Interfacial tuning in FeP/ZnIn2S4 Ohm heterojunction: Enhanced photocatalytic hydrogen production via Zn-P charge bridging.

Interfacial regulation is key to photocatalytic performance, yet modulating interfacial charge transfer in heterostructures remains challenging. Herein, a novel nanoflower-like FeP/ZnIn2S4 Ohm heterostructure is first designed, with Zn atoms in ZnIn2S4 (ZIS) acting as potential anchoring sites around P atoms, forming liganded Zn-P bonds. Combining 1D FeP nanowires and 2D ZIS nanosheets enhances the mobility of photogenerated electrons. The synergistic chain-type "electron pickup" mechanism of the Ohm heterojunction coupled with the Zn-P bond speeds up electron transport at the interface. The Ohm heterojunction initiates an internal electric field, creating a driving force to further transfer photogenerated electrons through the Zn-P rapid electron transport channel to FeP, which acts as a reservoir for active sites to release H2. The optimized FeP/ZIS demonstrates a remarkable H2 evolution rate at 4.36 mmol h-1 g-1, 3.6 times that of pristine ZIS. This work provides novel insights into optimizing photocarrier dynamics via interfacial microenvironment modulation.

Physiology, microcystin production, and transcriptomic responses of Microcystis aeruginosa exposed to calcium and magnesium.

Calcium ions (Ca2+) and magnesium ions (Mg2+) are pivotal in the community composition and stability of harmful cyanobacteria, yet the physiological and molecular responses remains poorly understood. This study aims to explore these responses in the high microcystin producer Microcystis aeruginosa (M. aeruginosa). Results indicate that the growth of M. aeruginosa is inhibited by Ca2+/Mg2+ exposure (0.5-10 mM), while Fv/Fm photosynthetic parameters and extracellular microcystin-leucine-arginine (MC-LR) concentrations increase. Additionally, MC-LR release is significantly elevated under exposure to Ca2+/Mg2+, posing potential aquatic environmental risks. Transcriptomic analysis reveals downregulation of genes related to cell architecture, membrane transport, and metabolism, while the genes linked to photosynthesis electron transmission and heavy metal-responsive transcriptional regulators are upregulated to adapt to environmental changes. Further analysis reveals that Ca2+ and Mg2+ primarily impact sulfur metabolism and transport of amino acids and mineral within cells. These findings provide insights into M. aeruginosa cells responses to Ca2+ and Mg2+ exposure.

Full-Spectrum Responsive Naphthalimide/Perylene Diimide with a Giant Internal Electric Field for Photocatalytic Overall Water Splitting.

The co-assembly naphthalimide/perylene diimide (NDINH/PDINH) supramolecular photocatalysts were successfully synthesized via a rapid solution dispersion method. A giant internal electric field (IEF) in co-assembly structure was built by the larger local dipole. NDINH coated on PDINH could reduce the reflected electric field over PDINH to improve its responsive activity to ultraviolet light. Resultantly, an efficient full-spectrum photocatalytic overall water splitting activity with H2 and O2 evolution rate of 317.2 and 154.8 µmol g-1 h-1 for NDINH/PDINH together with optimized O2 evolution rate with 2.61 mmol g-1 h-1 using AgNO3 as a sacrificial reagent were achieved. Meanwhile, its solar-to-hydrogen efficiency was enhanced to 0.13 %. The enhanced photocatalytic activity was primarily attributed to the IEF between NDINH and PDINH, significantly accelerating transfer and separation of photogenerated carriers. Additionally, a direct Z-Scheme pathway of carriers contributed to a high redox potential. The strategy provided a new perspective for the design of supramolecular photocatalysts.

Iron 3D-Orbital Configuration Dependent Electron Transfer for Efficient Fenton-Like Catalysis.

