and mesoplastics in six common fishes from the Bay of Bengal Coast.

Plastic particles have emerged as a growing threat to both ecosystems and human well-being, as they are being ingested and accumulate at different trophic levels. However, microplastic and mesoplastic contamination and its risk to coastal and marine water fish have not been well studied, particularly in the northern Bay of Bengal. In this study, the presence of small-scale plastic particles (micro- and meso-sized) in the gastrointestinal tract (GIT) and muscles of six edible fish species from the northern Bay of Bengal Coast were identified and analyzed. The overall range of microplastics was 1.74 ± 0.23-3.79 ± 2.03items/g in muscle and 0.54 ± 0.22-5.96 ± 3.16 items/g in the GIT, with 16.38 ± 8.08-31.88 ± 12.09 items/individual. No mesoplastics were found in muscle tissue, but they were present in the GIT at concentrations ranging from 0.33 ± 0.27 to 0.03 ± 0.02 items/g and from 0.51 ± 0.05to 1.38 ± 1.01 items/individual. Lepturacanthus savala accumulated the most microplastics in muscle, and Harpadon nehereus had the least. In addition, the highest levels of mesoplastics were detected in the GIT of Polynemus paradiseus and the lowest was detected in the GIT of Lutjenus sanguineus. Omnivorous fish showed higher plastic concentrations than carnivorous fish, which was linked to dietary habits, feeding strategies and digestive processes. Plastic material predominantly accumulated in the GIT rather than in the muscle. The majority of ingested plastic particles were fibres (95.18 %), were violet in color (34 %), and were < 0.5 mm in size (87 %). The dominant microplastic polymers included 38 % PE, 15 % PP, 33 % PU, and 14 % CES. In contrast, the prevalent mesoplastic polymers comprised 45 % PE, 19 % PP, 13 % PS, 16 % PA, and 7 % PET. Subsequently, a hazard analysis using the polymer hazard index (PHI) revealed that plastic contamination was of distinct hazard categories for different polymer types, ranging from grade I (<1) to grade IV (100-1000). The assessment of the contamination factor (1 < CF < 3) and pollution load index (PLI > 1) indicated moderate contamination of fish by the ingestion of plastic debris. This study provides the foremost evidence for the presence of mesoplastics and microplastics in coastal and marine fish in the study region, paving the way for future investigations and policy implementation.

Heavy metals in afforested mangrove sediment from the world's largest delta: Distributional mapping, contamination status, risk assessment and source tracing.

This study aims to assess seasonal and spatial variations, contamination status, ecological risks, and metal sources (Ni, Pb, Cr, Cu, Mn, and Zn) in human-afforested mangrove sediments in a deltaic region. Five sampling locations were sampled during dry and wet seasons. Heavy metal concentrations followed the order: Mn > Zn > Ni > Cr > Cu > Pb. Metal loads, except Cu and Pb, were higher during the dry season, aligning with national and international recommendations. Sediment quality guidelines, contamination factor, geoaccumulation index, enrichment factors, and pollution load index indicated uncontaminated sediment in both seasons. Potential ecological risk assessment showed low risk conditions in all sites. However, modified hazard quotient indicated moderate pollution risk from all metals except Pb. Analysis suggests anthropogenic sources, particularly evident near shipbreaking yards in Sitakunda. While initially uncontaminated, ongoing metal influx poses a potential risk to mangrove ecosystems.

Addressing the Carbonate Issue: Electrocatalysts for Acidic CO2 Reduction Reaction.

Electrochemical CO2 reduction reaction (CO2RR) powered by renewable energy provides a promising route to CO2 conversion and utilization. However, the widely used neutral/alkaline electrolyte consumes a large amount of CO2 to produce (bi)carbonate byproducts, leading to significant challenges at the device level, thereby impeding the further deployment of this reaction. Conducting CO2RR in acidic electrolytes offers a promising solution to address the "carbonate issue"; however, it presents inherent difficulties due to the competitive hydrogen evolution reaction, necessitating concerted efforts toward advanced catalyst and electrode designs to achieve high selectivity and activity. This review encompasses recent developments of acidic CO2RR, from mechanism elucidation to catalyst design and device engineering. This review begins by discussing the mechanistic understanding of the reaction pathway, laying the foundation for catalyst design in acidic CO2RR. Subsequently, an in-depth analysis of recent advancements in acidic CO2RR catalysts is provided, highlighting heterogeneous catalysts, surface immobilized molecular catalysts, and catalyst surface enhancement. Furthermore, the progress made in device-level applications is summarized, aiming to develop high-performance acidic CO2RR systems. Finally, the existing challenges and future directions in the design of acidic CO2RR catalysts are outlined, emphasizing the need for improved selectivity, activity, stability, and scalability.

