Removal Of 17α-ethinylestradiol Research Articles

Efficient removal of 17α-ethinylestradiol by algae-based red mud catalyst activated persulfate: Removal mechanism and defect of quenching

The synthesis and optimization of carbon-based materials, derived from various solid waste sources to activate peroxydisulfate (PDS), offer a practical approach that addresses both the recycling of solid waste resources and the removal of recalcitrant organic pollutants. In this study, stacked algae sludge and discarded red mud solid waste were repurposed to synthesize an algae-based red mud catalyst (AR-BC) using the carbon-thermal reduction technique. The obtained AR-BC catalyst exhibited efficient adsorption and degradation capabilities for 17α-ethinylestradiol (EE2). The results showed that AR-BC can adsorb 42.67 % of EE2 at equilibrium, with a maximum capacity of 8.0 mg/g. After the activation of PDS by the AR-BC catalyst, it was observed that EE2 was completely degraded within 20 min. The superior activation ability is mainly attributed to the presence of Fe3O4 and oxygen-containing functional groups in AR-BC. Both free radicals and non-free radicals coexisted in the AR-BC/PDS system, with the former predominantly influencing the EE2 degradation process. And hydroxyl radical was identified as the primary reactive oxygen species. Moreover, AR-BC exhibited robust adaptability and reusability in real water for efficient adsorption and degradation of EE2. This study presents a viable solution by seamlessly integrating resource recycling with pollutant removal, offering an innovation approach.

Removal of 17α-ethinylestradiol and total phosphorus in a sequencing batch reactor under two different sludge retention-time conditions

Sewage treatment systems can prevent the direct discharge of endocrine disruptors, such as 17α-ethinylestradiol (EE2), into the environment. Treatment systems capable of promoting total phosphorus (TP) removal, such as sequencing batch reactors (SBRs), are promising in this regard. Two lab-scale SBRs with different sludge retention times (SRTs) were assessed for their EE2 and TP removal rates. Anaerobic/aerobic/anoxic phases with cycles of 6 h were used to treat sewage containing EE2 at a concentration of 5 μg L-1. The removal rates of chemical oxygen demand and TP were approximately 80% for both the SBRs. Partial nitrification was observed in the SBRs. Initially, concentrations of EE2 above 1.0 μg L-1 in the treated sewage were measured. These concentrations were smaller in SBR 1, which used lower SRTs; EE2 was removed by sludge sorption. After the 56th cycle, the concentrations of EE2 in the treated sewage were below 0.1 μg L-1 in both the SBRs, indicating that its removal may have occurred by biodegradation due to acclimation to the process. Therefore, both TP removal and nitrification seem to play an important role in EE2 removal by SBRs.
 Keywords: A2O SBR, EE2 and TP removal, sewage treatments.

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.

Impact of zero-valent iron on nitrifying granular sludge for 17α-ethinylestradiol removal and its mechanism

Aerobic granulation of nitrifying activated sludge could enhance the removal of 17α-ethinylestradiol (EE2) via abiotic nitration induced by reactive nitrogen species, cometabolism by ammonia-oxidizing bacteria and biodegradation by heterotrophic bacteria. Zero-valent iron (ZVI), a promising and low-cost material, has previously been applied to effectively enhance biological wastewater treatment. The impact and the effect mechanism of ZVI on nitrifying granular sludge (NGS) for EE2 removal was investigated in this study. The results showed that the addition of ZVI achieved better EE2 removal, though ZVI was not conducive to the accumulation of nitrite in NGS which reduced the abiotic transformation of EE2. Moreover, ZVI enriched heterotrophic denitrifying bacteria such as Arenimonas, thus changing the EE2 removal pathway and improving the degradation and mineralization of EE2. In addition, ZVI reduced the emission risk of the greenhouse gas N2O and strengthened the stability of the granules. Metagenomic analysis further revealed that the functional genes related to EE2 mineralization, nitrite oxidation, N2O reduction and quorum sensing in NGS were enriched with ZVI addition. This study provides meaningful guidance for ZVI application in the NGS process to achieve efficient and simultaneous removal of ammonia and emerging contaminants.