Transition metals are excellent active sites to activate peroxymonosulfate (PMS) for water treatment, but the favorable electronic structures governing  reaction mechanism still remain elusive. Herein, the authors construct typical d-orbital configurations on iron octahedral (FeOh ) and tetrahedral (FeTd ) sites in spinel ZnFe2 O4 and FeAl2 O4 , respectively. ZnFe2 O4 (136.58 min-1 F-1 cm2 ) presented higher specific activity than FeAl2 O4 (97.47 min-1 F-1 cm2 ) for tetracycline removal by PMS activation. Considering orbital features of charge amount, spin state, and orbital arrangement by magnetic spectroscopic analysis, ZnFe2 O4 has a larger bond order to decompose PMS. Using this descriptor, high-spin FeOh is assumed to activate PMS mainly to produce nonradical reactive oxygen species (ROS) while high-spin FeTd prefers to induce radical species. This hypothesis is confirmed by the selective predominant ROS of 1 O2 on ZnFe2 O4 and O2 •- on FeAl2 O4 via quenching experiments. Electrochemical determinations reveal that FeOh has superior capability than FeTd for feasible valence transformation of iron cations and fast interfacial electron transfer. DFT calculations further suggest octahedral d-orbital configuration of ZnFe2 O4 is beneficial to enhancing Fe-O covalence for electron exchange. This work attempts to understand the d-orbital configuration-dependent PMS activation to design efficient catalysts.

Correlation analysis between the in vivo bioavailability and in vitro bioaccessibility of nitro PAHs in soil: Application of simplified FOREhST in vitro methods based on the Chinese pharmacopoeia.

In this study, the relative bioavailability (RBA) of nitrated polycyclic aromatic hydrocarbons (NPAHs) in soil samples (n = 30) was assessed using an in vivo mouse model. Based on the correlation between the bioaccessibility data obtained from the Tenax improved traditional Fed ORganic Estimation human Simulation Test (FOREhST) in vitro method (TITF) and the bioavailability data obtained from in vivo experiments, the TITF method was further optimized and simplified by referring to the "Pharmacopoeia of the People's Republic of China: Volume IV, 2020" to adjust the formulation and parameters of the gastrointestinal fluid (GIF) in order to establish a simpler and lower cost in vitro method for the determination of the bioaccessibilities of NPAHs. The dose-accumulation relationship of the in vivo experiment showed that the linear dose-response was better in adipose tissue (R2 = 0.77-0.93), and the accumulation of NPAHs in adipose tissue was higher than that in kidney or liver tissue. Depending on the mouse adipose model, the NPAHs-RBA ranged from 1.88 % to 73.92 %, and a strongly significant negative relationship (R2 = 0.94, p < 0.05) was found between the NPAHs-RBA and Log Kow. The simplified experiment of the TITF showed that the composition of the GIF medium had a significant effect on the bioaccessibilities of NPAHs. The NPAH bioaccessibilities measured by the Tenax improved simplified FOREhST method (TISF) (9.0-36.5 %) were higher than that of the traditional FOREhST method (6.8-22.8 %) but significantly lower than that of the TITF method (16.8-55.2 %). With an increase in the bile concentration in the GIF (from 6 to 10 g/L), the bioaccessibilities of NPAHs increased from 9.0 to 36.5 % to 12.9-42.4 %. The accuracies of the four in vitro methods for predicting the bioavailabilities of NPAHs was in the following order: Tenax improved simplified FOREhST method with increased bile concentration (TITF-IB) (R2 = 0.54-0.87) ≈ TITF (R2 = 0.55-0.85) > TISF (R2 = 0.41-0.77) > FOREhST (R2 = 0.02-0.68). These results indicated that the simple in vitro method could also effectively predict the bioavailabilities of NPAHs.

Converting peracetic acid activation by Fe3O4 from nonradical to radical pathway via the incorporation of L-cysteine.

