Electrochemical degradation of 17α-ethinylestradiol: Transformation products, degradation pathways and in vivo assessment of estrogenic activity.

Conventional water treatment methods are not efficient in eliminating endocrine disrupting compounds (EDCs) in wastewater. Electrochemical Advanced Oxidation Processes (eAOPs) offer a promising alternative, as they electro-generate highly reactive species that oxidize EDCs. However, these processes produce a wide spectrum of transformation products (TPs) with unknown chemical and biological properties. Therefore, a comprehensive chemical and biological evaluation of these remediation technologies is necessary before they can be safely applied in real-life situations. In this study, 17α-ethinylestradiol (EE2), a persistent estrogen, was electrochemically degraded using a boron doped diamond anode with sodium sulfate (Na2SO4) and sodium chloride (NaCl) as supporting electrolytes. Ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry was used for the quantification of EE2 and the identification of TPs. Estrogenic activity was assessed using a transgenic medaka fish line. At optimal operating conditions, EE2 removal reached over 99.9% after 120 min and 2 min, using Na2SO4 and NaCl, respectively. The combined EE2 quantification and in vivo estrogenic assessment demonstrated the overall estrogenic activity was consistently reduced with the degradation of EE2, but not completely eradicated. The identification and time monitoring of TPs showed that the radical agents readily oxidized the phenolic A-ring of EE2, leading to the generation of hydroxylated and/or halogenated TPs and ring-opening products. eAOP revealed to be a promising technique for the removal of EE2 from water. However, caution should be exercised with respect to the generation of potentially toxic TPs.

The comparative study on inhibitory effect of natural organic matters on the TiO2 and activated carbon/TiO2 composites for the removal of 17α-ethinylestradiol.

To reduce or eliminate the inhibition effect of natural organic matters (NOMs) in water on TiO2 photocatalysis for removal of emerging contaminants, four activated carbon/titanium dioxide (AC/TiO2) composites with different pore structure were prepared by hydrothermal method. The results showed that anatase TiO2 particles were uniformly distributed in the pores or onto the surface of activated carbons. The total removal rate of 6 mg L-1 17α-ethinylestradiol (EE2) on the four AC/TiO2 composites reached above 90%, 30% higher than that of EE2 on TiO2. The degradation rate constants of EE2 on four kinds of AC/TiO2 were much higher than that on TiO2. Further study indicated that the adsorption removal ratio of EE2 on the composites was slightly reduced mainly because competitive adsorption between hydrophilic NOMs (HA and FA) and EE2 molecules when HA and FA coexisted with EE2 in water. But importantly, the obvious inhibitory effect of FA for TiO2 photocatalysis was eliminated on four composites because the introduction of AC with excellent adsorption capacity can preferentially transfer hydrophobic EE2 molecules onto adsorption sites of TiO2/AC composites.

Algal organic matter and dissolved Mn cooperatively accelerate 17α-ethinylestradiol photodegradation: Role of photogenerated reactive Mn(III).

Algal extracellular organic matter (EOM), a major fraction of the dissolved organic matter found in eutrophic plateau lakes, can act as a photosensitizer to drive the abiotic oxidation of Mn(II). This process has the potential to generate reactive Mn(III) and influence the fate of organic pollutants. In this study, the photodegradation of 17α-ethinylestradiol (EE2) in the presence of Mn(II) and EOM was investigated with emphasis on the photogeneration mechanism of Mn(III). The results indicated that Mn(II) can accelerate EE2 photodegradation in EOM solution owing to the photogeneration of reactive Mn(III), and the enhancement was greater at higher Mn(II) concentrations. The generation of reactive Mn(III) was mainly attributable to the action of superoxide radical generated by photosensitization of EOM. In addition, the photodegradation of EE2 was slower at higher pH, possibly because of the deactivation of Mn(III) under alkaline conditions. Single-electron transfer was an indispensable process in the photodegradation. The differences in fluorophore content, pH, and NO3- concentrations are all important determinants for EE2 photodegradation in natural waters. The information obtained in this research would contribute to the understanding of reactions between Mn(II) and EOM, and provide new insights into the behaviors of reactive Mn(III) in eutrophic water irradiated by sunlight.

