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Abstract The growing population in urban area impacted the water quality of the urban rivers receiving treated municipal wastewater. Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (SPAHs) are corresponding to the population density. In this study, the concentrations of 16 PAHs and 17 SPAHs, including 4 methyl PAHs (MPAHs), 4 oxygenated PAHs and 9 chlorinated PAHs were investigated in the major urban rivers receiving the effluent from 5 major wastewater treatment plants (WWTPs) in the mega city Beijing. The concentrations of ΣSPAHs (307 ± 68 ng/L) were similar to ΣPAHs (321 ± 92 ng/L) in the total phase (aqueous + particulate) suggesting that SPAHs in the urban rivers should be taken into consideration. The lower concentrations of ΣPAHs and ΣMPAHs in this study than the wastewater receiving rivers and WWTPs effluent previously (2010–2013), as well as the lower concentration in the heating seasons than the non-heating season in the investigated year implied the reduction of coal combustion for heating and power generation in recent years. Although WWTPs effluent was theoretically the only source to the urban rivers in the investigated season, April and November, PAHs and SPAHs in most rivers were demonstrated to be originated from other unknown sources besides the WWTPs effluent. The reduction from the original source, coal combustion (33% and 30%), was more efficient than from the wastewater treatment upgrading (15%) for the reduction of PAHs and SPAHs in the urban rivers. Graphical abstract Image 1 Highlights • The concentrations of ΣSPAHs were similar to ΣPAHs. • Reduction of PAHs and MPAHs from 2010 to 2015 proved energy transformation. • Beside WWTP effluent, PAHs and MPAHs in rivers also originate from unknown sources. • Coal reduction more efficient than WWTP upgrading for PAHs and SPAHs reduction. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic compound (PAC) contamination in soil as a result of oil spills is a serious issue because of the huge global demand for fossil energy. This study assessed the vertical variation in polycyclic aromatic hydrocarbons (PAHs), derivatives of PAHs (dPAHs) and bacterial community structure in deep soil with long-term contamination by oil spillage. Our results suggest that the content of total PACs ranged from 1196.6 μg/kg to 14980.9 μg/kg and decreased with depth at all sites. PAHs were the most abundant PACs, with a mean concentration of 6640.7 μg/kg, followed by oxygenated PAHs (mean 156.3 μg/kg) and nitrated PAHs (mean 33.4 μg/kg). PAHs are mainly low molecular weight PACs such as naphthalene, fluorene and phenanthrene, while derivatives of PAHs are all low molecular weight PACs and mainly oxygenated PAHs. Low molecular weight PAHs were an important source of dPAHs under specific conditions. The bacterial community structure showed higher bacterial diversity and lower bacterial richness in shallow soil (2–6 m in depth) than in deep soil (8–10 m in depth). Spearman's analysis confirmed that dramatic bacterial community shifts are a response to contamination. At the genus level, the presence of PACs highly selected for Pseudomonas , belonging to Proteobacteria. Moreover, functional predictions based on Tax4Fun revealed that soil with long-term contamination had a strong potential for PAC degradation. In addition, statistical analysis showed that oxidation-reduction potential (Eh) was closely related to variations of bacterial community composition and function. Finally, Ramlibacter , Pseudomonas , Pseudonocardia , c_MB-A2-108 , f_Amb-16S-1323 , and Qipengyuania were identified by cooccurrence network analysis as keystone taxa contributing to the maintenance of bacterial ecological function. Together, our results provide evidence of tight bacterial effects of PAHs and dPAHs and a more complete understanding of the fate of PACs in deep contaminated soils. [Display omitted] • Total PAC concentrations decreased with increasing soil depth. • Low molecular weight PAHs were an important source of dPAHs. • Variations of Eh and PACs droved assembly of microbial communities. • Actinobacteria was more adaptable to higher PAC pollution than Proteobacteria. • The soil with long-term contamination had a strong potential for PACs biodegradation. [ABSTRACT FROM AUTHOR]