Recently, peracetic acid (PAA) based Fenton (-like) processes have received much attention in water treatment. However, these processes are limited by the sluggish Fe(III)/Fe(II) redox circulation efficiency. In this study, L-cysteine (L-Cys), an environmentally friendly electron donor, was applied to enhance the Fe3O4/PAA process for the sulfamethoxazole (SMX) abatement. Surprisingly, the L-Cys incorporation was found not only to enhance the SMX degradation rate constant by 3.2 times but also to switch the Fe(IV) dominated nonradical pathway into the •OH dominated radical pathway. Experiment and theoretical calculation result elucidated -NH2, -SH, and -COOH of L-Cys can increase Fe solubilization by binding to the Fe sites of Fe3O4, while -SH of L-Cys can promote the reduction of bounded/dissolved Fe(III). Similar SMX conversion pathways driven by the Fe3O4/PAA process with or without L-Cys were revealed. Excessive L-Cys or PAA, high pH and the coexisting HCO3-/H2PO4- exhibit inhibitory effects on SMX degradation, while Cl- and humic acid barely affect the SMX removal. This work advances the knowledge of the enhanced mechanism insights of L-Cys toward heterogeneous Fenton (-like) processes and provides experimental data for the efficient treatment of sulfonamide antibiotics in the water treatment.

Gas-particle partitioning of organophosphate esters in indoor and outdoor air and its implications for individual exposure.

The extensive utilization of organophosphate esters (OPEs) has resulted in their widespread presence in the environment, raising concerns about potential human health risks. In this study, 13 OPEs were analyzed in both gas and particle phases as well as in indoor and outdoor atmospheric environments. Moreover, human exposure to OPEs were investigated within a university environment, focusing on forehead contact and individual PM2.5 inhalation. The results showed similar distribution patterns of OPEs indoors and outdoors, although higher concentrations were found indoors. The average atmospheric concentration of ∑OPEs (combining particle and gaseous OPEs) was 1575 pg/m3 in the outdoor environment and 6574 pg/m3 ∑OPEs in the indoor microenvironments. The overwhelming majority of OPEs exhibit a pronounced propensity to adsorb onto PM2.5 particles. Notably, the concentration of OPEs on the forehead differed significantly from that in the atmospheric environment, whereas individual PM2.5 exposure was consistent with the concentration of indoor PM2.5. Intriguingly, some OPEs with high octanol-water partition coefficient (log Kow) were not detected in the environment but found on human foreheads. Gas-particle partitioning was predicted using the Harner-Bidleman and Li-Ma-Yang models and the results were in agreement with the monitoring data for approximately half of the OPE monomers. Correlations between OPEs exposure and gas-particle partitioning were found to be more significant for novel OPEs. No non-cancer risk to humans through individual exposure to OPEs was identified via forehead exposure or inhalation. The previously unreported relationship between individual exposure and the environmental occurrence of traditional and novel OPEs demonstrated in this study highlights the importance of evaluating the potential health risks associated with actual OPE exposure.

Atomic Cobalt-Silver Dual-Metal Sites Confined on Carbon Nitride with Synergistic Ag Nanoparticles for Enhanced CO2 Photoreduction.

Photocatalytic reduction of CO2 to value-added solar fuels is of great significance to alleviate the severe environmental and energy crisis. Herein, we report the construction of a synergistic silver nanoparticle catalyst with adjacent atomic cobalt-silver dual-metal sites on P-doped carbon nitride (Co1Ag(1+n)-PCN) for photocatalytic CO2 reduction. The optimized photocatalyst achieves a high CO formation rate of 46.82 µmol gcat-1 with 70.1% selectivity in solid-liquid mode without sacrificial agents, which is 2.68 and 2.18-fold compared to that of exclusive silver single-atom (Ag1-CN) and cobalt-silver dual-metal site (Co1Ag1-PCN) photocatalysts, respectively. The closely integrated in situ experiments and density functional theory calculations unravel that the electronic metal-support interactions (EMSIs) of Ag nanoparticles with adjacent Ag-N2C2 and Co-N6-P single-atom sites promote the adsorption of CO2* and COOH* intermediates to form CO and CH4, as well as boost the enrichment and transfer of photoexcited electrons. Moreover, the atomically dispersed dual-metal Co-Ag SA sites serve as the fast-electron-transfer channel while Ag nanoparticles act as the electron acceptor to enrich and separate more photogenerated electrons. This work provides a general platform to delicately design high-performance synergistic catalysts for highly efficient solar energy conversion.

