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Organophosphate esters (OPEs) are widely distributed in surface water systems, but limited information was available on the spatial occurrence and ecological risks of OPEs in the Bohai Sea. In this study, 89 water samples in the Bohai Sea and the five surrounding rivers were investigated for the determination of 15 OPEs. The concentration of ∑ 15 OPEs ranged from 373.20 to 2931.27 ng·L -1 in the river water and 137.81 to 2641.30 ng·L -1 in the seawater, with high levels of OPEs in Liaodong Bay. Tris(2-chloroethyl) phosphate (TCEP, 10- 92 %) and triethyl phosphate (TEP, 5- 64 %) were dominant for OPEs. The correlation analysis, principal component analysis and hierarchical cluster analysis suggested the conjunction of municipal wastewater via river input and maritime shipping was the main source of OPEs in the Bohai Sea. The ecological risk assessment indicated that the individual OPEs arise low ecological risks in the Bohai Sea, while medium ecological risks of ∑ 15 OPEs are in minority river samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The photochemical behavior of organic pollutants in ice is poorly studied in comparison to aqueous photochemistry. Here we report a detailed comparison of ice and aqueous photodegradation of two representative OH-PAHs, 2-hydroxyfluorene (2-OHFL) and 9-hydroxyfluorene (9-OHFL), which are newly recognized contaminants in the wider environment including colder regions. Interestingly, their photodegradation kinetics were clearly influenced by whether they reside in ice or water. Under the same simulated solar irradiation (λ > 290 nm), OHFLs photodegraded faster in ice than in equivalent aqueous solutions and this was attributed to the specific concentration effect caused by freezing. Furthermore, the presence of dissolved constituents in ice also influenced photodegradation with 2-OHFL phototransforming the fastest in 'seawater' ice (k = (11.4 ± 1.0) × 10 -2 min -1 ) followed by 'pure-water' ice ((8.7 ± 0.4) × 10 -2 min -1 ) and 'freshwater' ice ((8.0 ± 0.7) × 10 -2 min -1 ). The presence of dissolved constituents (specifically Cl - , NO 3 - , Fe(III) and humic acid) influences the phototransformation kinetics, either enhancing or suppressing phototransformation, but this is based on the quantity of the constituent present in the matrixes, the specific OHFL isomer and the matrix type (e.g., ice or aqueous solution). Careful derivation of key photointermediates was undertaken in both ice and water samples using tandem mass spectrometry. Ice phototransformation exhibited fewer by-products and 'simpler' pathways giving rise to a range of hydroxylated fluorenes and hydroxylated fluorenones in ice. These results are of importance when considering the fate of PAHs and OH-PAHs in cold regions and their persistence in sunlit ice., (Copyright © 2021. Published by Elsevier B.V.)

Pyrethroids are increasingly receiving attention as aqueous micropollutants, but their presence has been reported only in a few small coastal areas. In this study, we investigated the distribution, sources, and risks of nine pyrethroids in large marine zones. The 40 seawater samples were collected from the South Yellow Sea (SYS) and East China Sea (ECS) in China, during the spring of 2020, using a high-volume, solid-phase extraction method. The total pyrethroid concentrations ranged from 0.72 to 1.82 ng L -1 in the SYS and from 0.02 to 11.0 ng L -1 in the ECS. We used cluster analysis to classify pollutant sources into five categories, and discussed the influence of sources on the transport and distribution of pyrethroids in each group. Ecological risk assessment indicated that pyrethroids pose a high risk to crustaceans and a negligible risk to others. These results are important for understanding the behavior of pyrethroids in marine environments., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Wastewater from printing and dyeing processes often contains aniline and high salinity, which are hazardous to aquatic species. Glycophytic plants cannot survive under high-salinity conditions, whereas halophytes grow well in such an environment. In this study, we investigated the influence of NaCl on the antioxidant level in Suaeda salsa affected by aniline stress. The seedlings showed various growth toxicity effects under different concentrations of aniline. The results showed that the effect of the aniline was more severe for the root growth compared to that for the shoot growth. Aniline exposure significantly increased the total free radicals and ·OH radicals in the plants. Suaeda salsa exposure to aniline caused oxidative stress by altering the superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) activity, which resulted in the overproduction of H 2 O 2 and the inducement of lipid peroxidation. Analysis revealed that the malondialdehyde (MDA) content was enhanced after aniline exposure and that the chlorophyll content was significantly decreased. The results showed that aniline induced the production of free radicals and reactive oxygen species (ROS), and changed the antioxidant defense system. This ultimately resulted in oxidative damage in S. salsa; however, it was found that moderate salinity could mitigate the effects. In conclusion, salinity may alleviate the growth inhibition caused by aniline by regulating the antioxidant capacity of S. salsa., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Graphene Oxide (GO) has wide applications in many fields which has caused a large expected quantity of the graphene-based wastes. It is necessary to understand the toxic effects of the GO on the activated sludge (AS) considering its inevitable discharge to the wastewater treatment plants as the ultimate repositories for these wastes. In this study, the acute exposures of the multilayer Nano-graphene oxide (MNGO) at different dosages were conducted in order to investigate its integrated effects on the formation of the biofilm, mature biofilm and the microbial activity of the activated sludge. Raman spectroscopy and laser scanning confocal microscopy (LSCM) were adopted for the in-situ characterization of the biofilm with the exposure of the MNGO. The results showed that the activated sludge was tolerable to the acute exposure of the less than 100 mg/L of the MNGO, especially for the mature biofilm, and only a subtle decrease was found in the size and thickness during the formation of the biofilm, while the amount of 300 mg/L of the MNGO caused the sever deterioration on the activated sludge system. The microbial metabolic activity, viability, and the biological removal of the nutrients were significantly affected with the more than 100 mg/L of the MNGO. It was also demonstrated by the microbial cytotoxicity tests that the increase in the exposure of the MNGO was related to the increase in the reactive oxygen species (ROS) and the damaging degree of the cell membrane., (Copyright © 2020 Elsevier Inc. All rights reserved.)