The experimental design approach to removal of endocrine disrupting compounds from domestic wastewater by electrooxidation process

In this study, the treatment performance of the process in the removal of Endocrine Disrupting Compounds (EDCs) from domestic wastewater by a laboratory-scale electrooxidation process using Ti/IrO2/RuO2 electrodes as an anode was evaluated using the response surface method (RSM). The effect of pH (3.00–9.00), current density (10–20 A), and flow rate (8–16 mL/min) on the electrochemical removal of 17α-ethinylestradiol, β-estradiol, triclosan, and estrone has been studied. The Box-Behnken Design (BBD) was used to optimize the parameters that affect the removal efficiencies of the Electrooxidation process (EOP), and second-order quadratic models were developed for the EOP process. Under optimum conditions of current density = 10 A, pH = 3.00 and flow rate = 13.93 mL/min, the maximum removal efficiencies of triclosan, 17α-ethinylestradiol and β-estradiol, and minimum energy consumption are 91.65, 96.43 and 96.65% and 41.606 kWh/m3, respectively. The Response Surface Method predicted values that reasonably agreed with the experimental values. At the same time, the electrooxidation method is not successful in completely removing estrone from wastewater.

The high photocatalytic efficiency and stability of the Z-scheme CaTiO3/WS2 heterostructure for photocatalytic removal of 17α-ethinyl estradiol in aqueous solution

In this study, a new Z-scheme CaTiO3/WS2 heterostructure composed of CaTiO3 nanoparticles and WS2 nanosheets was rationally constructed and successfully fabricated through a facile ultrasonication strategy, a continuous stirring process and a heat treatment method, successively. As expected, the resultant Z-scheme CaTiO3/WS2 heterostructure displayed drastically improved photocatalytic performance of 17α-ethinyl estradiol (EE2) degradation in an aqueous solution under UV-light irradiation. Significantly, the optimization of the Z-scheme CaTiO3(20 wt%)/WS2 heterostructure revealed prominent photocatalytic activity for EE2 degradation rate up to 0.0024 min−1 under UV-light irradiation, which was about 12 and 4 times larger than those of pure WS2 and pristine CaTiO3, respectively. The Z-scheme CaTiO3(20 wt%)/WS2 heterostructure achieved the highest photodegradation rate of more than 96 % for EE2 photodegradation in 120 min under visible light irradiation. The improved photocatalytic performance could be mainly ascribed to the formation of a direct Z-scheme LaNiO3/g-C3N4 heterojunction, which results in the interfacial charge transfer efficiency and the strong redox ability of the photogenerated electrons and holes. Additionally, the degradation mechanism of EE2 by active species trapping showed that the synergistic effect of superoxide radicals (•O2–) and holes were the main active species and were responsible for the photodegradation of EE2. This work will provide a new design approach to construct high-performance Z-scheme WS2-based composite photocatalysts for photocatalyst degradation of EE2 and environmental remediation.

Response surface optimisation for highly efficient removal of 17α-ethinylestradiol by novel kenaf core modification in aqueous solution

Response surface optimisation for highly efficient removal of 17α-ethinylestradiol by novel kenaf core modification in aqueous solution

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 ± 20kPa (pure HPMC) to 917 ± 90kPa, 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 ± 1g 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 - 45kJ/mol. Column adsorption experiments of EE2 from aqueous solution on HPMC and HPMC50BG indicated adsorptive capacity (q0) values of 8.06mg/g and 4.07mg/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.

Silica-catalyzed ozonation of 17α -ethinyl-estradiol in aqueous media-to better understand the role of silica in soils

A promising route for thorough removal of 17α-ethinyl estradiol (EE2) from aqueous media was achieved through ozonation using mesoporous silicas such SBA-15, SBA-16, MCM-41 and MCM-48 as catalysts. Comparison with aluminosilicates along with Zeta potential and particle size measurements allowed demonstrating that EE2 interaction with silanols and hydrophobic –Si-O-Si– groups are essential requirements for the catalytic activity. Acid-base interactions, if any, should have minor contribution. EE2 hydroxylation appears to be an early step in the ozonation on all catalysts, but MCM-41 showed increased activity in phenolic ring cleavage. Confrontation of HPLC-UV and UV–Vis and HPLC-UV measurements revealed highest catalytic activity for MCM-41 and to a lesser extend of MCM-48 due to their higher specific surface area and weaker acid character. These results provide valuable findings for judiciously tailoring optimum [EE2-Silica:Water] interactions for thorough oxidative degradation of endocrine disrupting compounds (EDC).