[Sorption Characteristics and Site Energy Distribution Theory of Typical Estrogens on Microplastics].

Microplastics (MPs) and estrogens are high-profile emerging contaminants at present, and MPs might become the carrier of estrogens in the environment and induce combined pollution. To study the adsorption behavior of polyethylene (PE) microplastics to typical estrogens, the adsorption isothermal properties of the six estrogens[estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), estriol (E3), diethylstilbestrol (DES), and ethinylestradiol (17α-EE2)] in single-solute and mixed-solute systems were studied through batch equilibrium adsorption experiments, in which the PE microplastics before and after adsorption were characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Then, the site energy distribution theory of the adsorption of six estrogens on PE microplastics was further analyzed based on the Freundlich model. The results showed that the adsorption process of selected estrogens with two concentrations (100 µg·L-1 and 1000 µg·L-1) on PE were more consistent with the pseudo-second order kinetic model. The increase in initial concentration reduced the equilibrium time of adsorption and increased the adsorbing capacity of estrogens on PE. In the single system (one estrogen) or mixed system (six estrogens) with different concentrations (10 µg·L-1-2000 µg·L-1), the Freundlich model showed the best fitting effect for the adsorption isotherm data (R2>0.94). The results of isothermal adsorption experiments and XPS and FTIR spectra showed that the adsorption of estrogens on PE in the two systems was heterogeneous adsorption, and hydrophobic distribution and van der Waals forces were the principal factors in the process of adsorption. The occurrence of C-O-C (in only the DES and 17α-EE2 systems) and O-C[FY=,1]O (in only the 17α-EE2 system) indicated that the adsorption of synthetic estrogens on PE was affected slightly by chemical bonding function, but no obvious effects were observed for natural estrogens. The results of site energy distribution analysis showed that, compared with the single system, the adsorption site energy of each estrogen shifted to the high-energy region in its entirety in the mixed system, and the site energy increased by 2.15%-40.98%. The energy change in DES was the most significant among all of the estrogens, indicating its competitive advantage in the mixed system. The above results of this study can provide some reference for the study of adsorption behavior, mechanism of action, and environmental risks under the coexisting condition of organic pollutants and MPs.

Studies on competitive adsorption characteristics of bisphenol A and 17α-ethinylestradiol on thermoplastic polyurethane by site energy distribution theory.

Compound pollution of microplastics and estrogens is a growing ecotoxicological problem in aquatic environments. The adsorption isothermal properties of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) on polyamide (TPU) in monosolute and bisolute systems were studied. Under the same adsorption concentration (1-4 mg L-1), EE2 had a greater adsorption capacity than BPA in the monsolute system. Compared to the energy distribution features of the adsorption sites of EE2 and BPA, the BPA adsorption sites were located in the higher energy area and were more evenly distributed than those of EE2, while the quantity of BPA adsorption sites was less than that of EE2. In the bisolute system, the average site energy, site energy inhomogeneity, and adsorption site numbers of BPA increased by 1.674, -17.166, and 16.793%, respectively. In comparison, the average site energy, site energy inhomogeneity, and adsorption sites numbers of EE2 increased by 2.267, 4.416, and 8.585%, respectively. The results showed that BPA and EE2 had a cooperative effect on the competitive adsorption of TPU. XPS analysis showed that BPA and EE2 had electron transfer on TPU, although the chemisorption effects and hydrogen bonds between BPA and TPU were more significant. Comparing the changes in the relative functional group content of TPU in monosolute and bisolute systems, BPA and EE2 were synergistically absorbed on TPU. This study can provide a theoretical reference for the study of competitive adsorption between coexisting organic pollutants.

Triazole-based estradiol dimers prepared via CuAAC from 17α-ethinyl estradiol with five-atom linkers causing G2/M arrest and tubulin inhibition.