Inventory, source and health risk assessment of nitrated and parent PAHs in agricultural soils over a rural river in Southeast China.

Nitrated polycyclic aromatic hydrocarbons (NPAHs) have become a concerning topic because of their widespread occurrence and carcinogenicity. However, studies on NPAHs in soils, especially in agricultural soils, are still limited. In this study, a systematic monitoring campaign of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) was performed in agricultural soils from the Taige Canal basin in 2018, which is a typical agricultural activity area of the Yangtze River Delta. The total concentration of NPAHs and PAHs ranged from 14.4 to 85.5 ng g-1 and 118-1108 ng g-1, respectively. Among the target analytes, 1,8-dinitropyrene and fluoranthene were the most predominant congeners accounting for 35.0% of ∑15NPAHs and 17.2% of ∑16PAHs, respectively. Four-ring NPAHs and PAHs were predominant, followed by three-ring NPAHs and PAHs. NPAHs and PAHs had a similar spatial distribution pattern with high concentrations in the northeastern Taige Canal basin. The soil mass inventory of ∑16PAHs and ∑15NPAHs was evaluated to be 31.7 and 2.55 metric tons, respectively. Total organic carbon had a significant impact on the distribution of PAHs in soils. The correlation between PAH congeners in agricultural soils was higher than that between NPAH congeners. Based on diagnostic ratios and principal component analysis-multiple linear regression model, vehicle exhaust emission, coal combustion, and biomass combustion were the predominant sources of these NPAHs and PAHs. According to the lifetime incremental carcinogenic risk model, the health risk posed by NPAHs and PAHs in agricultural soils of the Taige Canal basin was virtually negligible. The total health risk in soils of the Taige Canal basin to adults was slightly higher than that to children.

Z-Scheme Modulated Charge Transfer on InVO4 @ZnIn2 S4 for Durable Overall Water Splitting.

The charge transfer within heterojunction is crucial for the efficiency and stability of photocatalyst for overall water splitting (OWS). Herein, InVO4 nanosheets have been employed as a support for the lateral epitaxial growth of ZnIn2 S4 nanosheets to produce hierarchical InVO4 @ZnIn2 S4 (InVZ) heterojunctions. The distinct branching heterostructure facilitates active site exposure and mass transfer, further boosting the participation of ZnIn2 S4 and InVO4 for proton reduction and water oxidation, respectively. The unique Z-scheme modulated charge transfer, visualized by simulation and in situ analysis, has been proved to promote the spatial separation of photoexcited charges and strengthen the anti-photocorrosion capability of InVZ. The optimized InVZ heterojunction presents improved OWS (153.3 µmol h-1  g-1 for H2 and 76.9 µmol h-1  g-1 for O2 ) and competitive H2 production (21090 µmol h-1  g-1 ). Even after 20 times (100 h) of cycle experiment, it still holds more than 88% OWS activity and a complete structure.

Insights into adsorption mechanisms of nitro polycyclic aromatic hydrocarbons on common microplastic particles: Experimental studies and modeling.

Nitro polycyclic aromatic hydrocarbons (NPAHs) and microplastics (MPs) are emerging contaminants that pose a threat to the aquatic ecosystem. Knowledge of the NPAHs and MPs interaction will help the understanding of their fate and risks in natural environment. Here, the adsorption behavior and mechanism of typical NPAHs on microplastics were investigated. The adsorption kinetic and isotherm data showed that the adsorption of NPAHs was controlled by chemical adsorption and hydrophobic partition, because of excellent fit of kinetic and isothermal equations (R2 > 0.9). The adsorption capacity (587-744 µg g-1) was largely dependent on the hydrophobicity of NPAHs. The experiment of environmental factors confirmed the important role of pollutant hydrophobicity, with 1-Npyr of the highest hydrophobicity having the greatest adsorption on MPs (adsorption rate >90%) and less affected by solution pH and ionic strength (changer <5%). In the mixture system, MPs displayed high adsorption capacity for each compound; Interestingly, because compounds with smaller size were easy to occupy the adsorption sites in the pores of MPs, the adsorption of 2-Nflu (724 µg g-1) was even greater than that of 9-Nant (713 µg g-1) and 1-Npyr (703 µg g-1). The model calculation of adsorption also shows that there is surface adsorption and hydrophobic distribution in the adsorption process. The findings provide new insights into the interactions of MPs with organic pollutants in complex environments.