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.

A tailored metal–organic framework applicable at natural pH for the removal of 17α-ethinylestradiol from surface water

A tailored metal–organic framework applicable at natural pH for the removal of 17α-ethinylestradiol from surface water

Aerobic granulation of nitrifying activated sludge enhanced removal of 17α-ethinylestradiol

The positive correlation between the nitrification activity of activated sludge and 17α-ethinylestradiol (EE2) removal has been widely reported. However, up to now the effect of the granulation of nitrifying activated sludge (NAS) on EE2 removal has not been determined. In this study, nitrifying granular sludge (NGS) exhibited more effective EE2 removal efficiency with 3.705 μgEE2∙(gMLSS∙h)−1 in a sequential batch reactor (SBR). Through the artificial neural network (ANN) model and Spearman correlation analysis, nitrite accumulation was demonstrated to be the key factor affecting EE2 removal. Notably, under the same aeration condition (0.15 L/min), nitrite accumulation was more easily achieved in NGS because of its dense structure. Full-length 16S rRNA gene sequencing suggested that EE2 could strongly influence the microbial communities of NAS and NGS. NGS exhibited an increase in community diversity and richness, but NAS exhibited a decrease. In addition, the relative abundance of Nitrosomonas (ammonia-oxidizing bacteria, AOB) decreased considerably in both NAS and NGS, whereas the expression of amoA and nirK genes in Nitrosomonas was upregulated. It was suggested that Nitrosomonas was forced to regulate its gene expression to resist the negative effects of EE2. Denitrifying bacteria, such as Comamonas, were enriched in both NAS and NGS, and there were more species of heterotrophs that can degrade micropollutants in NGS with exposure to EE2. The transformation pathways of EE2 were uniform in NAS and NGS. Ammonia monooxygenase (AMO) in AOB directly biotransformed EE2 while reactive species produced by AOB chemically transformed EE2. Heterotrophs degraded EE2 and its transformation products (TPs) generated by AOB. According to TPs and microbial structure, NGS exhibited better performance than NAS regarding the collaborative removal of EE2 by AOB and heterotrophs. These results provide important information for the development and application of NGS to treat wastewater containing estrogen and high-strength ammonium.

Efficient removal of 17α-ethinylestradiol from secondary wastewater treatment effluent by a biofilm process incorporating biogenic manganese oxide and Pseudomonas putida strain MnB1

This study proposes a biofilm process to immobilize biogenic manganese oxide (BMO) and Pseudomonas putida MnB1 (BMO-MnB1), which shows excellent synergistic effects for 17α-ethinylestradiol (EE2) from secondary wastewater treatment effluent (WWTE). Modified granular activated carbon (M-GAC) was used as the packing carrier, inoculated with Pseudomonas putida MnB1 and Mn(II) to form the BMO-MnB1 biofilm. Feasibility tests were performed to compare the EE2 removal efficiency with that of the conventional biofilm process (BAC) for heterogeneous microbial communities. Results show that in the BAC, EE2 was removed mainly by adsorption, with biodegradation contributing only slightly to the overall performance. In contrast, the BMO-MnB1 biofilter outperformed the BAC. Furthermore, less than 4% of the total EE2 removed was extracted from the biofilter medium over 150 days of operation, confirming that EE2 was biodegraded by P. putida MnB1 or chemically oxidized by BMO. Our results suggest that BMO-MnB1 biofilm processes have high potential for practical applications in removal of endocrine disrupting compounds from wastewater effluent.