Microtubule dynamic is exceptionally sensitive to modulation by small-molecule ligands. Our previous work presented the preparation of microtubule-targeting estradiol dimer (ED) with anticancer activity. In the present study, we explore the effect of selected linkers on the biological activity of the dimer. The linkers were designed as five-atom chains with carbon, nitrogen or oxygen in their centre. In addition, the central nitrogen was modified by a benzyl group with hydroxy or methoxy substituents and one derivative possessed an extended linker length. Thirteen new dimers were subjected to cytotoxicity assay and cell cycle profiling. Dimers containing linker with benzyl moiety substituted with one or more methoxy groups and longer branched ones were found inactive, whereas other structures had comparable efficacy as the original ED (e.g. D1 with IC50 = 1.53 µM). Cell cycle analysis and immunofluorescence proved the interference of dimers with microtubule assembly and mitosis. The proposed in silico model and calculated binding free energy by the MM-PBSA method were closely correlated with in vitro tubulin assembly assay.

Hydroxypropyl methylcellulose-sugarcane bagasse adsorbents for removal of 17α-ethinylestradiol from aqueous solution and freshwater.

Adsorbents made of hydroxypropyl methylcellulose (HPMC) and sugarcane bagasse (BG) microparticles were applied for the separation of 17α-ethinylestradiol (EE2) from aqueous solution in batch, and from aqueous solution and freshwater in fixed-bed columns. HPMC chains and BG microparticles were crosslinked by the esterification with citric acid. The adsorbents presented compression modulus values that increased from 208 ± 20 kPa (pure HPMC) to 917 ± 90 kPa, when the content of BG particles added to HPMC was 50 wt% (HPMC50BG). The porosity (~ 97%), specific surface area (1.16 ± 0.10 m2/g) and swelling degree (20 ± 1 g water/g) values were not affected by the addition of BG particles. The adsorption isotherms determined for EE2 on HPMC and on HPMC50BG fitted to the Langmuir and Freundlich models; the adsorption capacity of HPMC was slightly higher than that of composite HPMC50BG. Nevertheless, the addition of BG particles rendered outstanding mechanical reinforcement and dimensional stability to the adsorbents. The adsorption was driven by (i) hydrophobic interactions between EE2 methylene and aromatic groups and HPMC methyl groups, as evidenced by FTIR spectroscopy, and (ii) H bonds between HPMC and EE2 hydroxyl groups, as revealed by the adsorption enthalpy change (ΔHads) of - 45 kJ/mol. Column adsorption experiments of EE2 from aqueous solution on HPMC and HPMC50BG indicated adsorptive capacity (q0) values of 8.06 mg/g and 4.07 mg/g, respectively. These values decreased considerably for the adsorption of EE2 from river water, probably due to the competition of EE2 with humic substances dissolved in natural water. The HPMC adsorbents could be recycled retaining up to 83% of the original efficiency.

Removal effects and potential mechanisms of bisphenol A and 17α-ethynylestradiol by Biogenic Mn oxides generated by Bacillus sp. WH4.

Endocrine disrupting compounds (EDCs), such as bisphenol A (BPA) and 17α-ethynylestradiol (EE2), have increasingly negative effects on human and wildlife health. In this study, the biogenic Mn oxides (BMOs) generated by Bacillus sp. WH4 were characterized, and the removal effects and reaction kinetics of BPA and EE2 by BMOs under different pH values, initial organic concentrations, and dosages of BMOs were discussed. The results showed that the formation of BMOs was extracellular process, and Mn(II) was oxidized to Mn(III) and Mn(IV) with 23.56% and 76.44%, respectively. The degradation processes of BPA and EE2 by BMOs followed first-order reaction kinetics, and the removal effect decreased with increasing initial BPA/EE2 concentrations and increased with increasing dosages of BMOs. However, the removal effect of BPA by BMOs decreased and then increased with increasing pH, while the removal effect of EE2 by BMOs decreased with increasing pH. Under optimal conditions, the removal efficiency of BPA and EE2 exceeded 98.2% and 94.3%, respectively. Additionally, this study showed that BMOs degraded BPA by coupling, oxidative condensation, substitution, and elimination reactions to obtain sixteen intermediate products and EE2 by substitution and elimination reactions to obtain seven intermediate products.