Soil-slurry bioreactor based bioremediation of polycyclic aromatic hydrocarbons (PAHs) contaminated soil was studied through laboratory and pilot-scale trials, in which the degradation mechanism was explored. Indigenous PAH-degrading consortium was firstly screened out and it degraded 80.5% of total PAHs in lab-scale bioreactors. Then a pilot-scale trial lasting 410 days was conducted in two bioreactors of 1.5 m3 to examine the operating parameters and validate the optimum running conditions. During the initial 200 days, the crucial running parameters affecting PAH removal were evaluated and selected. Subsequently, an average PAH removal rate of 93.4% was achieved during 15 consecutive batches (210 days) under the optimum running conditions. The kinetic analysis showed that the reactor under optimum conditions achieved the highest PAH degradation rate of 0.1795 day−1 and the shortest half-life of 3.86 days. Notably, efficient mass transfer of PAHs and high biodegradation capability by bioaugmented consortia in soil-slurry bioreactors were two key mechanisms for appreciable PAH removal performance. Under the optimal operating conditions, the degradation rate of low-molecular-weight (LMW) PAHs was significantly higher than high-molecular-weight (HMW) PAHs; when the mass transfer was limited, there was no significant difference between their degradation behaviors. Both microbial co-metabolism and collaborative metabolism might occur when all PAHs demonstrated low degradation rates. The findings provide insightful guidance on the future assessment and remediation practices of PAH-contaminated sites. [Display omitted] • Indigenous bacterial consortium was more conducive to efficient degradation. • Kinetic analysis of the pilot-scale trial showed rapid and efficient remediation. • Aeration and water-soil ratio were main PAH degradation factors. • Mass transfer determined the PAH degradation behaviors. [ABSTRACT FROM AUTHOR]

Phenanthrene, as a widespread polycyclic aromatic hydrocarbons (PAHs) contaminant in vitro and in vivo of plant, has the characteristics of carcinogenicity, teratogenicity and mutagenicity. This work aimed to explore the phenanthrene metabolic mechanism by Phomopsis liquidambari in vitro, as well as the bioremediation ability through P. liquidambari -rice combination. This strain was able to use phenanthrene as source of carbon and energy to grow, more than 77% of added 50 mg L −1 phenanthrene was removed after 10 d in MSM. We identified the metabolic products via HPLC-MS and proposed two possible degradation pathways. Phenanthrene was firstly combined with oxygen to become phenanthrene 9,10-oxide, and then degraded to 9-phenanthrol, followed by oxidization to 9,10-dihydroxyphenanthrene. In addition, that epoxide (phenanthrene 9,10-oxide) was also hydrolyzed to phenanthrene trans -9,10-dihydrodiol, and then dehydrogenized to 9,10-dihydroxyphenanthrene, which was further degraded to 9,10-phenanthrenequinone; during this metabolic pathway, the changes of P450 monooxygenase, epoxide hydrolase, dehydrogenase and catechol 2,3-dioxygenase activities and their corresponding gene transcription levels were closely related. What's more, P. liquidambari could combine with rice to eliminate phenanthrene accumulated in vivo of rice seedlings, and the removal rate in inoculation treatment represented a significant difference (increased 25.68%) compared with uninoculation treatment after cultivation 30 d. Therefore, we concluded that P. liquidambari could not only respond to phenanthrene pollution stress in vitro but also exert a mitigation effect on plants accumulated phenanthrene. This work provides a foundation for applying endophytic fungi to PAHs bioremediation in vitro and in vivo. [ABSTRACT FROM AUTHOR]

This study aimed to develop an exact mass suspect screening approach to perform finding of multiple lipophilic marine toxins (LMTs) in seawater, suspended particulate matter (SPM), and marine sediment from marine aquaculture area using liquid chromatography-time of flight mass spectrometry (LC-TOF/MS). The method was validated and proven to be reliable for the screening of various LMTs. Then, the method was applied to screen LMTs in marine environmental samples collected from mariculture area of Jiaozhou Bay, China. Okadaic acid (OA), pectenotoxin 2 (PTX2), etc were detected and tentatively identified. Positive detection results were confirmed by liquid chromatography-tandem mass spectrometry (LC–MS/MS), and contents of OA and PTX2 in seawater, SPM and marine sediment were also quantified. The mean concentration of OA ranged from 2.71 to 14.06 ng L −1 in seawater and from 0.78 to 3.34 ng g −1 dry weight in marine sediment. The mean concentration of PTX2 ranged from 0.86 to 7.90 ng L −1 in seawater, from 1.56 to 10.67 ng in SPM obtained from 1 L seawater sample and from 0.95 to 2.23 ng g −1 dry weight in marine sediment. The above results suggested that the proposed method was convenient and reliable for the screening of LMTs in different marine environmental samples. In addition, typical LMTs exist in different marine environmental media of the mariculture area of Jiaozhou Bay, China. Follow-up studies should focus on improving current understanding on the environmental behavior of these LMTs in the marine aquaculture environment. [ABSTRACT FROM AUTHOR]

