Organophosphate Esters (OPEs) Flame Retardants in Water: A Review of Photocatalysis, Adsorption, and Biological Degradation.

As a substitute for banned brominated flame retardants (BFRs), the use of organophosphate esters (OPEs) increased year by year with the increase in industrial production and living demand. It was inevitable that OPEs would be discharged into wastewater in excess, which posed a great threat to the health of human beings and aquatic organisms. In the past few decades, people used various methods to remove refractory OPEs. This paper reviewed the photocatalysis method, the adsorption method with wide applicability, and the biological method mainly relying on enzymolysis and hydrolysis to degrade OPEs in water. All three of these methods had the advantages of high removal efficiency and environmental protection for various organic pollutants. The degradation efficiency of OPEs, degradation mechanisms, and conversion products of OPEs by three methods were discussed and summarized. Finally, the development prospects and challenges of OPEs' degradation technology were discussed.

Visible-light-assisted persulfate activation by SnS2/MIL-88B(Fe) Z-scheme heterojunction for enhanced degradation of ibuprofen.

Herein, a highly efficient Z-scheme SnS2/MIL-88B (Fe) (SnSFe) heterojunction was successfully synthesized to use both as photocatalysts and persulfate (PS) activator for ibuprofen (IBP) degradation. Flower-liked SnS2 was uniformly loaded on MIL-88B (Fe), and SnSFe retained the original polyhedral morphology of MIL-88B (Fe). The highest removal of IBP was achieved in the presence of SnSFe with 0.5% SnS2(SnSFe0.5). Characteristic results and density functional theory calculations demonstrated that the enhanced degradation of IBP was due to the difference in Fermi energy levels of SnS2 and MIL-88B (Fe) leading to electrons transferred from SnS2 to MIL-88B (Fe), and SnO bond was formed in SnSFe. , OH and O2- were the main active species in SnSFe0.5/PS/visible light system. Z-scheme heterojunction of SnSFe was constructed to propose the degradation mechanism. This research revealed that the synergism of photocatalysis and PS activation using SnS2/Fe-based MOFs composites possessed great potentials in wastewater remediation.

Ibuprofen degradation by a synergism of facet-controlled MIL-88B(Fe) and persulfate under simulated visible light.

The photocatalysis/persulfate (PS) hybrid system has proven to be a promising method for degrading organic pollutants from aqueous solutions. In this study, three MIL-88B(Fe) iron-based metal-organic framework (MOF) phases with different facet content were prepared and used both as photocatalysts and catalysts for PS activation to remove ibuprofen (IBP). The results showed that there was a close correlation between the exposed facets and the catalytic activity. MIL-88B(Fe)-1 (M88B1) with exposed {100} facets and proportionally more {101} facets showed the best catalytic activity. The optimum PS dosage used in this study was 60 mg/L. The presence of Cl-, SO42-, and NO3- all inhibited the degradation of IBP. X-ray photoelectron spectroscopy (XPS) showed that M88B1 possessed more Fe2+ than the other two MIL-88B(Fe) MOF phases, making it easier to generate active radicals through PS activation. The UV-vis diffuse reflectance spectra (DRS), photoluminescence (PL), and electrochemical analysis indicated that M88B1 possessed the highest light absorption, most active sites, and fastest charge transfer ability. Radical scavenging and electron spin resonance (ESR) experiments demonstrated that SO4-•, •OH, O2-•, and 1O2 species participated in the IBP degradation process. Furthermore, density functional theory (DFT) calculations were performed to identify the crystallographic facets, band structure, and total density of states of MIL-88B(Fe) to further confirm the mechanism of MIL-88B(Fe) as a photocatalyst and a PS activator. This work provides new insights into the synergism between photocatalysis and persulfate activation by facet-controlled MOFs for environmental remediation.

Boron nitride nanosheets decorated MIL-53(Fe) for efficient synergistic ibuprofen photocatalytic degradation by persulfate activation.

In this study, based on one-step hydrothermal method, boron nitride nanosheets (BNNs) and MIL-53(Fe) composites (BNFe-X) were successfully prepared and the catalytic performance of BNFe-X on persulfate (PS) activation for ibuprofen (IBP) photodegradation was investigated. The introduction of BNNs changed the morphology of MIL-53(Fe) to be a unique prism-like structure and enhanced the degradation efficiency of IBP, which followed the pseudo-first-order rate kinetics. Among the prepared composites, BNFe-3 (3% BNNs) exhibited the highest IBP degradation activity and possessed strong stability after four cycles. Over 99% IBP removal was achieved at the irradiation time of 60 min. The promoted decomposition rate of IBP could be ascribed to be the activation of PS and the enhanced electrons transfer efficiency between BNNs and MIL-53(Fe). The scavenger studies and electron spin-resonance spectroscopy (ESR) demonstrated the generation of SO2-, OH and O2-, and all these radicals had the different contributions in IBP degradation. Based on the LC-MS-MS and TOC results, the possible decomposition pathways of IBP in BNFe-3/PS system were proposed. This work suggested that the BNNs/Fe-based MOFs composites and PS system had great potential in organic pollutants degradation in aqueous solution.

The fate and risk assessment of psychiatric pharmaceuticals from psychiatric hospital effluent.

