Deconjugation potentials of natural estrogen conjugates in sewage and wastewater treatment plant: New insights from model prediction and on-site investigations.

Natural estrogen conjugates play important roles in municipal wastewater treatment plant (WWTP), but their deconjugation potentials are poorly understood. This work is the first to investigate the relationships between the enzyme activities of arylsulfatase/ß-glucuronidase and deconjugation potentials of natural estrogen conjugates. This work led to three important findings. First, the enzyme activity of ß-glucuronidase in sewage is far higher than that of arylsulfatase, while their corresponding activities in activated sludge were similar. Second, a model based on ß-glucuronidase could successfully predict the deconjugation potentials of natural estrogen glucuronide conjugates in sewage. Third, the enzyme activity of arylsulfatase in sewage was too low to lead to evident deconjugation of sulfate conjugates, which means that the deconjugation rate of estrogen sulfates can be regarded as zero. By comparing their theoretical removal based on enzyme activity and on-site investigation, it is reasonable to conclude that reverse deconjugation of estrogen conjugates (i.e., conjugation of natural estrogens to form conjugated estrogens) likely exist in WWTP, which explains well why natural estrogen conjugates cannot be effectively removed in WWTP. Meanwhile, this work provides new insights how to improve the removal performance of WWTP on natural estrogen conjugates. SYNOPSIS: This work is the first to show how arylsulfatase/ß-glucuronidase could affect deconjugation of natural estrogen conjugates and possible way to enhance their removal in wastewater treatment plant.

Ten bisphenol analogues in Chinese fresh dairy milk: high contribution ratios of conjugated form, importance of enzyme hydrolysis and risk evaluation.

This study investigated concentration levels of ten bisphenols (BPs) in 13 Chinese commercial fresh low temperature dairy milk samples (fresh milk) of main local and national brands with or without enzyme hydrolysis. The results showed that at least two BPs were detected in each fresh milk sample without enzyme hydrolysis and the respective mean concentrations of bisphenol AF (BPAF), bisphenol B (BPB), bisphenol C (BPC), bisphenol F (BPF), bisphenol A (BPA), bisphenol S (BPS), bisphenol AP (BPAP), bisphenol PP (BPP), bisphenol Z (BPZ), and bisphenol E (BPE) were 0.73, 0.61, 1.86, 0.87, 0.42, 0.11, 1.06, 1.42, 1.5, and 0.04 ng/mL, while their respective detection frequencies ranged from 23.1-92.3%. These results indicated the frequent detection of BPs in fresh milk samples. With enzyme hydrolysis, the respective mean concentrations of BPAF, BPA, BPB, BPC, BPF, BPS, and BPAP were increased 7.1-107.1%, indicating the long-ignored importance of enzyme hydrolysis. The respective average estimated daily intakes (EDIs) of BPA by adult and children in China via fresh milk were 32.5 and 37.5 ng/kg bw/d, indicating that BPA in fresh milk was a crucial source to human. Six out of nine other BPs had higher average EDIs than that of BPA, among which the EDI of BPAP was almost three times that of BPA, suggesting the widespread contamination of other BPs in Chinese fresh milk.

Hydrogen-Donor-Controlled Polybrominated Dibenzofuran (PBDF) Formation from Polybrominated Diphenyl Ether (PBDE) Photolysis in Solutions: Competition Mechanisms of Radical-Based Cyclization and Hydrogen Abstraction Reactions.

Polybrominated dibenzofurans (PBDFs) are characteristic dioxin-like products of polybrominated diphenyl ether (PBDE) photolysis. In this study, competition mechanisms of radical-based cyclization and hydrogen abstraction reactions are proposed in PBDF formation. Commonly, the ortho C-Br bond dissociation during photolysis generates aryl radicals, which undergo intramolecular cyclization to form PBDFs or hydrogen abstraction with hydrogen donors (such as organic solvents and water) to form lower brominated PBDEs. By using 2,4,4'-tribromodiphenyl ether (BDE-28) as the model reactant, the experimental PBDF formation ratios in various solutions are explained quantitatively by the calculated rate constants of cyclization and hydrogen abstraction reactions using the density functional theory (DFT) method. The solvent effect of pure and mixed solvents on PBDF formation is illustrated successfully. The structure-related hydrogen donation ability for hydrogen abstraction controls the bias of competition reactions and influences PBDF formation. Water resulted to be the most significant generation of PBDFs. Fulvic and humic acid display higher hydrogen donation ability than small-molecule organics due to the partitioning effect in aqueous solution. Quantitative structure-activity relationship (QSAR) models of the calculated rate constants for 512 cyclization and 319 hydrogen abstraction reactions using 189 PBDEs as the initial reactants in water are established, revealing the high risk of PBDF formation in aqueous solution.

17α-ethynylestradiol and its two main conjugates in seven municipal wastewater treatment plants: Analytical method, their occurrence, removal and risk evaluation.