Photoelectrocatalytic simultaneous removal of 17α-ethinylestradiol and E. coli using the anode of Ag and SnO2-Sb 3D-loaded TiO2 nanotube arrays

Reclaimed water contains both residual contaminants and pathogenic microorganisms while their simultaneous removal has not been fully addressed. Thus, a photoelectrocatalytical system (PEC) was engineering herein using an innovatively synthesized composite of TiO2 nanotube arrays (TNTs) decorated with antimony doped tin oxide (SnO2-Sb) and silver nanoparticles (Ag) in three dimensions (TNTs-Ag/SnO2-Sb) to realize the simultaneous removal of 17α-ethinylestradiol (EE2) and Escherichia coli (E. coli). The optical and electrochemical properties of TNTs were improved after the loading of Ag and SnO2-Sb with an excellent the stability for reuse. A 68% removal of EE2 and more than 5-log removal of E. coli were achieved in 1 h in PEC. The DNA activity of E. coli was nearly completely lost after PEC treatment and the cytotoxicity of PEC treated EE2 solution was significantly reduced. Reactive species (HO and H2O2) and degradation products of EE2 were identified, and the transformation pathways were proposed accordingly. This study generates valuable information of the transformation kinetics and mechanism for simultaneous removal of EE2 and E coli. It also provides an effective and innovative technology for water reuse.

Removal of 17α-ethinylestradiol and caffeine from wastewater by UASB-Fenton coupled system

ABSTRACT In aquatic systems, some substances considered as endocrine disruptors have been detected, which can be due to their incomplete elimination in wastewater treatment plants (WWTPs) and inadequate disposal of pharmaceuticals. Among these contaminants are 17α-ethinylestradiol (EE2) and caffeine (CAF). Moreover, it has been reported that this kind of contaminants may provoke different adverse effects in many aquatic organisms. Because of that, in the present study, up-flow anaerobic sludge blanket reactors (UASB) coupled with the Fenton process was evaluated for EE2 and CAF removal spiked in wastewater samples. First, the best reaction conditions were established in each process. For UASB reactor, two hydraulic retention times (HRT 8 and 24 h) were evaluated, achieving the highest chemical organic demand (COD) removal (70 %) and drug elimination (84 %–86 %) with HRT 24 h. Subsequently, Fenton process was conducted at pH 3 with different levels of Fe2+ (0.05–0.5 mmol/L) and molar ratios Fe2+:H2O2 (1:1–1:10). Better results were obtained with 0.5 mmol Fe2+/L, and 1:10 ratio molar Fe2+:H2O2. Finally, UASB-Fenton coupled system allowed 80 % of COD decrease, almost complete removal of drugs and the toxicity of samples on Vibrio fischeri was reduced from 73 % to 30 %, demonstrating that this coupled system is a promising and efficient system for pharmaceutical compounds removal from wastewater.

Rice grass used for water phytoremediation with varying concentrations of 17α-ethinylestradiol hormone

17α-ethinylestradiol (EE2), an endocrine disruptor (ED) excreted by women and is found in contraceptive and hormone replacement pills used at menopause. An increase in EDs requires alternative means of water and sewage treatment, since these compounds threaten human health and the environment, even at trace levels. Phytotechnology stands out from other processes because it is sustainable, given that plants are used to recover the contaminated environment. Thus, the objective of this study was to evaluate rice grass performance in the removal of 17α-ethinylestradiol (EE2), and determine the effect of this hormone on the root anatomy and chlorophyll content of the species. A completely randomized design was used with 4 replications: EE2 concentration composed of 4 study treatments (420, 300, 180 and 60 μg L-1 EE2) and 2 control treatments (positive and negative). The effect of the treatments was evaluated over time (1, 7 and 15 days). EE2 removal from the solution was analyzed by HPLC. Chlorophyll was analyzed by UVvis spectrophotometry, showing that EE2 does not interfere with the photosynthetic activity of rice grass. Aerenchyma was analyzed by microphotographs of root sections, revealing a higher proportion in plants exposed to the hormone, indicating morpho-anatomical adaptations to survive in this medium. Thus, it can be concluded that rice grass has significant phytoremediation potential after 7 days’ exposure, surviving and adapting to the contaminated environment, and can be used to complement water and sewage treatments.

