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Nitrated polycyclic aromatic hydrocarbons (NPAHs) are widespread organic pollutants that possess carcinogenic and mutagenic properties, so they may pose a risk to the environment and human health. In this study, the concentrations of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) in 30 surface water samples and 26 sediment samples were measured in 2018 from the Taige Canal, one of the main rivers flowing into Taihu Lake, China. The total NPAH concentrations in water and sediment ranged from 14.7 to 235 ng/L and 22.9 to 96.5 ng/g dw, respectively. 9-nitrophenanthrene (nd-76.3 ng/L) was the dominant compound in surface water, while 2+3-nitrofluoranthene (1.73-18.1 ng/g dw) dominated in sediment. Among PAHs, concentration ranging from 1,097 to 2,981 ng/L and 1,089 to 4,489 ng/g dw in surface water and sediment, respectively. There was a strong positive correlation between the log octanol-water partition coefficient (K

Employing perylene diimide supermolecule (PDI) as metal-free cocatalyst, a novel PDI/g-C

The difficulty in Fe(III)/Fe(II) conversion in the Fe(III)/peroxymonosulfate (PMS) process limits its efficiency and application. Herein, L-cysteine (Cys), a green natural organic ligand with reducing capability, was innovatively introduced into Fe(III)/PMS to construct an excellent Cys/Fe(III)/PMS process. The Cys/Fe(III)/PMS process, at room temperature, can degrade a variety of organic contaminants, including dyes, phenolic compounds, and pharmaceuticals. In subsequent experiments with acid orange 7 (AO7), the AO7 degradation efficiency followed pseudo-first-order kinetic which exhibited an initial “fast stage” and a second “slow stage”. The rate constant values ranged depending on the initial Cys, Fe(III), PMS, and AO7 concentrations, reaction temperature, and pH values. In addition, the presence of Cl−, NO3−, and SO42− had negligible impact while HCO3− and humic acid inhibited the degradation of AO7. Furthermore, radical scavenger experiments and methyl phenyl sulfoxide (PMSO) transformation assay indicated that sulfate radical, hydroxyl radical, and ferryl ion (Fe(IV)) were the dominant reactive species involved in the Cys/Fe(III)/PMS process. Finally, based on the results of gas chromatography-mass spectrometry, several AO7 degradation pathways, including N=N cleavage, hydroxylation, and ring opening were proposed. This study provided a new insight to improve the efficiency of Fe(III)/PMS process by accelerating Fe(III)/Fe(II) cycle with Cys.

Based on single metal-organic framework (MOF) composite catalyst ZIF-67/g-C3N4 (ZG), the composite catalysts ZIF-67/MOF-74(Ni)/g-C3N4 (ZNG) and ZIF-67/MIL-100(Fe)/g-C3N4 (ZMG) with double MOFs were synthesized, used to effectively activate peroxymonosulfate (PMS) for degrade venlafaxine (VEN). Various characterization methods (XRD, FT-IR, Raman, SEM, EDS, TEM and TG) showed that ZIF-67 and g-C3N4; ZIF-67, MOF-74(Ni) and g-C3N4; as well as ZIF-67, MIL-100(Fe) and g-C3N4 successfully formed heterostructures. The series of catalytic degradation results showed that within 120 min, the degradation rate of VEN by ZMG achieved 100% and the mineralization rate reached 51.32%. The removal rate of VEN by ZNG was 91.38%, while that by ZG was only 27.75%. Free radical quenching tests and EPR further confirmed the production of •OH and SO4•-, which could be conducive to the degradation of VEN. The mechanism analysis of PMS activation confirmed that the interaction of ≡Fe2+/≡Co3+ was stronger than that of ≡Ni2+/≡Co3+, and it was an important driving force to significantly enhance the synergistic effect. Finally, Gauss theory calculation and HPLC-MS/MS were used to analyze the intermediate products of VEN. It was verified that the main chemical reactions in the degradation process of VEN were hydroxylation, dehydration, demethylation and tertiary amine substitution.

Phytate-modified nano-ferrous sulfide (IP6-nano-FeS) was successfully prepared to overcome the low efficiency of heavy metal removal by nano-ferrous sulfide (nano-FeS) due to the agglomeration and easy oxidization of this reducing agent. The results showed that IP6-nano-FeS improved the dispersion of nano-FeS particles, and the maximum Cr(VI) removal reached 436.94 ± 25.40 mg/g. A more novel contribution of this study is that Cr(VI) removal by IP6-nano-FeS was enhanced in the presence of Mg2+, Ca2+, and O2. The removal efficiency increased by ∼10% and ∼8.5% in the presence of conventional cations (Mg2+ and Ca2+: 2–10 g/L) and O2, respectively. The application potential of IP6-nano-FeS for the rapid removal of Cr(VI)-contamination in the presence of aerobic and coexisting cations was confirmed in this study.

