A model of natural degradation of 17-α-ethinylestradiol in surface water and identification of degradation products by GC-MS

Over the past decade, the environment has been polluted by a wide spectrum of exogenous chemicals and environmental analysis has become one of the most progressive parts of analytical research. The aim of this work was to determine the kinetics of natural degradation, and to identify the degradation products of the massively used estrogenic drug, 17-α-ethinylestradiol. The photodegradation, oxidation and thermostability conditions were selected according to ICH requirements for pharmaceutical stability testing. A simple 72-h photodegradation study in purified water exhibited significant first-order kinetics with the kinetic constant k = 0.0303 h^?1, and degradation halftime 22.8 h. The basic halftime could be reduced to 17.1 h by the addition of sea salt, and increase in temperature. Monohydroxy, dihydroxy and dehydrogenated derivatives of ethinylestradiol with intact steroidal structure were identified as major degradation products resulting from simple photodegradation. The addition of an oxidative agent significantly accelerated the degradation rate; combined with higher temperature, the degradation halftime was reduced to 1.1 h with the first-order kinetic constant k = 0.632 h^?1. TOC analysis showed a notable decrease of organic mass (18% in 3 days) during oxidation experiments, and confirmed the degradation of steroidal structure.

     

Microbial transformation of synthetic estrogen 17α-ethinylestradiol

Natural estrogens such as estrone, 17β-estradiol, estriol, and the particularly recalcitrant synthetic estrogen 17α-ethinylestradiol used as oral contraceptive, accumulate in the environment and may give rise to health problems. The processes participating in their removal from soil, wastewater, water-sediments, groundwater-aquifer material, and wastewater or sewage treatment plant effluents may involve the action of bacterial and microbial consortia, and in some cases fungi and algae. This review discusses the different efficiencies of bacterial degradation of 17α-ethinylestradiol under aerobic and anaerobic conditions, the role of sulfate-, nitrate-, and iron-reducing conditions in anaerobic degradation, and the role of sorption. The participation of autotrophic ammonia oxidizing bacteria and heterotrophic bacteria in cometabolic degradation of estrogens, the estrogen-degrading action of ligninolytic fungi and their extracellular enzymes (lignin peroxidase, manganese-dependent peroxidase, versatile peroxidase, laccase), and of algae are discussed in detail.     

Fabrication of ZnO–SnO2 nanocomposite and its photocatalytic activity for enhanced degradation of Biebrich scarlet

Environmental Science and Pollution Research - The n–n-type ZnO–SnO2 nanocomposite was fabricated using malic acid following a simple one-pot co-precipitation method. The fabricated...     

Synthesis of γ-Fe2O3/La/Bi2WO6 composites for enhanced visible light-driven photocatalytic degradation of tetracycline hydrochloride

Environmental Science and Pollution Research - γ-Fe2O3/La/Bi2WO6 heterojunction composites have been successfully synthesized by simple and convenient hydrothermal method. The photocatalytic...     

Novel PVA/chitosan composite membrane modified using bio-fabricated α-MnO2 nanoparticles for photocatalytic degradation of cationic dyes

Environmental Science and Pollution Research - By integrating the benefits of poly vinyl alcohol (PVA) and chitosan (CS) with α-MnO2 nanoparticles (MNPs), a novel type of nano-polymer...     

TiO₂ supported over SBA-15: an efficient photocatalyst for the pesticide degradation using solar light

Photocatalytic degradation and mineralization of pesticides are studied over TiO(2) supported mesoporous SBA-15 composite system using solar light. TiO(2) is immobilized over SBA-15 by solid sate dispersion method. The catalysts are characterized by XRD, surface area, UV-Vis diffused reflectance spectra, SEM and TEM. The detailed photocatalytic degradation studies are carried out over TiO(2), SBA-15 and different TiO(2) wt% supported SBA-15. The activity evaluation parameters such as catalyst amount, pH, and pollutant initial concentration are studied taking isoproturon as a model compound and established conditions for pesticide degradation. The optimum degradation is achieved over 10 wt% TiO(2)/SBA-15 within 30 min and the reaction is following pseudo-first order kinetics. The isoproturon mineralization is monitored with TOC reduction and it takes around 9h for disappearance. The commercial pesticide solutions containing imidacloprid and phosphamidon are also successfully degraded over these composites with the established conditions. The data indicates that 10 wt% TiO(2)/SBA-15 composite is an effective and highly active system for the pesticide degradations.     