Biocatalytic System Made of 3D Chitin, Silica Nanopowder and Horseradish Peroxidase for the Removal of 17α-Ethinylestradiol: Determination of Process Efficiency and Degradation Mechanism.

The occurrence of 17α-ethinylestradiol (EE2) in the environment and its removal have drawn special attention from the scientific community in recent years, due to its hazardous effects on human and wildlife around the world. Therefore, the aim of this study was to produce an efficient enzymatic system for the removal of EE2 from aqueous solutions. For the first time, commercial silica nanopowder and 3D fibrous chitinous scaffolds from Aplysina fistularis marine sponge were used as supports for horseradish peroxidase (HRP) immobilization. The effect of several process parameters onto the removal mechanism of EE2 by enzymatic conversion and adsorption of EE2 were investigated here, including system type, pH, temperature and concentrations of H2O2 and EE2. It was possible to fully remove EE2 from aqueous solutions using system SiO2(HRP)-chitin(HRP) over a wide investigated pH range (5-9) and temperature ranges (4-45 °C). Moreover, the most suitable process conditions have been determined at pH 7, temperature 25 °C and H2O2 and EE2 concentrations equaling 2 mM and 1 mg/L, respectively. As determined, it was possible to reuse the nanoSiO2(HRP)-chitin(HRP) system to obtain even 55% EE2 degradation efficiency after five consecutive catalytic cycles.

Biodegradation of synthetic estrogen using bioelectrochemical system and degradation pathway analysis through Quadrupole-time-of-flight-mass spectrometry.

Synthetic estrogenic compounds such as 17α-ethinylestradiol (EE2) are significant environmental contaminants. This research studied the biodegradation of EE2 utilizing the EE2 adapted cells isolated from a dairy farm waste site in suspension flask vis-a-vis Bioelectrochemical System (BES) and compared the power output in the BES with and without EE2 as a co-substrate. 78% removal of EE2 was observed in the BES as against 60% removal in suspension flasks. The maximum power density in the BES increased about 53% when EE2 is used as a co-substrate. The EE2 biodegradation studied using HPLC and Q-TOF methods, also proposes a hypothetical pathway for EE2 degradation by the newly isolated strain Rhodopseudomonas palustris MDOC01 and reports the significant metabolites like nicotinic acid and oxoproline being detected during bioelectrochemical treatment process of EE2. Study also suggests that Plasma peroxide treatment of anode material enhanced the overall performance in terms of biodegradation efficiency and power output.

The Effect of a Synthetic Estrogen, Ethinylestradiol, on the hERG Block by E-4031.

Inhibition of K+-conductance through the human ether-a-go-go related gene (hERG) channel leads to QT prolongation and is associated with cardiac arrhythmias. We previously reported that physiological concentrations of some estrogens partially suppress the hERG channel currents by interacting with the S6 residue F656 and increase the sensitivity of hERG blockade by E-4031. Although these studies suggested that clinically used synthetic estrogens with similar structures have the marked potential to alter hERG functions, the hERG interactions with synthetic estrogens have not been assessed. We therefore examined whether ethinylestradiol (EE2), a synthetic estrogen used in oral contraceptives, affects hERG function and blockade by drugs. Supratherapeutic concentrations of EE2 did not alter amplitudes or kinetics of the hERG currents elicited by train pulses at 20 mV (0.1 Hz). On the other hand, EE2 at therapeutic concentrations reduced the degree of hERG current suppression by E-4031. The administration of EE2 followed by E-4031 blockade reversed the current suppression, suggesting that the interaction of EE2 and E-4031 alters hERG at the drug-binding site. The effects of EE2 on hERG blockade raised the possibility that other estrogens, including synthetic estrogens, can alter hERG blockade by drugs that cause QT prolongation and ventricular arrhythmias.

Optimizing Adsorption of 17α-Ethinylestradiol from Water by Magnetic MXene Using Response Surface Methodology and Adsorption Kinetics, Isotherm, and Thermodynamics Studies.