Nanorod-like CoP nanoparticles were fabricated from different precursors of Co(OH)2 and Co3O4 by gas-solid reaction, then further embedded into g-C3N4 nanosheets to form intimate heterojunctions via the (0 1 1) crystal planes of CoP nanoparticles. The heterojunction hybrid obtained from Co(OH)2 exhibits superior activity in photo, electro and photoelectrochemical water splitting processes. In photocatalytic water half-splitting for hydrogen evolution reaction, the as-obtained 0.5% CoP-CN achieved a rate at 959.4 μmol·h−1·g−1 and 59.1 μmol·h−1·g−1 when irradiated by simulated sunlight and visible light respectively, almost 3.1 times and 15.8 times that of pristine g-C3N4, For photocatalytic water full-splitting, a stoichiometric evolution of H2 (14.7 μmol·h−1·g−1) and O2 (7.6 μmol·h−1·g−1) was observed on 3%Pt-0.5% CoP-CN composite. The onset potential for electrochemical HER process was drastically reduced after deposition with 0.5% CoP. Meanwhile, a higher photocurrent response and larger anodic photocurrent was detected over 0.5% CoP-CN photoanode during the photoelectrochemical water splitting process, relative to pristine g-C3N4 and its analogues. The comprehensive enhancements for catalytic activity of 0.5% CoP-CN could be attributed to its reduced over-potentials, more negative photo-reductive potentials, boosted interfacial charge transfer efficiency, as well as a much higher solar to hydrogen efficiency. The contrastive redox roles of CoP in both photocatalytic water half-splitting and full-splitting processes have been fully explored and revealed. This design on covalent organic framework of highly efficient CoP-based heterojunctions holds great promise for direct water splitting applications in utilizing solar energy.

Because polycyclic aromatic compounds (PACs) are persistent, universal, and toxic pollutants, understanding the potential source and ecological risk thereof in lakes is critical to the safety of the aquatic environment. Here, a total of 25 sedimentary samples were collected from Lake Taihu, China, in 2018. The total concentrations of 16 parent polycyclic aromatic hydrocarbons (PAHs), 15 nitrated PAHs (NPAHs), nine oxygenated PAHs (OPAHs), and five hydroxy-PAHs (OH-PAHs) ranged from 294 to 1243, 3.0 to 54.5, 188 to 1897, and 8.3 to 51.7 ng/g dw, with the most abundant compounds being fluoranthene, 1,8-dinitropyrene, 6H-Benzo[cd]pyren-6-one, and 2-phenylphenol, respectively. The spatial distribution of PACs in sediments of Lake Taihu showed elevated concentrations from east to west due to economic development and transportation. The positive correlations between most paired PAHs indicate that these compounds likely originated from similar sources. The total organic carbon and organic matter contents affected the distribution characteristics of PACs in sediments. Diagnostic ratios, principal component analysis-multiple linear regression (PCA-MLR), and positive matrix factorization (PMF) were integrated to identify the sources. PACs had various sources including combustion, petroleum leakage, traffic emissions, hydroxyl metabolism, and other oxidation pathways in sediments of Lake Taihu. The PMF (R

Ferrous sulfide (FeS) nanoparticles constitute an effective hexavalent chromium (Cr(VI)) treatment reagent. However, FeS nanoparticles aggregate easily, significantly limiting their engineering applicability. To overcome this shortcoming and further improve Cr(VI) removal efficiency, this study used tannic acid (TA) to modify FeS nanoparticles. The results demonstrated that TA-modified FeS nanoparticles, TA-nano-FeS, had a significantly reduced tendency to agglomerate, and maintained particle diameters of 10–100 nm, which were much shorter than diameters of FeS nanoparticles. In addition, TA-nano-FeS could combine the surface-active functional groups of TA. The maximum removal capacity of TA-nano-FeS was 381.04 mg/g, which was 2.92 and 1.83 times higher than those of TA and nano-FeS, respectively. Furthermore, the acidic condition was more beneficial for Cr(VI) removal, and the coexisting cations (Ca2+ and Mg2+) slightly decreased the removal efficiency of Cr(VI). Adsorption, reduction, and co-precipitation were the removal mechanisms, and the reaction products included FeCr2O4, Cr2O3, Fe2O3, Cr(OH)3, and S8. The results provided valuable information for the practical application of TA-nano-FeS in Cr(VI) removal.