This work shows the existence of both 17-ethinylestradiol-3-sulfate (EE2-3S) and 17-ethinylestradiol-3-glucuronide (EE2-3G) in seven municipal WWTPs with substantial concentrations (n.d-50.10 ng/L). The calculated removal efficiencies of 17-ethinylestradiol (EE2) in the seven municipal WWTPs ranged from 40.8%-100% with an average removal efficiency of 83.3%. However, upon the inclusion of EE2 concentration transformed from EE2-3S and EE2-3G, the corresponding removal efficiencies were increased to 91.4%-100% with an average removal efficiency of 97.3%. This work is the first to clearly illustrate that EE2 conjugates in raw wastewater could greatly underestimate the removal effectiveness of municipal WWTPs on EE2, indicating the importance of the EE2 conjugates in municipal wastewater having been hardly paid with attention. The EE2-derived estrogen equivalence (EEQ) values in the effluents of seven WWTPs ranged from 0 to 0.98 ng E2/L having an average level of 0.45 ng E2/L, which were relatively low. However, upon the inclusion of EE2 transformable from EE2-3S and EE2-3G in effluents, the EE2-derived EEQ values in effluents would be increased to 0.77-4.85 ng E2/L having an average level of 2.71 ng E2/L, which clearly suggested that ignorance of EE2 conjugates in effluent would largely underestimate EE2's environmental risk to receiving water bodies.

Extraction of alumina from aluminum dross by a non-hazardous alkaline sintering process: Dissolution kinetics of alumina and silica from calcined materials.

The aluminum dross (AD), which causes numerous problems of its management and disposal to environment is a useful resource to extract alumina. This study explains a novel process to extract highly pure alumina (Al2O3) from AD at a high extraction rate without producing the residues and exhaust gases. An experimental set up was designed to perform the grinding of AD for the decomposition of aluminum nitride (AlN) and the removal of salts. Thereby, the desalted dross was used to detect the optimum alkaline (NaOH) calcination parameters and leaching conditions, as well as the dissolution kinetics of alumina and silica. The leaching residues were used to produce Ettringite mineral with calcium-based compounds (including CaO and CaSO4) to avoid the problems of solid waste disposal from the leaching process. Moreover, to purify the alumina, slightly soluble CaSO4 was added in leaching solution to precipitate silicate and the optimum additive/solution ratio (g/mL) was determined. The aluminum hydroxide (Al(OH)3), precipitated after the carbonization was calcinated at 900.0 °C for 2 h to produce γ-alumina. The morphological and mineralogical characterizations of AD, γ-Al2O3 and the synthesized Ettringite mineral were studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and X-ray fluorescence (XRF). It was observed that activation temperature of 1000.0 °C, Na2O/Al2O3 molar ratio of 1.4, leaching temperature of 60.0 °C, leaching time of 40.0 min, and the leaching liquid/solid ratio (mL/g) of 25/1 were the optimal parameter conditions to extract alumina with the extraction rate at 86.7% and purity of more than 98%. The results of leaching kinetics' study showed that the dissolution of alumina and silica were both controlled by layer diffusion process with the apparent activation energy of 11.4010 kJ·mol-1 and 2.0556 kJ·mol-1, respectively.

Comparison of radical and non-radical activated persulfate systems for the degradation of imidacloprid in water.

The study focuses on degradation efficiency of non-radical activation and radical activation systems of persulfate (PS) to degrade imidacloprid (IMI) by using sodium persulfate (SPS) as PS source. Copper oxide (CuO)-SPS and CuO/biochar (BC)-SPS were selected as PS non-radical activation systems, and pyrite (PyR)-SPS was selected as PS radical activation system. The degradation by CuO-SPS, CuO/BC-SPS and PyR-SPS systems was investigated from acidic to basic conditions (pH 3.0-11.0). Highest degradation by CuO-SPS and CuO/BC-SPS systems was achieved over pH 11.0. In contrast, highest degradation by PyR-SPS system was achieved over pH 3.0, however, PyR-SPS system was also found effective up to pH 9.0. It was found that degradation was more efficient in PS radical activation system, indicating that IMI could be oxidized by radicals rather than by activated PS. Electron paramagnetic resonance (EPR) analysis was carried out to investigate the generation of sulfate (SO4-) and hydroxyl (OH) radicals, which indicated the presence of SO4- and OH in CuO-SPS, CuO/BC and PyR-SPS systems. However, free radical quenching analysis indicated that radicals were main reactive oxygen species for degradation. The lower degradation in PS non-radical activation systems was probably resulted from radicals existed as minor reactive oxygen species. The findings indicated that non-radical oxidation systems showed low reality for degradation and good degradation could be achieved by radical oxidation system. The degradation was also carried out in real waters to investigate the potential applicability of applied systems, which supported PyR-SPS system for effective degradation.

Simultaneous autotrophic removal of sulphate and nitrate at different voltages in a bioelectrochemical reactor (BER): Evaluation of degradation efficiency and characterization of microbial communities.

The autotrophic removal of sulphate and nitrate in bioelectrochemical reactors was investigated at different external voltages (0.2, 0.4, 0.6, 0.8 and 1.0 V) under anaerobic conditions. Sulphate and nitrate removal, nitrite accumulation, reduction trend of nitrate and sulphate and microbial community structure were explored. Results indicate the highest removal efficiencies of nitrate and sulphate at 43.3 ±â€¯2.8 and 7.1 ±â€¯0.2 mg·l-1·d-1 when the voltage is 0.6 V. Moreover, nitrite accumulation decreases with increased voltage from 0.2 V to 1.0 V. Illumina high-throughput sequencing results show similar richness and diversity of bacterial species with increased voltage from 0.2 V to 0.8 V. However, with further increased voltage to 1.0 V, bacterial diversity and richness decrease significantly. Overall, significant differences in community compositions are observed at different voltages.