Magnetic MXene composite Fe3O4@Ti3C2 was successfully prepared and employed as 17α-ethinylestradiol (EE2) adsorbent from water solution. The response surface methodology was employed to investigate the interactive effects of adsorption parameters (adsorption time, pH of the solution, initial concentration, and the adsorbent dose) and optimize these parameters for obtaining maximum adsorption efficiency of EE2. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. Optimization of the process variables for maximum adsorption of EE2 by Fe3O4@Ti3C2 was performed using the quadratic model. The model predicted maximum adsorption of 97.08% under the optimum conditions of the independent variables (adsorption time 6.7 h, pH of the solution 6.4, initial EE2 concentration 0.98 mg L-1, and the adsorbent dose 88.9 mg L-1) was very close to the experimental value (95.34%). pH showed the highest level of significance with the percent contribution (63.86%) as compared to other factors. The interactive influences of pH and initial concentration on EE2 adsorption efficiency were significant (p < 0.05). The goodness of fit of the model was checked by the coefficient of determination (R2) between the experimental and predicted values of the response variable. The response surface methodology successfully reflects the impact of various factors and optimized the process variables for EE2 adsorption. The kinetic adsorption data for EE2 fitted well with a pseudo-second-order model, while the equilibrium data followed Langmuir isotherms. Thermodynamic analysis indicated that the adsorption was a spontaneous and endothermic process. Therefore, Fe3O4@Ti3C2 composite present the outstanding capacity to be employed in the remediation of EE2 contaminated wastewaters.

Investigation of the binding interactions between 17α-ethinylestradiol with bovine serum albumin by multispectroscopy.

To understand the effect of 17α-ethinylestradiol (EE2) on the conformation changes of bovine serum albumin (BSA), the binding mechanisms of EE2 with BSA were investigated by fluorescence spectroscopy, time-resolved fluorescence spectroscopy, synchronous fluorescence spectroscopy, three-dimensional fluorescence spectroscopy, UV-visible spectroscopy, circular dichroism (CD) spectroscopy and molecular docking. The quenching constants, binding constants, the number of binding sites, thermodynamic parameters, binding distance and the secondary structure changes of BSA were determined. The results of fluorescence quenching experiment suggested that the fluorescence quenching of BSA by EE was due to the formation of complex through static quenching, which was also confirmed by time-resolved fluorescence measurements. The thermodynamic parameters indicated that the binding of EE2 to BSA was driven mainly by van der Waals forces and hydrogen bonding. The conformation alterations of BSA upon EE2 binding were studied by UV-vis spectroscopy and CD spectroscopy. The results of site marker competitive experiments and molecular docking showed that the binding sites of EE2 were mainly located within site I in the subdomain IIA of BSA.

Influence of humic acids on fungal laccase-initiated 17α-ethynylestradiol oligomerization: Transformation kinetics and products distribution.

Fungal laccase has aroused great concern in rapidly removing estrogens because of its ability to accelerate humification and oligomerization. Here, the effect of two humic acids (HAs) on the reaction kinetics and products distribution of 17α-ethynylestradiol (EE2) in laccase-initiated humification and coupling was systematically elucidated. Laccase from Trametes versicolor exhibited over 98.3% removal rate for EE2 at pH 5.0 within 120 min, while HAs invariably restrained EE2 transformation by competing with target-substrate for the enzymatic catalytic center. EE2 removal followed pseudo-first-order kinetics, and the rate constant was decreased markedly with increasing concentration of two HAs (0-60 mg L-1). Additionally, laccase heightened the aromaticity and humification degrees (A250 nm/A365 nm ratio) of HAs probably due to the formation of new humic polymers such as (HA)m and/or (HA)m-(EE2)n (m and n represent the number of HA and EE2 units, respectively). Three major EE2 oligomers were identified, in accordance with a mechanism involving the phenoxy radical-driven polymerization to yield a wide variety of self-coupling products. Notably, HAs diminished the extent of EE2 self-coupling but aggrandized the cross-coupling between EE2 and HAs, and the inhibition degree of EE2 self-coupling increased with the concentration of HAs. One major reason is EE2 could be covalently incorporated into humic molecules to produce (HA)m-(EE2)n cross-coupling products via radical-caused C-C, C-O-C, and/or C-O-C bonds, thereby reducing EE2 self-oligomerization. These findings highlight that HAs play a vital role in the fungal laccase-induced humification and oligomerization of EE2, which obviously alter the geochemical fate and transport of EE2 in natural aquatic ecosystems.