Photocatalysis Combined with Microalgae to Promote the Degradation and Detoxification of Tetracycline Hydrochloride.

The continuous discharge of antibiotics into the environment poses a serious threat to the ecological environment and human health. In this study, photocatalysis and microalgae were combined to study the removal of tetracycline hydrochloride (TCH) and its photodegradation intermediates in water. The results showed that after photocatalytic treatment, the removal rate of TCH reached 80%, but the mineralization rate was only 17.7%. While Chlorella sp. alone had poor tolerance to high concentrations of TCH, the combined treatment of photocatalysis and microalgae completely removed TCH and increased the mineralization efficiency to 35.0%. Increased cell density was observed, indicating that TCH and the intermediates produced in the photocatalysis process could be utilized by algae for growth. Meanwhile, TCH degradation pathways were proposed based on Liquid Chromatograph Mass Spectrometer analysis, and the toxicity of intermediates detected was predicted using ECOSAR software, which showed that the type and quantity of highly toxic intermediates decreased significantly after subsequent algal treatment. The results demonstrate that photocatalysis and microalgae combined treatment is an efficient and eco-friendly method for the removal of antibiotics in water.

Bioaccessibility and bioavailability of NPAHs in soils using in vitro-in vivo assays: Comparison of laboratory and outdoor environmental aging effect.

Aging process is one of the most important factors that markedly reduces bioaccessibility and bioavailability (bioac-bioav) of organic contaminants. However, only few data on comparison of the effects of laboratory artificial aging (LAA) and outdoor environmental aging (OEA) processes on nitrated polycyclic aromatic hydrocarbons (NPAHs) bioac-bioav are available. In the current study, oral bioac-bioav of NPAHs in LAA and OEA soils (aging time intervals: 0, 45, 90, 120 and 150 d) were measured by in vitro traditional Fed ORganic Estimation human Simulation Test (FOREhST) and Tenax improved FOREhST (TI-FOREhST) methods, and in vivo mouse model. Tenax significantly increased the bioaccessibility of NPAHs in freshly spiked and aging soils from 0.3-40.9 % to 15.6-95.3 %, and 0.3-40.9 % to 1.0-84.5 %, respectively. Aging significantly reduced the NPAHs bioaccessibility (from 36.5 % to 10.7 %, and 12.1 % to 5.1 % as measured by FOREhST and TI-FOREhST, respectively) and bioavailability (from 27.7 % to 9.9 %, as measured by mouse model). The changes in bioac-bioav were mainly observed within the first 120 d of aging. The statistical analyses of NPAHs bioac-bioav showed no significant difference (p > 0.05) among the aging time intervals in LAA and OEA soils, which demonstrated that the LAA can relatively represent the OEA. Determination of TOC content in LAA and OEA soil can intuitively reflect whether the difference of NPAHs bioac-bioav between two aging treatment groups is significant. The mean bioaccessibility of NPAHs in soil measured by TI-FOREhST (mean 20.6 %) is closer to the bioavailability measured by mouse model (mean 19.4 %), indicating that Tenax improved in vitro method is more reliable than traditional methods, to predict the bioavailability of NPAHs.

Predicting the bioavailability of nitro polycyclic aromatic hydrocarbons in sediments: ZIF-8/h-BN solid-phase microextraction versus Tenax extraction.

