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Advanced oxidation processes (AOPs) can significantly alter the structural properties, environmental behaviors and human exposure level of microplastics in aquatic environments. Three typical microplastics (Polyethylene (PE), polypropylene (PP), and polystyrene (PS)) and three AOPs (Heat-K2S2O8 (PDS), UV-H2O2, UV-peracetic acid (PAA)) were adopted to simulate the process when microplastics exposed to the sewage disposal system. 2-Nitrofluorene (2-NFlu) adsorption experiments found the equilibrium time decreased to 24 hours and the capacity increased up to 610 µg g-1, which means the adsorption efficiency has been greatly improved. The fitting results indicate the adsorption mechanism shifted from the partition dominant on pristine microplastic to the physical adsorption (pore filling) dominant. The alteration of specific surface area (21 to 152 m2 g-1), pore volume (0.003 to 0.148 cm3 g-1) and the particle size (123 to 16 µm) of microplastics after AOPs are implying the improvement for pore filling. Besides, the investigation of bioaccessibility is more complex, AOPs alter microplastic with more oxygen-containing functional groups and lower hydrophobicity detected by XPS and water contact angle, those modifications have increased the sorption concentration, especially in the human intestinal tract. Therefore, this indicates the actual exposure of organic compounds loaded in microplastic may be higher than in the pristine microplastic. This study can help to assess the human health risk of microplastic pollution in actual environments.

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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.

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Owing to their bioavailability and toxicity, the dissolved polycyclic aromatic hydrocarbons (PAHs-d) loaded in rivers are harmful to both inland and marine ecosystems. Thus, exploring the changes in PAHs-d levels and sources is important for controlling PAHs pollution. In this study, the concentration of PAHs-d in the mainstream of the Yangtze River during dry and wet seasons was investigated and the source was analyzed using the positive matrix factorization (PMF) model to assess the response of PAHs-d to hydrological and anthropogenic activities changes. The concentration of PAHs-d in the wet season (166.2 ± 52.51 ng/L) was significantly higher than that in the dry season (89.05 ± 20.89 ng/L) (ANOVA, P < 0.001), and the sampling sites with high pollution were mainly distributed in the downstream urban agglomeration. Herein, 2-3 rings were identified to play a dominant role in the composition of PAHs-d. Compared with the dry season, the proportion of the low molecular weight (LMW) PAHs-d were relatively depleted and the high molecular weight (HMW) PAHs-d were accumulated in the wet season. Coal and coke combustion were identified as the main sources of PAHs-d (65.9% in the dry season and 59.2% in the wet season), followed by vehicle emissions, petroleum sources, and biomass combustion. Owing to the change in energy consumption structure and climate characteristics, the sources of PAHs-d displayed seasonal variation and spatial heterogeneity. Further, flow was identified as the most important factor affecting PAHs-d in the hydrological parameters. Increases of flow, pH, and SPM decreased the proportion of LMW PAHs-d, and increased that of HMW PAHs-d. The increase in anthropogenic activities intensified the residual levels of 2-3rings and 5-6 rings in water, but had no significant impact on the levels of 4 rings.

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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 (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.

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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.

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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.

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Nitro-polycyclic aromatic hydrocarbons have been detected in various environmental media. However, determination in sediment matrix is challenging due to the lack of a suitable method. In this study, a reliable method for determining 15 nitro-polycyclic aromatic hydrocarbons in sediments was developed based on accelerated solvent extraction and solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry. The accelerated solvent extraction and solid-phase microextraction are sample pre-treatment techniques that have advantages, such as rapid operation and minimal sample volume. Initially, the solid-phase microextraction was optimized using five commercial fibers and from that 65 µm polydimethylsiloxane/divinylbenzene fiber was selected as the best fiber. Further, the accelerated solvent extraction conditions were optimized by Taguchi experimental design, such as extraction temperature (120℃), extraction solvent (dichloromethane), number of cycles (two), static extraction period (4 min), and rinse volume (90%). The method parameters, such as limits of quantitation, and intraday and interday accuracy and precision, were in the range of 0.067-1.57 ng/g, 75.2-115.2%, 69.9-115.4%, and 1.0-16.5%, respectively. Upon meeting all the quality criteria, the method was applied successfully to analyze real sediment samples. Therefore, our study creates a new prospect for the future application of direct immersion solid-phase microextraction in sediment analysis.