Photocatalytic toluene oxidation with nickel-mediated cascaded active units over Ni/Bi2WO6 monolayers.

Adsorption and activation of C-H bonds by photocatalysts are crucial for the efficient conversion of C-H bonds to produce high-value chemicals. Nevertheless, the delivery of surface-active oxygen species for C-H bond oxygenation inevitably needs to overcome obstacles due to the separated active centers, which suppresses the catalytic efficiency. Herein, Ni dopants are introduced into a monolayer Bi2WO6 to create cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs. Experimental characterizations and density functional theory calculations reveal that these special sites can establish an efficient and controllable C-H bond oxidation process. The activated oxygen species on unsaturated W are readily transferred to the Bi/O sites for C-H bond oxygenation. The catalyst with a Ni mass fraction of 1.8% exhibits excellent toluene conversion rates and high selectivity towards benzaldehyde. This study presents a fascinating strategy for toluene oxidation through the design of efficient cascaded active units.

Enriching surface-ordered defects on WO3 for photocatalytic CO2-to-CH4 conversion by water.

Defect engineering has been widely applied in semiconductors to improve photocatalytic properties by altering the surface structures. This study is about the transformation of inactive WO3 nanosheets to a highly effective CO2-to-CH4 conversion photocatalyst by introducing surface-ordered defects in abundance. The nonstoichiometric WO3-x samples were examined by using aberration-corrected electron microscopy. Results unveil abundant surface-ordered terminations derived from the periodic {013} stacking faults with a defect density of 20.2%. The {002} surface-ordered line defects are the active sites for fixation CO2, transforming the inactive WO3 nanosheets into a highly active catalyst (CH4: O2 = 8.2: 16.7 µmol h-1). We believe that the formation of the W-O-C-W-O species is a critical step in the catalytic pathways. This work provides an atomic-level comprehension of the structural defects of catalysts for activating small molecules.

Risk Assessment and Sources Apportionment of Toxic Metals in Two Commonly Consumed Fishes from a Subtropical Estuarine Wetland System.

The widespread occurrence of heavy metals in aquatic environments, resulting in their bioaccumulation within aquatic organisms like fish, presents potential hazards to human health. This study investigates the concentrations of five toxic heavy metals (Pb, Hg, Zn, Cu, and Cr) and their potential health implications in two economically important fish species (Otolithoides pama and Labeo bata) from a subtropical estuarine wetland system (Feni estuary, Bangladesh). Muscle and gill samples from 36 individual fish were analyzed using energy dispersive X-ray fluorescence (EDXRF). The results revealed that the average quantities of heavy metals in both fishes' muscle followed the declining order of Zn (109.41-119.93 mg/kg) > Cu (45.52-65.43 mg/kg) > Hg (1.25-1.39 mg/kg) > Pb (0.68-1.12 mg/kg) > Cr (0.31-5.82 mg/kg). Furthermore, Zn was found to be present in the highest concentration within the gills of both species. While the levels of Cu, Zn, and Cr in the fish muscle were deemed acceptable for human consumption, the concentrations of Pb and Hg exceeded the permissible limits (>0.5 mg/kg) for human consumption. Different risk indices, including estimated daily intake (EDI), target hazard quotient (THQ), hazard index (HI), and carcinogenic or target risk (TR), revealed mixed and varying degrees of potential threat to human health. According to the EDI values, individuals consuming these fish may face health risks as the levels of Zn, Cu, and Cr in the muscle are either very close to or exceed the maximum tolerable daily intake (MTDI) threshold. Nevertheless, the THQ and HI values suggested that both species remained suitable for human consumption, as indicated by THQ (<1) and HI (<1) values. Carcinogenic risk values for Pb, Cr, and Zn all remained within permissible limits, with TR values falling below the range of (10-6 to 10-4), except for Zn, which exceeded it (>10-4). The correlation matrix and multivariate principal component analysis (PCA) findings revealed that Pb and Cr primarily stemmed from natural geological backgrounds, whereas Zn, Cu, and Hg were attributed to human-induced sources such as agricultural chemicals, silver nanoparticles, antimicrobial substances, and metallic plating. Given the significance of fish as a crucial and nutritious element of a balanced diet, it is essential to maintain consistent monitoring and regulation of the levels and origins of heavy metals found within it.