Psychiatric pharmaceuticals are gaining public attention because of increasing reports of their occurrence in environment and their potential impact on ecosystems and human health. This work studied the occurrence and fate of 15 selected psychiatric pharmaceuticals from 3 psychiatric hospitals effluent in Shanghai and investigated the effect of hospitals effluent on surface water, groundwater, soil and plant. Amitriptyline (83.57ng) and lorazepam (22.26ng) showed the highest concentration and were found frequently in hospital effluent. Lorazepam (8.27ng), carbamazepine (83.80ng) and diazepam (79.33ng) showed higher values in surface water. The concentration of lorazepam (46.83ng) in groundwater was higher than other reports. Only six target compounds were detected in all three soil points in accordance with very low concentration. Alkaline pharmaceuticals were more easily adsorbed by soil. Carbamazepine (1.29ng) and lorazepam (2.95ngg-1) were frequently determined in plant tissues. The correlation analyses (Spearman correlations > 0.5) showed the main source of psychiatric pharmaceuticals pollutants might be hospital effluents (from effluent to surface water; from surface water to groundwater). However, hospital effluents were not the only pollution sources from the perspective of the dilution factor analysis. Although the risk assessment indicated that the risk was low to aquatic organism, the continuous discharge of pollution might cause potential environment problem.

Hexabromocyclododecane and tetrabromobisphenol A in tree bark from different functional areas of Shanghai, China: levels and spatial distributions.

The concentrations and spatial distributions of hexabromocyclododecane (HBCDD) and tetrabromobisphenol A (TBBPA) were measured in tree bark from different functional areas of Shanghai. ΣHBCDD (sum of α-, ß-, and γ-HBCDD) concentrations ranged from 1.2 × 102 to 6.6 × 103 ng g-1 lw (median 5.7 × 102 ng g-1 lw) and TBBPA concentrations ranged from 48 to 7.2 × 104 ng g-1 lw (median 2.8 × 102 ng g-1 lw). The concentrations of ΣHBCDD and TBBPA all followed the order of industrial areas > commercial areas > residential areas. The mean percentage of α-HBCDD in bark samples (44%) from Shanghai was higher than that in technical HBCDD products, but comparable with that in air. The concentrations of TBBPA and individual HBCDD diastereoisomers between industrial areas and commercial areas were correlated. Based on the concentrations of HBCDD in the bark, the corresponding atmospheric HBCDD concentrations were estimated. Compared with the published data for HBCDD in urban air, the estimated atmospheric HBCDD concentrations in Shanghai had a relatively high level, and more attention should be paid to the pollution status of HBCDD in Shanghai.

Polybrominated diphenyl ethers (PBDEs) in soil and outdoor dust from a multi-functional area of Shanghai: levels, compositional profiles and interrelationships.

In this study, 14 polybrominated diphenyl ethers (PBDEs) congeners were investigated in soil and outdoor dust taken from Jiading District, Shanghai City. The concentrations of Σ13PBDEs (BDE-17, BDE-28, BDE-47, BDE-66, BDE-71, BDE-85, BDE-99, BDE-100, BDE-138, BDE-153, BDE-154, BDE-183 and BDE-190) and BDE-209 ranged from 0.37 to 32.9ngg(-1) and 4.31 to 141.8ngg(-1) dry weight (dw) in soil. Concentrations in outdoor dust ranged from 1.03 to 112.5ngg(-1) and 6.71 to 342.1ngg(-1) (dw) for Σ13PBDEs and BDE-209. BDE-209 was the predominant congener both in soil and outdoor dust, but the BDE-209 contribution was much lower in dust compared with that in soil. A significant correlation between PBDEs congeners and specific land use type was observed, and principal component analysis (PCA) revealed that the major source of PBDE in samples was associated with prevalent use of technical Deca-BDE, which also suggested the contributions from Penta-BDE and Octa-BDE mixtures. Canonical correlation analysis suggested the two sets of PBDEs data (soil and outdoor dust) were uncorrelated, and Spearman correlation coefficient matrix implied that the degradation pathways of PBDEs were different between soil and outdoor dust.

Polybrominated diphenyl ethers in human hair from the college environment: comparison with indoor dust.

Eight Polybrominated diphenyl ether (PBDE) congeners (BDE 28, 47, 99, 100, 153, 154, 183 and 209) were determined to examine the hair burden at low concentrations, and the relationship between PBDE concentrations in human hair and indoor dust from a college environment (Shanghai University campus). Chemical analyses showed that the total concentrations of PBDEs in hair ranged from 4.04 to 99 ng/g dw, and were found to be fourfold higher in females than in males (p < 0.05). The total PBDEs concentrations in indoor dust samples ranged from 170 to 1,360 ng/g dw. Significantly positive correlations were observed between human hair and indoor dust for BDE 47 (r = 0.44, p = 0.048) and BDE 99 (r = 0.68, p = 0.025). However, no significant association was noted between other PBDE congeners in human hair and indoor dust in the present study.

Polybrominated diphenyl ethers in surface sediments from principal watersheds of Shanghai, China: levels, distribution, influencing factors, and risk assessment.

Fourteen and 17 sediment samples were collected from three main rivers of Shanghai in July and November, respectively. Eight polybrominated diphenyl ether (PBDE) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209) were detected in these samples to clarify the pollution status in the metropolis. Instrumental analyses showed that the concentrations of ∑8PBDEs ranged from 10.97 to 64.05 ng/g dry weight (dw), with an average value of 29.71 ng/g dw. BDE-209 was the predominant congener accounting for more than 97% of total PBDEs, followed by BDE-47 and BDE-99. Remarkable spatial and seasonal distributions of PBDE concentrations were observed, suggesting that local sources, seasonal climates, and hydrologic conditions might be the influencing factors. Moderate correlations (r (2) = 0.28-0.51, p < 0.05) were found between total organic carbon and PBDEs, which indicated that organic carbon content influenced the distributions of PBDEs in sediment of Shanghai at some extent. Hazard quotients revealed PBDEs posed no potential risk to benthic organisms in the study area at present.