Here, the bio-nanocomposite (n-HFP + n-HFS)@ An was developed to simultaneously immobilize Pb, Cd and As in the severely contaminated soil. The immobilization rates of diethylenetriaminepentaacetic acid (DTPA)/decarbonate-extracted bioavailable Pb, Cd and As were 59.87%, 31.28% and 62.30%, and the immobilization rates of their water-soluble forms were 63.12%, 60.02% and 89.39%, respectively. Moreover, the ten-year acid rain simulated leaching assay showed that the maximum cumulative release contents of Pb, Cd and As in the treated soil samples were decreased by 2.94, 2.46 and 40.60 times, comparing to the un-treated ones. Additionally, the results of SBRC (Solubility Bioaccessibility Research Consortium) revealed that the bioaccessible rates of the three metals in intestinal phase were lower than in gastric phase, and both of them decreased with increasing the immobilization time. The gastric bioaccessibility of Pb, Cd and As had a higher correlation with the contents of water-soluble forms, while the intestinal bioaccessibility was more strongly positively associated with the bioavailable forms. • A novel bio-nanocomposites simultaneously immobilize Pb, Cd and As in soil. • Bioavailable and water-soluble Pb, Cd and As were significantly immobilized. • Immobilized metals were stable in the ten-year acid rain simulated leaching assay. • Gastric bioaccessibility had a higher correlation with water-soluble metals. • Intestinal bioaccessibility was more strongly associated with bioavailable metals. [ABSTRACT FROM AUTHOR]

The reductive degradability and decomposition pathways of linear perfluorooctanesulfonate (L-PFOS) were investigated in a biomimetic system consisting of Ti(III)-citrate and Vitamin B 12. Biomimetic degradation of L-PFOS could well be described by a first-order exponential decay model. Accompanied by the release of fluoride ion, technical PFOS could not only be transformed to perfluorocarboxylates (PFCAs) and perfluoroalkylsulfonates (PFSAs) with perfluoroalkyl carbon chain length < C8 (thereafter referred as carbon-chain-shortened degradation products), but also be transformed to PFCAs with perfluoroalkyl carbon chain length ≥ C8 (thereafter referred as carbon-chain-lengthened degradation products). Perfluorohexanesulfonate and perfluorotetradecanoate were the most abundant carbon-chain-shortened and -lengthened degradation products of technical PFOS, respectively. Based on the various degradation products detected during biomimetic reduction of linear [1,2,3,4–13C 4 ]-PFOS, the degradation pathways of L-PFOS were proposed as follows: L-PFOS was first reduced to C 8 F 17 • radical by cleavage of C–S bond, and then transformed to PFOA through hydrolysis. However, the carbon-chain-shortened products were not generated through the sequential chain-shortening via C 8 F 17 • radicals and/or L-PFOS, while the carbon-chain-lengthened products were not formed via C 8 F 17 • radicals by stepwise addition of CF 2 moiety. In fact, C 8 F 17 • radical and/or L-PFOS were further reduced to form C n F 2n+1 • (n = 1, 2, 3, 4) radicals, and these radicals were chain-lengthened by stepwise addition of C 4 F 8 moiety and eventually transformed to various degradation products via hydrolysis (PFCAs) or combination reaction with sulfonyl hydroxide (PFSAs). All carbon-chain-lengthened chemicals were first reported as the degradation products during the decomposition of L-PFOS, while carbon-chain-shortened compounds were first identified as the biomimetic reduction products of L-PFOS. Image 1 • L-PFOS degradation can be well described by an exponential decay model • Biomimetic degradation of L-PFOS to short- & long-chain perfluorinated products • Perfluorinated products of L-PFOS were first detected in a biomimetic system [ABSTRACT FROM AUTHOR]