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 × 10-2 h-1 (R2 > 0.98). The extraction rates ranking of NPAHs in sediments was 2-nitrobiphenyl>1-nitropyrene>5-nitroacenaphthene>2-nitrofluorene. Compared with SPME, NPAH concentrations reached equilibrium after 168 h for the Tenax extraction. The orders of magnitude of fast, slow, and very slow desorption rate constants were 10-1, 10-2, and 10-4, respectively. At extraction equilibrium (168 h), the SPME was close to the bioavailability of the NPAHs in sediments to Cipangopaludina chinensis with a slope statistically approximated to one. In addition, the linear regression for SPME (R2 = 0.7285) was slightly higher than that of the Tenax extraction (R2 = 0.7168) over a short time (6 h). This could be because the coating material of ZIF-8/h-BN can rapidly adsorb freely dissolved NPAHs, and the SPME fibers can accurately predict the bioaccumulated concentrations of NPAHs in exposed organisms by measuring the concentration of NPAHs in the pore water of sediment. This study provides a time-saving and easy procedure to predict the bioavailability of NPAHs in sediments.

Sedimentary spatial variation, source identification and ecological risk assessment of parent, nitrated and oxygenated polycyclic aromatic hydrocarbons in a large shallow lake in China.

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 (R2 > 0.9824), which showed better optimal performance compared with PCA-MLR (R2 > 0.9564) for PAHs and derivatives, is recommended as the preferred model for quantitative source analysis. Ecological risk assessment showed that the risk quotient values of OPAHs in sediments were much higher than those of other PACs and should be given special attention.

Occurrence and risk of iodinated X-ray contrast media in source and tap water from Jiangsu province, China.

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.

Preparation of nano-ferrous sulfide modified with phytate for efficient Cr(VI) removal in aqueous solutions.

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.

Occurrence, partition behavior, source and ecological risk assessment of nitro-PAHs in the sediment and water of Taige Canal, China.

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 (Kow) and log sediment-water partition coefficient due to hydrophobic interaction. The fugacity fraction value increased with the decrease of log Kow, and chrysene was transferred from water into sediment. The residual NPAHs in surface water and sediment of the Taige Canal have partial correlation. Diesel engine and coal combustion emissions were probably the principal sources of NPAHs in surface water and sediment. The results of ecological risk assessment showed that some NPAHs in water (e.g, 1-nitropyrene and 6-nitrochrysene) and sediment (e.g., 2-nitrobiphenyl, 5-nitroacenaphthene, 9-nitrophenanthrene and 2+3-nitrofluoranthene) had moderate ecological risks, which should be of concern.

Heterogeneous Fenton-like removal of tri(2-chloroisopropyl) phosphate by ilmenite (FeTiO3): Kinetic, degradation mechanism and toxic assessment.

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 FeTiO3 was synthesized by the sol-gel method and employed as the catalyst for the degradation of TCPP by activating persulfate (PS) under UV irradiation. The degradation processes were fitted by the pseudo-first-order kinetic. The kobs value in UV/FeTiO3/PS system was up to 0.0056 min-1 and much higher than that in UV/PS (0.0014 min-1), UV/FeTiO3 (0.0012 min-1) and FeTiO3/PS (0.0016 min-1) systems, demonstrating a distinct synergistic effect in TCPP removal. The degradation efficiency of TCPP increased with the increase of UV intensity, PS concentration and catalyst dosage, and with the decrease of pH. By quenching experiment and EPR analysis, ·OH was confirmed to be the dominant radical in the reaction of the UV/FeTiO3/PS system. The possible degradation pathways of TCPP were dechlorination, dealkylation, and further oxidation of alkyl groups based on the theoretical calculation of frontier molecular orbits. The toxicity of degradation intermediates evaluated by luminescence inhibition rate of photoluminescence was higher than TCPP. Thus, TCPP can be degraded in the UV/FeTiO3/PS system effectively at the premise of introducing controlling measures to reduce the toxicity of degradation intermediates.

Removal kinetics and mechanisms of tetrabromobisphenol A (TBBPA) by HA-n-FeS colloids in the absence and presence of oxygen.

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 (1O2 and •O2-) played a minor role in the removal of TBBPA by the HA-n-FeS colloids with oxygen, where 13% of TBBPA was removed by 1O2 and •O2-. Therefore, in practical applications, the aeration method can be used to significantly improve the removal efficiency of TBBPA by HA-n-FeS colloids in water.