Optimization of laccase–alginate–chitosan-based matrix toward 17 α-ethinylestradiol removal

Laccase extract (LE) from Pycnoporus sanguineus was immobilized on calcium and copper alginate–chitosan beads and applied for the removal of 17α-ethinylestradiol (EE2). Effects of immobilization conditions such as: sodium alginate (SA) concentration; LE/SA ratio and chitosan/ion (Ca+2 or Cu+2) ratio on the immobilization yield were investigated. Immobilized LE on Ca-beads and Cu-beads was then used to degrade an EE2 solution. The optimal conditions for LE immobilization on Ca-beads were: 1.5% (w/v) SA, 1:5 (v/v) LE/SA and 3:7 (v/v) chitosan/ion (Ca+2). The optimal conditions for immobilization on Cu-beads were 2.0% (w/v) SA, 0.5:5 (v/v) LE/SA and 3:7 (v/v) chitosan/ion (Cu+2). The best result was obtained for immobilized LE on Ca-beads in buffer-absent medium. Furthermore, the immobilized enzyme was reused in five cycles for EE2 removal. The formation of EE2 dimers by LE treatment has been demonstrated by electrospray ionization coupled to time of flight mass spectrometer (ESI–TOF–MS). The results evidenced that immobilized LE in alginate–chitosan–divalent cation bead is an effective alternative for EE2 removal.

Stability of immobilized laccase on Luffa Cylindrica fibers and assessment of synthetic hormone degradation

In this work were studied the pH, thermal, and storage stability of free and immobilized laccases. Enzymes were produced by Pleurotus ostreatus on potato dextrose (PD) broth and potato dextrose modified (PDM) broth, and immobilized using Luffa cylindrica fibers as support. Both free and immobilized enzymes were assessed on their respective enzymatic activities and for 17α-ethinylestradiol (EE2) degradation. The optimum pH conditions concerning laccase activity ranged from 3.6 to 4.6, while temperature ranged between 30 °C and 50 °C for both free and immobilized enzyme. Laccase produced using PD broth presented greater storage stability and thermal stability than that of PDM. Best EE2 removals were of 79.22% and 75.00% for the free and immobilized enzymes, respectively. Removal rates were assessed during 8 h at pH 5. The removal of 17α-ethinylestradiol was stabilized in the fourth cycle of use. Results imply that immobilization promoted stability towards pH and temperature variations, although media played a decisive role in the enzymatic activity. Both free and immobilized laccases of P. ostreatus were able to degrade EE2, whereas immobilized laccase in PDM medium presented possible reuse applicability, albeit removal was not optimal when compared to other reports.

Photocatalytic Removal of 17α-Ethinyl Estradiol Using the Bi2O3/Bi2O4 Photocatalyst

A series of Bi2O3/Bi2O4 composites were prepared by calcining raw materials with different NaBiO3/KOH mass ratios. The Bi2O3/Bi2O4 photocatalysts were characterized by the various measurements and their photocatalytic performance was assessed by degradation of 17α-ethinyl estradiol (EE2). The Bi2O3/Bi2O4 photocatalysts have wider visible light absorption and lower fluorescence emission intensity than the commercial Bi2O3. So, they displayed superior performance in the degradation of EE2. After the adsorption equilibrium of EE2 was reached, the degradation efficiency of Bi2O3/Bi2O4 for EE2 can reach a maximum value of ~ 100% in 12 min under the visible-light illumination. Degradation analysis results indicated that both holes (h+) and superoxide radical (·O2−) can affect the degradation efficiency of EE2.

Influence of natural organic matter on horseradish peroxidase-mediated removal of 17α-ethinylestradiol: Role of molecular weight

Ubiquitous natural organic matter (NOM) plays a crucial role in the peroxidase-mediated transformation of phenolic pollutants in aquatic environment. As a poorly defined polydispersed mixture of assorted organic substances with wide molecular weight (MW) distribution, NOM has far prevented researchers from finding out the primarily responsible components for the specific effect. In this work, MW fractionated NOMs (Mf-NOMs) were used to investigate their roles on horseradish peroxidase (HRP)-mediated transformation of 17α-ethinylestradiol (EE2). The removal rate of EE2 was restrained in the presence of pristine or Mf-NOMs, and the inhibitory mechanism was MW-dependent. Low Mf-NOMs restrained the enzymatic reaction by acting as competitive substrates, while high Mf-NOMs retained freely dissolved EE2 which reduced its availability for enzymatic reaction. The contribution of these two processes to the inhibition induced by pristine NOM was further quantified and found to be relevant to the reaction conditions, especially EE2 concentration. The findings of this work reveal more complex influences of NOM on the enzymatic reaction than ever demonstrated, which aids in understanding the fate of EE2 and other congener contaminants in natural and municipal water.