Recent advances on bismuth oxyhalides for photocatalytic CO2 reduction.

Photocatalytic conversion of CO2 into fuels such as CO, CH4, and CH3OH, is a promising approach for achieving carbon neutrality. Bismuth oxyhalides (BiOX, where X = Cl, Br, and I) are appropriate photocatalysts for this purpose due to the merits of visible-light-active, efficient charge separation, and easy-to-modify crystal structure and surface properties. For practical applications, multiple strategies have been proposed to develop high-efficiency BiOX-based photocatalysts. This review summarizes the development of different approaches to prepare BiOX-based photocatalysts for efficient CO2 reduction. In the review, the fundamentals of photocatalytic CO2 reduction are introduced. Then, several widely used modification methods for BiOX photocatalysts are systematacially discussed, including heterojunction construction, introducing oxygen vacancies (OVs), Bi-enrichment, heteroatom-doping, and morphology design. Finally, the challenges and prospects in the design of future BiOX-based photocatalysis for efficient CO2 reduction are examined.

Cu2O/WO3 S-scheme heterojunctions for photocatalytic degradation of levofloxacin based on coordination activation.

Heterogeneous photocatalytic degradation of antibiotic involves the activation of antibiotic molecules and the photocatalytic oxidation process. However, the simultaneous improvement of these processes is still a challenge. Herein, S-scheme heterojunctions consisted of Cu2O nanocluster with defective WO3 nanosheets were constructed for efficient photocatalytic degradation of levofloxacin (LVX). The typical CNS-5 composite (5 wt% Cu2O/WO3) achieves an optimal LVX degradation efficiency of 97.9% within 80 min. The spatial charge separation and enhancement of redox capacity were realized by the formation of S-scheme heterojunction between Cu2O and WO3. Moreover, their interfacial interaction would lead to the loss of lattice oxygen and the generation of W5+ sites. It is witnessed that the C-N of piperazine ring and CO of carboxylic acid in LVX are coordinated with W5+ sites to build the electronic bridge to activate LVX, greatly promoting the further degradation. This work highlights the important role of selective coordination activation cooperated with S-type heterojunctions for the photocatalytic degradation and offers a new view to understand the degradation of antibiotics at molecular level.

Initial Clinical Images From a Second-Generation Prototype Silicon-Based Photon-Counting Computed Tomography System.

RATIONALE AND OBJECTIVES: To demonstrate the feasibility and potential of using a second-generation prototype photon-counting computed tomography (CT) system to provide simultaneous high spatial resolution images and high spectral resolution material information across a range of routine imaging tasks using clinical patient exposure levels. MATERIALS AND METHODS: The photon-counting system employs an innovative silicon-based photon-counting detector to provide a balanced approach to ultra-high-resolution spectral CT imaging. An initial cohort of volunteer subjects was imaged using the prototype photon-counting system. Acquisition technique parameters and radiation dose exposures were guided by routine clinical exposure levels used at the institution. Images were reconstructed in native slice thickness using an early version of a spectral CT reconstruction algorithm Samples of images across a range of clinical tasks were selected and presented for review. RESULTS: Clinical cases are presented across inner ear, carotid angiography, chest, and musculoskeletal imaging tasks. Initial reconstructed images illustrate ultra-high spatial resolution imaging. The fine detail of small structures and pathologies is clearly visualized, and structural boundaries are well delineated. The prototype system additionally provides concomitant spectral information with high spatial resolution. CONCLUSION: This initial study demonstrates that routine imaging at clinically appropriate patient exposure levels is feasible using a novel deep-silicon photon-counting detector CT system. Furthermore, a deep-silicon detector may provide a balanced approach to photon-counting CT, providing high spatial resolution imaging with simultaneous high-fidelity spectral information.

Quantification, characterization and risk assessment of microplastics from five major estuaries along the northern Bay of Bengal coast.