Efficacy assessment of peracetic acid in the removal of synthetic 17α-ethinyl estradiol contraceptive hormone in wastewater.

Increasing concerns have been raised on endocrine disrupting chemicals like the sex hormone 17α-ethinylestradiol (EE2), the more since traditional wastewater (WW) treatments appear to be ineffective for their removal. The efficacy of the relatively novel disinfectant peracetic acid (PAA) in EE2 removal was evaluated, as well as its potential effects on WW quality parameters. The treatments tested for EE2 removal were also evaluated in terms of toxicity, through the determination of biochemical responses (antioxidant enzymes, lipid peroxidation and vitellogenin induction) using zebrafish (Danio rerio) as a biological model. PAA contact times less than 20 min appeared insufficient regardless of the PAA dose tested, but a 100% EE2 removal was attained at a PAA concentration of 15 mg/L with a contact time of 20 min. Total suspended solids, chemical oxygen demand and pH in PAA treatments remained well within levels set in European legislation for WW discharge. EE2 induced significant increased vitellogenin (VTG) levels in both female and male fish, indicating increased estrogenic activity, especially in males suggesting an endocrine disruption effect. With the addition of PAA (15 mg/L), however, VTG levels in both sexes returned to control values. Although this PAA treatment showed increased levels of the antioxidant enzyme catalase, the lipid peroxidation levels were similar or even lower than in controls. Overall the results suggest that the use of PAA appears a promising way forward as a less toxic alternative to chlorine disinfection with high efficiency in the removal of EDC like EE2.

QbD Based Approach to Enhance the In-Vivo Bioavailability of Ethinyl Estradiol in Sprague-Dawley Rats.

Lyophilized nanosuspension of poorly soluble Ethinyl estradiol (EE) was fabricated to enhance its solubility and bioavailability using a quality-by-design (QbD) approach. With the help of the Ishikawa diagram, prospective risk factors were identified and screened by Placket-Burman design to investigate the effects of formulation and process variables on dependent variables. The number of cycles (X4), the concentration of soya lecithin (X5) and the concentration of tween 80 (X7) were identified as significant factors (P<0.05), which were further optimized using Central Composite Design. The mean particle size, zeta potential, drug content and entrapment efficiency of optimized lyophilized EE nanosuspension (EENPs) was 220±0.37 nm, -19.3±6.73 mV, 92.23±0.45%, 99.52±0.52%, respectively. Significantly, EENPs enhances Cmax and AUC0-t by 1.5, 1.7 folds and relative bioavailability by 2-fold with its distribution being at higher concentrations in the liver, spleen, and stomach. Thus, QbD based approach for the development of nanosuspension could be an absolute, optimistic approach to identify the critical process parameters and critical quality attributes.

Predictive role of spectral slope ratio towards 17α-ethynylestradiol photodegradation sensitized by humic acids.

Humic acids (HAs) have been shown to dominate the photodegradation of steroid estrogens in natural waters. Nevertheless, how the photosensitizing ability of HAs relates to their structural and optical characteristics remains largely unknown. In this study, 17α-ethynylestradiol (EE2) was selected as a model compound to study to what extent easily-measurable characteristics of HAs might be used to predict their photosensitization potency. HAs were extracted from sediments of two different sources, and then subjected to structural and optical properties characterization using elemental analyzer, UV-vis spectroscopy and fluorescence spectroscopy. Photochemical experiments show that the HAs from the two sources can effectively meditate EE2 photodegradation. Although with drastically different structural and optical properties, the photosensitizing ability of these HAs towards EE2 can be well described by simple linear regressions using a spectroscopic index, the spectral slope ratio (SR). This optical indicator is correlated with various physicochemical properties of HAs, including the molecular weight, lignin content, charge-transfer interaction potential, photobleaching extent and sources. No universal prediction model could be established for predicting EE2 photodegradation kinetics on the basis of SR, but in specific waters SR could be a powerful indictor for predicting the EE2 photodegradation sensitized by HAs.