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Visible light driven plasmonic Ag/Ag3PO4/g-C3N4 heterojunction nanocomposite with regular morphology was prepared via a modified facile method. The two-dimensional ultrathin g-C3N4 nanosheet is uniformly wrapped on the surface of Ag3PO4 nanopolyhedron. A charge transfer bridge was built between Ag3PO4 nanopolyhedron and g-C3N4 nanosheet due to the reduction of Ag nanoparticles. This structure can inhibit the recombination of photogenerated electron-hole pairs and promote the transfer of photogenerated carriers, so as to produce more active species for participating in the photocatalytic reaction. In addition, the surface plasmon resonance (SPR) of appropriate Ag nanoparticles enhanced the absorption and utilization of visible light. Compared with Ag3PO4 and Ag/Ag3PO4, Ag/Ag3PO4/g-C3N4 showed higher photocatalytic activity. Under visible light irradiation, the degradation rate of phenanthrene (PHE) was 0.01756 min-1, which was 3.14 times and 2.38 times that of Ag3PO4 and Ag/Ag3PO4, respectively. After four cycles of photocatalytic reaction, the Ag/Ag3PO4/g-C3N4 photocatalyst still maintained high photocatalytic activity. The active sites of PHE were predicted by Gaussian simulation calculation and combined with intermediate products identification of GC-MS, the possible degradation pathway of PHE was speculated. This research has reference significance for the construction of plasmonic heterojunction photocatalyst in the field of environmental pollution remediation.

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Developing sheet-on-sheet (2D/2D) heterostructure with built-in electric field (BIEF) is effective in boosting the performance of photocatalysts for emerging contaminants degradation. Herein, the 2D/2D microtopography and (-)TiO2/(+)Bi2MoO6 BIEF were precisely integrated into hierarchical nanosheets, which can provide the basis and driving force for charge transfer both in in-plane and interface of heterojunction. The prepared photocatalyst (TiO2/Bi2MoO6) showed high-efficiency and stable performance for photocatalytic amoxicillin (AMX) degradation, which was 18.2 and 5.7 times higher than TiO2 and Bi2MoO6, respectively. More importantly, TiO2/Bi2MoO6 showed more efficient photocatalytic activity and photogenerated charge separation than TiO2@Bi2MoO6 (different morphology). Besides, four possible pathways of AMX degradation were proposed depending on Gaussian calculations and intermediates analysis by GC-MS and HPLC-TOFMS. This work sheds light on the design and construction of unique 2D/2D heterostructure photocatalysts for AMX degradation.

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Nitrated polycyclic aromatic hydrocarbons (NPAHs) have toxic potentials that are higher than those of their corresponding parent polycyclic aromatic hydrocarbons (PAHs) and thus have received increasing attention in recent years. In this study, the occurrence, distribution, source, and human health risk assessment of 15 NPAHs and 16 PAHs were investigated in the surface water from 20 sampling sites of Lake Taihu during the dry, normal, and flood seasons of 2018. The ΣPAH concentrations ranged from 255 to 7298 ng/L and the ΣNPAH concentrations ranged from not-detected (ND) to 212 ng/L. Among the target analytes, 2-nitrofluorene (2-nFlu) was the predominant NPAH, with a detection frequency ranging from 85% to 90% and a maximum concentration of 56.2 ng/L. The three-ringed and four-ringed NPAHs and PAHs comprised the majority of the detected compounds. In terms of seasonal variation, the highest levels of the ΣNPAHs and ΣPAHs were in the dry season and flood season, respectively. Diagnostic ratio analysis indicated that the prime source of NPAHs was direct combustion, whereas in the case of PAHs the contribution was predominantly from a mixed pattern including pollution from unburned petroleum and petroleum combustion. The human health risk of NPAHs and PAHs was evaluated using a lifetime carcinogenic risk assessment model. The carcinogenic risk level of the targets ranged from 2.09 × 10-7 to 5.75 × 10-5 and some surface water samples posed a potential health risk.