The occurrence of nitrated polycyclic aromatic hydrocarbons (NPAHs) in sediments has been widely reported, but research on NPAH bioavailability is lacking. In this study, a self-made zeolite imidazolate framework-8/hexagonal boron nitride (ZIF-8/h-BN) solid-phase microextraction (SPME) fiber and commercial Tenax are compared as efficient tools to predict the bioavailability of NPAHs in sediments with bioassays using Cipangopaludina chinensis. During the process of SPME, the NPAH concentrations on the ZIF-8/h-BN fibers reached extraction equilibrium after 72 h. The fiber extraction of NPAHs in sediments was well-fitted by the pseudo first-order kinetic model with a rate constant of 2 × 10

Microcontaminants in the water environment have received increasing attention due to their adverse effects on human health and wildlife. However, iodinated X-ray contrast media (ICM), a type of microcontaminants, have not yet been systematically documented in source and tap water. This study investigated ICM in water samples via a sampling activity from 25 drinking water sources and their corresponding 30 household taps in south-central Jiangsu Province, China. The total concentrations of ICM ranged from 14.2 to 138.5 ng/L in source water and 3.7 to 101.3 ng/L in tap water, respectively. The calculated average water treatment efficiency to remove ICM is 38.3% with large variation under different processes (ranging from 7.3% to 75.7%), which implied that ICM could not be effectively removed using current treatment technologies. By integrating other ICM into the predominant compound iohexol with relative potency factors, the health risks of total ICM through water consumption were assessed using the Monte Carlo simulation. The results concluded that the risk of ingesting ICM through tap water was not a major health concern for adults, teens, or children in the study area. Nevertheless, due to the lack of long-term toxicity data relevant for humans for ICM, this risk may be underestimated, which requires further research.

The g-C3N4/Y-TiO2 Z-scheme heterojunction photocatalysts were successfully synthesized. Powder X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used for characterization. The photocatalytic activity of the as-prepared samples was investigated via the degradation efficiency of rhodamine B (RhB) under visible-light irradiation, and 20 mg L−1 RhB was completely degraded in 90 min. The results showed that the photocatalytic degradation of RhB conformed to pseudo-first-order kinetic fitting, and the kinetic constants of g-C3N4/Y-TiO2 were 4.27 times higher than those of g-C3N4/TiO2 and 14.18 times higher than those of Y-TiO2, respectively. The enhanced photocatalytic activity of g-C3N4/Y-TiO2 was due to the formation of a Z-scheme heterojunction by Y at the g-C3N4/TiO2 interface. Formation of the Z-scheme heterojunction resulted in the suppression of photo-generated electron–hole pair recombination and the increase of their lifetimes, which was demonstrated by the transient photocurrent response, electrochemical impedance spectroscopy, and the time-resolved photoluminescence spectra. The superoxide radical and photo-generated holes played a dominant role in the photocatalytic degradation process of RhB by g-C3N4/Y-TiO2.

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H2O2 oxidation process. The removal rate of TCEP in the UV/H2O2 system was 89.1% with the production of Cl− and PO43− of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H2O2 system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min−1 (R2=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO• and H2O and the oxidation reaction with H2O2 were found during the degradation pathway of 5 mg/L TCEP in the UV/H2O2 system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H2O2 system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.

Tri(2-chloroisopropyl) phosphate (TCPP), a common organophosphate flame retardant, was frequently detected in the environment and posed threats to human health. In this work, the main component of ilmenite FeTiO

The colloid of ferrous sulfide modified by humic acid (HA-n-FeS) shows good reduction and immobilization efficiency for variable-valence heavy metals in wastewater. The removal efficiency of HA-n-FeS for halogenated organic pollutants, however, remains unclear, especially in the absence and presence of oxygen. This study addressed this issue by exploring the effect and mechanism of dissolved oxygen on the degradation of tetrabromobisphenol A (TBBPA) by the HA-n-FeS colloid in water. The results showed that the removal efficiency of different concentrations of TBBPA (5,10, and 20 μm) by the HA-n-FeS colloid was 33.16%, 20.48%, and 22.37% in the absence of oxygen, respectively. When TBBPA reacted with the HA-n-FeS colloid, the concentration of Fe(II) and S(-II) remained stable. The adsorption of HA-n-FeS was the main mechanism of removing TBBPA in the absence of oxygen. In the presence of oxygen, the removal efficiency of TBBPA by the HA-n-FeS colloid was 82.37%, 56.80%, and 43.78% (for the above-mentioned TBBPA concentrations), respectively. In addition, the removal capacity of TBBPA by HA-n-FeS was 39.63, 52.21, and 89.75 mg/g, respectively. The concentration of Fe(II) and S(-II) decreased rapidly in time. Among them, the HA-n-FeS colloid removed part of the TBBPA through chemical adsorption. The main way of chemical adsorption was pore adsorption and functional group (olefin CC, phenolic hydroxyl group O-H, alcohol group C-O) combination. Besides, the HA-n-FeS colloid degraded part of the TBBPA into BPA through reduction, in which 17.72% of TBBPA was removed by the reduction of HA-n-FeS colloid. Fe(II) was the main contributor to the reductive degradation of TBBPA. Furthermore, active species (