In this paper, a process combining biodegradation and Fenton oxidation was proposed for the removal of polydiallyldimethylammonium chloride-acrylic-acrylamide-hydroxyethyl acrylate (PDM) in aqueous phase. Biodegradation of PDM was investigated in activated sludge systems, and the effects of the solution pH, mixed liquid suspended solids (MLSS), salinity, co-substrate, and initial substrate concentration, were studied. The biodegradation process was well-described with the Monod model and the values of the kinetics parameters v max , k s were 0.05 h -1 and 333 mg/L. The optimal biodegradation conditions in the experimental range were determined to be: pH = 7.0, 0%-0.01% (w/v) NaCl, 4000 mg/L of MLSS, and 500 mg/L of glucose as co-substrate. FT-IR analysis indicated that PDM molecules biodegradation partly. The microbial community structures and dehydrogenase activity analysis revealed that PDM showed some toxicity to microorganisms in activated sludge. The effects of several parameters, including the pH and chemical doses, were investigated for removing PDM in Fenton oxidation process. The optimal Fenton oxidation process conditions in the experimental range were pH = 2.0, Fe 2+ concentration of 40 mg/L, and H 2 O 2 dosage of 23 mL/L. PDM was treated by biodegradation and subsequent Fenton oxidation under the optimal operating conditions. The removal efficiency was 44.5% after the biodegradation process and further increased to 85.5% after Fenton oxidation. The combined process was revealed to be a promising solution for achieving effective and economical removal of PDM., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Various organic compounds extensively used in the leather industry could influence the performance of alkaline precipitation with Cr(III). This study focused on two typical Cr(III)-bearing complexes (Cr(III)-collagen and Cr(III)-citrate) ubiquitous in tannery effluent yet with distinct treatment efficiencies, as Cr(III) was much more difficult to remove in the Cr(III)-citrate solution. Comprehensive analytical methods were employed to explore the intrinsic mechanism. It was found that a lower removal efficiency towards Cr(III) was significantly associated with higher oligomers. The molecular size of the Cr(III)-citrate complex continued to increase with rising pH, making it larger overall than Cr(III)-collagen species. The growing oligomer moiety of dissolved Cr(III)-complex species could persist in the stronger basic pH range, leading to the large amount of residual Cr(III) in the Cr(III)-citrate system. Combining this result with potentiometric titration and X-ray photoelectron spectroscopy data, it was believed that the polymeric species other than monomers facilitated resisting the attack from hydroxide ions, and the postulated Cr(III)-citrate species towards higher oligomers were discovered. Beyond that, both charge neutralization and sweeping effects were presented among the gradually emerging flocs in the Cr(III)-collagen system together with the electric double layer compression effect derived from salinity, thus resulting in a larger floc size and higher Cr(III) removal efficiency in saline solutions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The European "Community Bureau of Reference" (BCR) sequential extraction procedure, diffusive gradient in thin-films technique (DGT), and physiologically based extraction test were applied to assess metal bioavailability in sediments of Lake Taihu (n = 13). Findings from the three methods showed that Cd was a significant problem in the western lake whereas Cu, Zn, and Ni pollution was most severe in the northern lake. Results from the sequential extraction revealed that more than 50 % of the Cu and Zn were highly mobile and defined within the extractable fraction (AS1 + FM2 + OS3) in the majority of the sediments, in contrast extractable fractions of Ni and Cd were lower than 50 % in most of the sampling sites. Average Cu, Zn, Ni, and Cd bioaccessibilities were <50 % in the gastric phase. Zn and Cd bioaccessibility in the intestinal phase was ∼50 % lower than the gastric phase while bioaccessibilities of Cu and Ni were 47-57 % greater than the gastric phase. Linear regression analysis between DGT and BCR measurements indicated that the extractable fractions (AS1 + FM2 + OS3) in the reducing environment were the main source of DGT uptake, suggesting that DGT is a good in situ evaluation tool for metal bioavailability in sediments.