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The role of illumination and cathode is important to improve the efficiency of photoelectro-Fenton (PEF) system. In this study, cathodes with black carbon-poly tetra fluoro ethylene (BC-PTFE) for increase the concentration of hydrogen peroxide in PEF. A new PEF system using EIEL and BC-PTFE air-diffusion cathode was established. The electrode performance was tested and the influence factors, degradation kinetics, intermediates, pathway and mechanism of the model compound methyl orange (MO) were studied. The capacities of concentration decays and total organic carbon (TOC) removals were compared between different electrochemical advanced oxidation processes. The experimental conditions were optimized for a current density of 20 mA cm-2 with 0.5 mM Fe2+ and 100 mg L-1 MO at 20 °C and pH 3.0 in an 8 L reservoir. The higher MO concentration was, the smaller pseudo-first-order kinetic constants of concentration decays and TOC removals were. Intermediate products were identified by gas chromatography-mass spectrometry and ion-exclusion high performance liquid chromatograph in EIEL-PEF. Combined with frontier electron density, the degradation pathway was deduced as follows: destruction of azo bond, substitution of •OH, dehydrogenation and oxidation, opening-ring and mineralization. In EIEL-PEF, the concentration of oxalic acid and oxamic acid reached the maximum value 9.2 and 1.5 mg L-1 at 60 and 90 min, respectively. The photolysis of N-intermediates produced NH4+-N was released in more proportion than NO3--N and oxamic acid-N. The study indicated that PEF system has the potential to remove organic pollutants in aquatic environments.

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It is important to establish an available analytical method for polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs (nitro-PAHs), oxygenated forms of PAHs (oxy-PAHs), and hydroxy-PAHs (OH-PAHs) in sediment samples due to the fact that they co-exist in various environmental mediates, particularly in sediment. In this study, an analytical method has been developed and validated for the quantification of PAHs, nitro-PAHs, oxy-PAHs, and OH-PAHs in sediment samples. The sediment samples were extracted by accelerated solvent extraction and cleaned up with SPE alumina-n combining with aminopropyl cartridges. The extracts were further fractionated by using different solvents. The fractionated extracts were analyzed via gas chromatography of single and triple quadrupole mass spectrometry in the electron ionization and negative ion chemical ionization with selective ion monitoring and selective reaction monitoring mode and liquid chromatography-triple quadrupole mass spectrometry. Each group of analytes was determined by different instrument modes such as GC-EI-SIM for PAHs, GC-NICI-SRM for nitro-PAHs, GC-EI-SRM for the oxy-PAHs and LC-ESI-MS/MS for OH-PAHs. A total of 44 analytes (16 PAHs, 14 nitro-PAHs, 9 oxy-PAHs, and 5 OH-PAHs) and 6 deuterated surrogates were performed. Most of recovery percentage varied from 52.8% up to 114.1% for the targeted analytes verified at three concentration levels (100 ng/g, 400 ng/g and 1000 ng/g for PAHs and 10 ng/g, 50 ng/g and 400 ng/g for their derivatives). The repeatability determined by the relative standard deviation percentage of triplicate trials was less than 10% for most analytes. The limit of detection ranged from 0.01 to 0.02 ng/g for PAHs, 0.002-0.067 ng/g for nitro-PAHs, 0.01-0.1 ng/g for oxy-PAHs, and 0.003-0.006 ng/g for OH-PAHs. Most of the compounds were detectable in the sediments collected from a local River, which illustrates the developed method could be a practical and suitable technique for detection of PAHs and their derivatives in real sediment samples.

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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.

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A solid-phase microextraction coupled with gas chromatography and mass spectrometry method has been developed for the determination of ten nitrated polycyclic aromatic hydrocarbons in water samples. Five different kinds of commerical fibers were used to compare the extraction efficiency, including 65 µm polydimethylsiloxane/divinylbenzene, 100 µm polydimethylsiloxane, 30 µm polydimethylsiloxane, 7 µm polydimethylsiloxane, and 85 µm polyacrylate fibers. Five factors were also selected to optimize conditions, including extraction temperature, time, stirring speed, salt concentration, and headspace volume. Taguchi design was applied to design the experiments and obtain the best parameters. The results show that 65 µm polydimethylsiloxane/divinylbenzene fiber directly immersed into aqueous solution for 35 min at 55°C with a constant stirring rate of 1150 rpm were the optimal conditions. Under these conditions, the limits of quantification were 0.007-0.063 µg/L, and the relative standard deviation based on six replicates ranged from 2.8 to 9.5%. The spiked recoveries ranged from 69.1 to 110.1%. Intra- and inter day relative standard deviations at three concentration levels were less than 12%, and the recoveries were 66.4-111.5%. The proposed method is reliable for analyzing nitrated polycyclic aromatic hydrocarbons in different water samples.