Effect of biochar amendment on sorption-desorption and dissipation of 17α­ethinylestradiol in sandy loam and clay soils.

Animal manure application in agricultural land has caused the release of steroid estrogens in the soil environment and further movement to aquatic systems. The objective of this study was to investigate the effects of biochar addition on sorption-desorption and dissipation behaviors of 17α­ethinylestradiol (EE2) in two different textured soils. A Commerce sandy loam and a Shakey clay were selected and subjected to sterilization. Soil samples with and without sterilization were reacted with a series of EE2 solutions of different concentrations for sorption followed by desorption and quantification using HPLC-MS/MS. Long-term dissipation of EE2 in the same soils was also evaluated over a 30-d incubation. Biochar amendment increased the maximum EE2 sorption capacity but decreased its water desorption in both sandy loam and clay soils. On other hand, biochar addition increased the Koc in the clay soil which had low EE2 sorption efficiency but decreased Koc in the sandy loam which had high EE2 sorption efficiency. Biochar did significantly increase both desorbable and non-extractable fractions of EE2, while it reduced the bioavailability of EE2 to microbial degradation. The dissipation of EE2 in non-sterilized soils fit to the first-order kinetic model, whereas it was better described by zero-order kinetic for sterilized soil. Biochar increased the half-life of EE2 dissipation in non-sterilized Commerce sandy loam soil by 48% (from 3.63 to 5.37 d) and in non-sterilized Sharkey clay soil by 67% (from 2.28 to 3.81 d). Overall, this study demonstrated positive impacts of biochar on the retention of estrogen hormones in soils.

Biosorption of 17α-ethinylestradiol by yeast biomass from ethanol industry in the presence of estrone.

Yeast biomass from ethanol industry (YB) was evaluated as a biosorbent to 17α-ethinylestradiol (EE) alone and along with estrone (EST). This material is rich in sorption sites and has a good cost-benefit ratio, since it is an industrial residue largely produced (around 30 g for each liter of ethanol). A 2k-factorial design was carried out to evaluate the sorption capacity of YB for EE considering the variables pH, biosorbent dose (BD), and ionic strength (IS), at two hormone concentration (HC) levels. The best conditions assessed for individual EE adsorption (pH = 10, IS = 0.1 mol/L, and BD = 0.5 mg/L) were also established for adsorption carried out in the presence of EST. Individuals EE and EST experimental sorption capacities (SCexp) were, respectively, 24.50 ± 0.07 and 0.80 ± 0.07 mg/g, fairly similar to Qmax (EE, 21.41 ± 1.27 mg/g; EST, 0.93 ± 0.075 mg/g) from Langmuir model. The Freundlich model best fitted the experimental data for EE adsorption (r2 = 0.9925; χ2 = 0.5575). The study carried out in the presence of EST showed an associative/competitive sorption process between EE and EST, which may be explained by their similar chemical structures and organic carbon-water partition coefficients Koc.

Sorption-desorption behavior of sulfamethoxazole, carbamazepine, bisphenol A and 17α-ethinylestradiol in sewage sludge.

The occurrence of trace organic contaminants (TOrCs) at detectable levels in wastewater and surface waters led to a growing concern over the persistence of toxicological effects in the environment. Sorption is significant process in municipal wastewater treatment plants to remove TOrCs due to low water solubility and high hydrophobic of most TOrCs. The work herein explored the sorption behavior of four typical TOrCs onto sludge solids. The sorption process was spontaneous and exothermic. Greater sorption amount was observed for EE2 that 60.9% of EE2 in liquid phase was removed, followed by BPA (49.4%) and SMX (35.8%), while only 19.5% of CBZ was adsorbed. Sorption of CBZ, BPA and EE2 was primarily a physical process dominated by partition function, while SMX was mainly sorbed through multiple interactions, and this strong affinity between SMX and activated sludge resulted in least desorption rate. Deep insight into the pathway of SMX in SBR revealed that total removal rate in a period was about 50.22%. Sorption process was observed in anaerobic stage, and biological degradation was mainly occurred in aerobic stage with biodegradation rate of 29.18%.