Microplastics (MPs) as hazardous contaminants has drawn the rapid attention of the general public due to their omnipresence and adverse impacts on ecosystems and human health. Despite this, understanding of MPs contamination levels in the estuarine ecosystems along the Bay of Bengal coast remains very limited. This research focused on the presence, spatial distribution, morpho-chemical characteristics and ecological implications of MPs in water and sediment from five key estuaries (Meghna, Karnaphuli, Matamuhuri, Bakkhali, and Naf rivers) within the Bengal delta. Out of the five estuaries, the Meghna exhibited the least amount of MPs in both surface water (150.00 ± 65.62 items/m3) and sediment (30.56 ± 9.34 items/kg). In contrast, the highest occurrence of MPs was recorded in Karnaphuli river water (350.00 ± 69.22 items/m3) and Matamuhuri river sediment (118.33 ± 26.81 items/kg). ANOVA indicated a statistically significant distinction (p < 0.01) among the examined estuaries. Most identified MPs were fibers and < 0.5 mm in size in both water and sediment samples. Transparent MPs were dominant in both water (42.28%) and sediment (45.22%). Besides violet, red, blue, pink and green colored MPs were also observed. Various polymer types, including PE, PP, PET, PS, Nylon, EVA, and ABS, were detected, with PE being the dominant one. Based on the polymer risk index (PHI), the estuaries were classified as hazard level V, signifying a severe level of MP contamination. However, the potential ecological hazardous index (PHI), potential ecological risk index (RI), and pollution load index (PLI) indicated moderate pollution levels. This study offers initial insights into the pollution caused by MPs in major estuaries of Bengal delta, which policymakers can utilize to implement suitable management strategies.

Microplastics in Different Tissues of a Commonly Consumed Fish, Scomberomorus guttatus, from a Large Subtropical Estuary: Accumulation, Characterization, and Contamination Assessment.

Microplastics (MPs) ingestion by fish signifies a worldwide threat to human health but limited research has examined their existence within the consumable portions (muscle) of fish. Thus, this study was undertaken to unveil the prevalence, characterization, and contamination extent of MPs across various body tissues, including the muscle of the king mackerel (S. guttatus) from the lower Meghna estuary in Bangladesh-a pioneering investigation in this region. In our analysis, we identified a total of 487 MPs, with an average abundance of 48.7 ± 20.3 MPs/individual. These MPs were distributed across different tissues, with respective concentrations of 0.84 ± 0.45 items/g in the digestive tract, 2.56 ± 0.73 items/g in the gills, and 0.3 ± 1.72 items/g in the muscle tissue. The observed variations among these tissue types were statistically significant (p < 0.05). Moreover, a significant positive correlation indicated that fish with higher weight had higher MPs in their gills and DT (digestive tract). The majority were <0.5 mm in size (97.74%) and exhibited a fiber-like shape (97.74%), with a notable prevalence of transparent (25.87%) and a pink coloration (27.92%). Remarkably, the majority of MPs were discovered within the size range of <0.5-1 mm (100%), particularly in the muscle tissue, signifying a substantial transfer of MPs into the human diet. Besides, we discovered only three polymer types of microplastics which could be attributed to the extensive use of food packaging, plastic containers, wrapping plastics, residential garbage, and plastic pipes that end up in the aquatic environment via river discharges. The contamination factor (CF) values of fish muscle (5.75) and the digestive tract (5.50) indicated that these fish organs were considerably contaminated (3 < CF < 6) with MPs. The pollution index of MPs (PLI > 1) indicated a high contamination level for MPs pollution of S. guttatus in the lower Meghna River estuary.

Photocatalysis with atomically thin sheets.

Atomically thin sheets (e.g., graphene and monolayer molybdenum disulfide) are ideal optical and reaction platforms. They provide opportunities for deciphering some important and often elusive photocatalytic phenomena related to electronic band structures and photo-charges. In parallel, in such thin sheets, fine tuning of photocatalytic properties can be achieved. These include atomic-level regulation of electronic band structures and atomic-level steering of charge separation and transfer. Herein, we review the physics and chemistry of electronic band structures and photo-charges, as well as their state-of-the-art characterization techniques, before delving into their atomic-level deciphering and mastery on the platform of atomically thin sheets.

Nitrogen activation and surface charge regulation for enhancing the visible-light-driven N2 fixation over MoS2/UiO-66(SH)2.