Based on single metal-organic framework (MOF) composite catalyst ZIF-67/g-C

Permanganate (Mn (VII)) is an environmentally-friendly mild oxidant in the field of advanced oxidation treatment, however, manganese colloids are produced as byproducts, which is difficult to separate from water, resulting in secondary pollution. This study used potassium methyl silicates (PMS) as surface modifiers to improve the aggregation of colloidal particles by increasing the hydrophobicity of the colloidal surface, and then explored the oxidation of bisphenol A (BPA) by Mn (VII) under the influence of potassium methyl silicate and the solid-liquid separation performance of the reaction system. The results showed that PMS and sodium silicate (SS) substantially enhanced the degradation of BPA by Mn (VII), and the promotion effect of potassium methyl silicate was greater than that of sodium silicate. PMS provided not only enough adsorption sites for MnO

In this study, three kinds of Zeolite imidazolate framework-8 (ZIF-8), synthesized by solvothermal, stirring and ball-milling method, were fabricated on the stainless steel wire via sol-gel technique. These fibers were used as solid phase microextraction (SPME) coating materials and applied for analyzing 16 polycyclic aromatic hydrocarbons (PAHs) and 11 nitro polycyclic aromatic hydrocarbons (NPAHs) in environmental water samples by gas chromatography-tandem mass spectrometry (GC–MS). The optimal pH, ionic strength, extraction time, extraction temperature, desorption temperature and desorption time were 6.0, without salt addition, 45 min, 35 °C, 260 °C and 5 min, respectively. The extraction mechanism of the ZIF-8 fiber might be the hydrophobicity, molecular penetration and π-π stacking interactions. Under the optimized conditions, the as-proposed fiber provides a wide linearity range from 10 to 20,000 ng L−1 and a low detection limit of 0.3–27.0 ng L−1 for PAHs and NPAHs analysis. The single fiber and fiber to fiber relative standard deviations were observed in the range of 3.0%–13.9% and 3.5%–12.3%, respectively. The method shows great potential in environmental analysis field.

Bi2S3 nanoribbons were dispersed in situ on Bi2WO6 ultrathin nanosheets with exposed {001} facet via a simple one-set hydrothermal route forming Bi2S3/Bi2WO6 heterojunctions with high active surface, in which the quantity of Bi2S3 nanoribbons was tuned by changing the amount of thiourea in solution. The obtained composites were characterized by various measurements and their photocatalytic activities under visible-light irradiation were also investigated. The 7%-Bi2S3/Bi2WO6 nanocomposites exhibited excellent photocatalytic activities in degradation of ofloxacin (OFL). A plausible degradation pathway for OFL was proposed via combining LC-MS and GC–MS detections with Gaussian calculations. The probable photocatalytic and formation mechanism of catalysts were discussed on the basis of the obtained experimental results and density function theory (DFT) calculations. An enhanced photocatalytic mechanism attributed to the synergistic effect between the exposed {001} facet and heterojunction with shape-crystalline integrity, significantly improving band structure and visible light absorption, increasing reactive sites, and suppressing the recombination of charges. The findings provide new insights for designing highly active and stable heterojunction catalysts to remove environmental pollutants and promote solar energy conversion efficiently.

Synthesis of three-dimensional (3D) hierarchical hollow spheres with exposed {0 0 1} active facets are of huge significance in the field of semiconductor photocatalysis. Herein, we demonstrate a facile ionic liquid-in-water (IL/W) microemulsion approach for the fabrication of Bi-rich Bi3O4Br hierarchical hollow spheres assembled with {0 0 1}-facets exposed nanosheets. The size and {0 0 1}-facets exposure ratio of Bi3O4Br hierarchical hollow spheres can be fine-tuned by adjusting the concentration of surfactant TX-100. A possible formation mechanism of Bi3O4Br hierarchical hollow spheres assembled with {0 0 1}-facets exposed nanosheets by microemulsion template and dissolution-recrystallization was proposed based on SEM and XRD results. The actual photocatalytic activity was extensively investigated by degrading multiform phenol derivatives with different substituents and substitution positions, including acetaminophen (APAP), 4-tert-butylphenol (PTBP), o-nitrophenol (ONP), methylparaben (MPB). The Bi3O4Br hierarchical hollow spheres assembled with {0 0 1}-facets exposed nanosheets not only exhibit significantly promoted visible-light photocatalytic activity, but also have robust and nonselective photooxidation ability. The photocurrent and impedance results indicated that significantly strengthened charge separation and transfer efficiency that derived from the advantages of Bi3O4Br {0 0 1} active facets and hollow structures were responsible for the high photo-activity. The study may provide some new hints on designing and developing novel 3D hierarchical hollow structures with exposing {0 0 1} active facets for heterogeneous photocatalysis.