Effective arsenic removal from highly laden industrial wastewater is an important but challenging task. Here, a combined coprecipitation/nano-adsorption process, with ferric chloride and calcium chloride as coprecipitation agents and polymer-based nanocomposite as selective adsorbent, has been validated for arsenic removal from tungsten-smelting wastewater. On the basis of operating optimization, a binary FeCl3 (520 mg/L)-CaCl2 (300 mg/L) coprecipitation agent could remove more than 93% arsenic from the wastewater. The resulting precipitate has proved environmental safety based on leaching toxicity test. Fixed-bed column packed with zirconium or ferric-oxide-loaded nanocomposite was employed for further elimination of arsenic in coprecipitated effluent, resulting in a significant decrease of arsenic (from 0.96 to less than 0.5 mg/L). The working capacity of zirconium-loaded nanocomposite was 220 bed volumes per run, much higher than that of ferric-loaded nanocomposite (40 bed volumes per run). The exhausted zirconium-loaded nanocomposite could be efficiently in situ regenerated with a binary NaOH-NaCl solution for reuse without any significant capacity loss. The results validated the combinational coprecipitation/nano-adsorption process to be a potential alternative for effective arsenic removal from highly laden industrial effluent.

This work set out to study the effects of cadmium (Cd) in sediments on the antioxidant enzyme activities in the digestive gland of Asian clam Corbicula fluminea and to explore the potential for applying these responses to evaluate the Cd-contaminated sediment. Additionally, diffusive gradients in thin-films (DGT) technique was used to predict the response of its antioxidant defense system. The sediments, collected from Taihu Lake, were spiked with Cd at different concentrations (0.72, 0.91, 1.62, 2.59, 11.2, 20.4 and 40.6 mg kg(-1), dry weight). Asian clam was cultivated for 28 days. Concentrations of Cd in the body of Asian clam had a good relationship with concentrations of Cd in overlying water and sediments, as measured by DGT. Cd affected these biochemical parameters significantly, especially for superoxide (SOD), peroxidase (POD) and glutathione (GSH), which began to show higher sensitivity and have a significant difference in low dosage (0.91 mg Cd kg(-1)) compared with blank. Contents of MDA and MT, which were induced by Cd, increased with the increasing Cd concentration in sediments and reached peak values at 11.2 and 20.4 mg kg(-1), respectively, after 28 days exposure. All of these results suggested that biochemical responses cooperated in detoxifying and maintaining cellular metabolic homeostasis. The R(2) of regression analysis between the contents of MT and the concentrations of Cd measured by DGT, in sediments and soft body were 0.71, 0.94 and 0.88 after 28 days exposure. This suggested that DGT measurement could predict the response of MT. Cd accumulation, GSH and MT were indispensable biomarkers and the MDA content and DGT appeared to be promising biomarkers. The results clearly indicated that Cd could induce oxidative stress in the digestive gland of Asian clam. The combination of biomonitors with DGT can obtain different information about Cd bioavailability and confirm the significance of applying a suite of biomarkers rather than a selective index to assess the sublethal effect. It also offered theoretical methods for the prediction of sediment Cd pollution.

Three azo dyes (Methyl Orange, Direct Brown and Direct Green) were treated by catalytic wet air oxidation (CWAO) with the catalysts CuO/γ-Al(2)O(3) prepared by consecutive impregnation. The relationship of decolorization extent, chemical oxygen demand (COD) removal extent and total organic carbon (TOC) in dye solution were investigated. The results indicated that the CuO/γ-Al(2)O(3) catalyst had excellent catalytic activity in treating azo dyes. Almost 99% of color and 70% of TOC were removed in 2h. The high removal extent of color and TOC indicated that the CWAO obtained perfect decomposition for pollutants. The degradation pathway of azo dyes was analyzed by UV-Vis, FTIR and MS. According to the examined results, the hydroxyl ((·)OH) radicals induced strong oxidizing effects in the target solution and destroyed the chromophoric groups of azo-benzene conjugated of the molecular structure. Considering characteristics of the dye structure, the azo bond (-N=N-) would first be attacked by the hydroxyl radical and other free radicals. With the continuous oxidization and the long reaction time at high temperature, these intermediates could be oxidized to the final oxidation products, such as water and carbon dioxide., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Six stations in the lower reach region of Changjiang River within Baguazhou Island, Nanjing reach were chosen to investigate the toxic metals pollution characteristic in suspended particle material (SPM). SPM concentration, as well as reflectance spectroscopy characteristic, toxic metal concentrations, and lead isotopes of suspended particle material were studied. SPM concentrations were obtained from fluvial cross-sectional sampling near the surface (20 cm) and the study presents the cross-sectional averages. SPM concentrations varied around 170-300 mg L(-1). Reflectance spectroscopy measurements differed from each other over each cross-section but no common pattern characterizing the cross-sectional behavior of the measurements was observed. The metal concentrations in the SPM decreased in the sequence: Mn>Zn>Cu>Cr>Pb>Cd. The result of lead isotopes analysis proved that lead isotopes composition in SPM are mainly produced by natural contributions and influenced by anthropogenic activity at the same time.