A series of dehydrated MoS2/UiO-66(SH)2 (MS/UiS) composites has been prepared as photocatalysts for N2 fixation. Typically, 10% MS/UiS exhibits the best performance with an NH4+ yield rate of 54.08 µmol∙g-1∙h-1. 15N isotope test confirmed that the sample 10% MS/UiS was most effective for reducing N2 to ammonia. Such enhanced activity was due to the presence of abundant unsaturated Zr and Mo sites which would synergistically promote the adsorption and activation of N2. The photogenerated electrons would transfer to the unsaturated Zr-O clusters while part of photogenerated electrons at the interface migrate to MS via MoVI-O interactions between MS and UiS. These two electron transfer pathways effectively promote the separation of photogenerated carriers. The activated N2 is reduced to ammonia by the synergistic effect of protonated hydrogen and photogenerated electrons. Finally, a possible N2 fixation mechanism is proposed which emphasizes the significant roles of nitrogen activation and interface interaction in composites photocatalyst for improving photocatalytic performance.

Heavy metals in wild and cultured shrimp, supplied feeds, and their habitats: Assessing public health risk.

The contamination and risk assessment of heavy metals (HMs) in highly priced tiger shrimp and its associated ecosystems and farming conditions (hatcheries and commercial grow-out ponds) were scarcely investigated in South Asian countries. In this study, we determined the five HMs (Cu, Zn, Pb, Cd, and Cr) concentrations in PL14 (fourteen days of Post-Larva) of Penaeus monodon, commercial diets, surface water, and sediments from hatcheries, farms, rivers using ICP-MS for two years. The results revealed that surface sediments of rivers and hatcheries had the highest amounts of Cr (65.85 ± 0.82 and 72.50 ± 0.42 mg/kg), Cu (18.82 ± 3.96 and 19.26 ± 4.61 mg/kg), and Zn (63.74 ± 11.14 and 87.42 ± 17.96 mg/kg), whereas commercial farms had the greatest levels of Cd (0.09 ± 0.05 mg/kg). Pb was significantly higher in sediment of hatcheries and farms than in other sites. Except for Zn in surface waters, all metals were found above the recommended limit. In case of supplied feed, all values were in the safe limit excepting Cr (3.39 ± 1.45 to 108.92 ± 3.49 mg/kg). On the other hand, among the metals, only Cr (VI) ranging from 1.75 ± 1.39 mg/kg in P. monodon samples exceeded the suggested international guidelines. The Igeo values of all the metals were Igeo <0, indicating that the study areas were practically unpolluted. PLI values in every station were found to be below 1 which indicates the perfection of the sediment. The Potential Risk Index (PERI) values were less than 150 suggesting low risk of metals in sediments. The public health risk assessment estimated through the calculated daily intake (EDI), target hazard quotient (THQ) and hazard index (HI) has shown that the shrimp was safe for consumers except for Cd and Cr. The THQ for Cd and Cr were higher than the threshold (>1) indicating potential health hazards. The low CR values for Cd, Cr Pb were 3.1 × 10-4, 3.7 × 10-4 and 1.6 × 10-4, respectively indicates no cancer risks upon consuming P. monodon.

Potential Toxic Elements and Their Carcinogenic and Non-Carcinogenic Risk Assessment in Some Commercially Important Fish Species from a Ramsar Site.

Potentially toxic elements (PTEs) such as Hg, As, and Pb have become concentrated in the aquatic ecosystem as a result of increased human activities. However, these substances frequently have synergistic or antagonistic effects on the human body or other animals. As a result, there are concerns world-wide that commercially available food products, especially fish, may be contaminated with hazardous elements. In this study, samples of four selected fishes, Gutum (Lepidocephalichthys guntea), Baim (Macrognathus pancalus), Baila (Glossogobius giuris), Meni (Nandus nandus) were analyzed from one of the largest freshwater wetlands (designed as a Ramsar Site) in South Asia to evaluate PTEs contamination status and human health risk assessment. The result demonstrated that the degree of contamination for six PTEs decreased in the following sequences for fish: Fe > Zn > Cu > Pb > As > Hg. The edible part of G. giuris had the maximum value for Hg (0.42 µg/g dw), while N. nandus predominantly accumulated As (<0.41 µg/g dw). The estimated daily intake (EDI) values ranged from 0.003 to 1.75, which was much lower than the recommended values. The hazard index (HI), THQ, total target hazard quotient (TTHQ) scores through consuming fish followed the decreasing order of Fe > Hg > Cu > Zn > Pb. The values for each index were less than 1, indicating that there were no substantial health risks for the consumers. The carcinogenic risks (CR) derived from the intake of Pb ranged from 4.92 × 10-8 to 4.14 × 10-8 for males and 5.45 × 10-8 to 4.59 × 10-8 for females, which also did not exceed the standard limit (1.00 × 10-6). This study demonstrated that, under the existing consumption rate, there was no potential health harm to consumers from consuming the studied fishes. This study offers a chance to regularly check PTEs in this environment, reducing the contamination of heavy metals.