People are inevitably exposed to phthalates (PEs) ubiquitously existing in environment. Our previous studies, simulating the actual situations of people exposure to PEs, have shown that the sub-chronic exposure to low-doses PEs mixture (MIXPs) impaired reproductive function in male rats. Zinc is an important element in maintaining male reproductive functions. However, it is still unknown whether zinc supplement could mitigate PEs-induced male reproductive toxicity or not with sub-chronic low-dose mixture exposure. This study aimed to explore the effect of zinc supplement on the reproductive toxicity caused by sub-chronic MIXPs exposure (160 mg/(kg•body weight)/d, for 90 days) in male rats, and further to reveal the underlying mechanisms. Testosterone (T), FSH and LH in serum, early toxicity indicators in urine, PIWI proteins (PIWIL1 and PIWIL2) expression in testes and pathological examination were performed for toxicity evaluation. Steroidogenic proteins (17β-HSD, StAR, CYP17A1, P450scc and SRD5A) were measured for mechanisms of exploration. The results indicated that zinc supplement could inhibit the T, LH, FSH level decreases in serum, abolish the effect of 5 early toxicity indicators' levels in urine, restrain the alteration of PIWI proteins expression and improve the constructional injury of testes. These effects might be relevant with the suppressed alteration of the expression of steroidogenic proteins induced by MIXPs in rat testicular cells. This work may offer further insights into reducing health risks of MIXPs exposure. • The study reflects actual integrated exposure to phthalates in repeated dose model. • 5 early toxicity indicators in urine were performed for the toxicity evaluation. • Zinc could inhibit the reproductive toxicity of phthalates' mixture. • The toxic effects of phthalates were associated with androgen metabolism. [ABSTRACT FROM AUTHOR]

The dye wastewater treatment by membrane separation technology has obtained extensive attention in recent years. Nevertheless, it was rare for research on the removal of differently charged mixed dyes. In this study, several UiO-66-NH 2 composite membranes were prepared and optimization experiments were conducted. The performance of composite membranes were evaluated by the removal of cationic (Methylene blue, MB), neutral (Rhodamine B, RB), and anionic (Congo red, CR) dyes. The optimization results demonstrated that the UiO-66-NH 2 /graphene oxide (UNG) composite membrane (PUF/PDA/UNG) which was loaded on polyurethane foam modified with polydopamine (PUF/PDA) had the best properties. In filtration experiments, the solution pH exhibited greater effect on the removal efficiency of MB and CR than RB. When NaCl, KCl, CaCl 2 and Na 2 SO 4 coexisted in the dye solution, the removal efficiency of MB by PUF/PDA/UNG membrane were 96.62%, 98.17%, 86.39% and 99.34% respectively. The presence of humic acid showed slight inhibitory effect on the removal of MB by PUF/PDA/UNG membrane (71.93%). The experimental results for mixed dyes filtration showed that PUF/PDA/UNG membrane could effectively remove MB, RB and CR in binary (i.e., MB/RB and RB/CR) and ternary (i.e., MB/RB/CR) systems through secondary filtration. And PUF/PDA/UNG membrane could remove MB and CR simultaneously through one-time filtration in MB/CR binary system. The removal mechanism was mainly attributed to the aggregation of mixed dyes, electrostatic interaction between dye molecules and the membrane surface, and hydrogen bonding. All results suggested that the as-prepared PUF/PDA/UNG membrane have great potential in practical treatment of dye wastewater. Image 1 • Several UiO-66-NH 2 composite membranes loaded on polyurethane foam were fabricated. • PUF/PDA/UNG membrane showed best properties in series of optimization experiments. • PUF/PDA/UNG composite membrane exhibited excellent removal efficiency towards MB. • PUF/PDA/UNG composite membrane could simultaneously remove RB, MB, and CR. • Electrostatic interaction and hydrogen bonding were contributed to the dyes removal. [ABSTRACT FROM AUTHOR]