Seasonal variation, contamination and ecological risk assessment of heavy metals in sediments of coastal wetlands along the Bay of Bengal.

Functioning of coastal wetland habitats is essential for the ecosystem integrity and sustainability of coastal development that enables human progress along transitional waterways. However, these habitats are continuously being affected by a variety of pollutants including metallic elements. In this study, seasonal variation, pollution status and ecological risks of heavy metals (Cr, Mn, Co, Ni, As, Cu, Zn and Pb) in surface sediment of the several types of coastal wetlands (estuaries, mudflats, sandy beaches, mangroves, and saltmarshes) were detected by using X-ray fluorescence (EDXRF) spectrometry. The results showed that the mean concentration level of metals in the surficial sediment samples followed the order of Cu (84.06 ± 8.60 µg/g) > Zn (51.00 ± 8.97 µg/g) > Mn (38.25 ± 11.34 µg/g) > Cr (3.52 ± 0.91 µg/g) > Pb (0.27 ± 0.13 µg/g) > Co (0.24 ± 0.13 µg/g) > As (0.21 ± 0.12 µg/g) > Ni (0.16 ± 0.08 µg/g). In comparison to the pre-monsoon period, the post-monsoon season had higher concentrations of heavy metals while the overall accumulation level of metals in the wetlands exhibited a pattern of estuarine wetland (28.47 ± 31.35 µg/g) > mangrove (22.23 ± 30.79 µg/g) > mudflat (21.79 ± 29.71 µg/g) > sandy beach (21.47 ± 28.15 µg/g) > saltmarsh (21.28 ± 30.02 µg/g). Although, the pollution assessment indices e.g., contamination factor (CF), degree of contamination (CD), geoaccumulation index (Igeo) and pollution load index (PLI) showed minimal levels of contamination in the studied sites, enrichment factor (EF) suggested greater enrichment of the metals in the pre-monsoon season but with the lowest ecological risk (RI < 40) in both seasons. Cluster analysis, principal component analysis (PCA), and Pearson's correlation were performed to determine the sources of heavy metals in collected samples which specified that Pb, As, Co and Ni predominantly came from natural sources whereas Cu, Mn, Zn and Cr emerged from anthropogenic sources such as industrial effluents, domestic wastewater, fertilizer or pesticide consumption on farmland along the riverbank, vessel emissions, and the confluence of tributary rivers.

Size Effects of Highly Dispersed Bismuth Nanoparticles on Electrocatalytic Reduction of Carbon Dioxide to Formic Acid.

Electrocatalytic reduction of carbon dioxide into value-added chemical fuels is a promising way to achieve carbon neutrality. Bismuth-based materials have been considered as favorable electrocatalysts for converting carbon dioxide to formic acid. Moreover, size-dependent catalysis offers significant advantages in catalyzed heterogeneous chemical processes. However, the size effects of bismuth nanoparticles on formic acid production have not been fully explored. Here, we prepared Bi nanoparticles uniformly supported on porous TiO2 substrate electrocatalytic materials by in situ segregation of the Bi element from Bi4Ti3O12. The Bi-TiO2 electrocatalyst with Bi nanoparticles of 2.83 nm displays a Faradaic efficiency of greater than 90% over a wide potential range of 400 mV. Theoretical calculations have also demonstrated subtle electronic structural evolutions induced by the size variations of Bi nanoparticles, where the 2.83 nm Bi nanoparticles display the most active p-band and d-band centers to guarantee high electroactivity toward CO2RR.

Plasma-Enhanced Chemical-Vapor-Deposition Synthesis of Photoredox-Active Nitrogen-Doped Carbon from NH3 and CH4 Gases.

Earth's primordial atmosphere was rich in ammonia and methane. To understand the evolution of the atmosphere, these two gases were used to make photoredox-active nitrogen-doped carbon (NDC). Photocatalysts such as NDC might play an important role in the development of geological and atmospheric chemistry during the Archean era. This study describes the synthesis of NDC directly from NH3 and CH4 gases. The photocatalyst product can be used to selectively synthesize imines by photo-oxidization of amines, producing H2 O2 simultaneously in the photoreduction reaction. Our findings shed light on the chemical evolution of the Earth.