Life cycle assessment of waste printed wiring board–derived Ag photocatalyst for sustainable fermentable sugar production

Environmental Science and Pollution Research - An exploratory work involving waste printed wiring board (WPWB)–derived inexpensive silver oxide (Ag2O)–grafted silica-alumina composite...     

Ultrafiltration ceramic membrane as oxidant-catalyst/water contactor to promote sulfate radical AOPs: a case study on 17β-estradiol and 17α-ethinylestradiol removal

Environmental Science and Pollution Research - This work highlights the performance of an ultrafiltration ceramic membrane as photocatalyst support and oxidant-catalyst/water contactor to promote...     

Sorption of carbamazepine, 17α-ethinylestradiol, iopromide and trimethoprim to biomass involves interactions with exocellular polymeric substances

The sorption of carbamazepine (CBZ), iopromide (IOP), trimethoprim (TMP) and 17α-ethinylestradiol (EE2) was evaluated using four biomass types (pure ammonia oxidizing bacterial culture, two heterotrophic enrichment cultures with varying levels of oxygenase activity, and a full-scale nitrifying activated sludge (NAS) culture). CBZ and IOP did not sorb to the four biomass types. EE2 did not sorb to the pure culture but sorbed significantly to the heterotrophic cultures and NAS. TMP sorbed to the heterotrophic cultures and NAS, and was not evaluated for the pure culture. Three floc characteristics (hydrophobicity, median particle size, organic matter content) correlated moderately well with the EE2 organic matter sorption coefficient (K_OM,EE2). Zeta potential did not correlate well with K_OM,EE2 but did with K_OM,TMP, indicating that TMP sorption is more influenced by electrostatic factors than EE2. Once divalent cation-linked exocellular polymeric substances (EPS) were removed from flocs, EE2 and TMP sorption to the non-EPS (cellular) fraction decreased by approximately 50%. The correlation between K_OM,EE2 for the non-EPS cellular fraction deteriorated while the correlation between K_OM,TMP improved. EE2 seemed to sorb more strongly to EPS protein whereas TMP sorbed equally to polysaccharide and protein EPS. Attempts to develop predictive models were not successful. Pharmaceuticals that sorbed to biomass samples underwent biodegradation whereas those that did not sorb were not biodegraded, suggesting a relationship between sorption and pharmaceutical biotransformation.     

Preparation,characterization, and photocatalytic activity evaluation of Fe–N-codoped TiO2/fly ash cenospheres floating photocatalyst

Nitrogen-doped titanium dioxide (TiO₂) and Fe–N-codoped TiO₂ layers on fly ash cenospheres (FAC) as floating photocatalyst were successfully prepared through sol–gel method. Photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)–Vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption analyses for Brunauer–Emmett–Teller (BET) specific surface area. Photocatalytic efficiency of the prepared catalyst was evaluated through using the decomposition of Rhodamine B (RhB) as a model compound under visible light irradiation. Photocatalytic activity and kinetics of catalyst under visible light were detected in details from different Fe/Ti mole ratios by detecting photodegradation of RhB. Experimental results show that when the calcination temperature was 550 °C, the dosage of FAC was 3.0 g, and the mole ratio of Fe/Ti was 0.71 %; the synthesized Fe–N-TiO₂/FAC photocatalyst presented as anatase phase and that N and Fe ions were doped into TiO₂ lattice. The material’s specific surface area was 34.027 m²/g, and UV–Vis diffuse reflectance spectroscopy shows that the edge of the photon absorption has been red shifted up to 400–500 nm. Fe–N-codoped titanium dioxide on FAC had excellent photocatalytic activity during the process of photodegradation of RhB under visible light irradiation.

     

Structured photocatalytic systems: photocatalytic coatings on low-cost structures for treatment of water contaminated with micropollutants—a short review

Environmental Science and Pollution Research - The persistence of many micropollutants in water and wastewater is of great concern to the contemporary scientific community. Several types of...     

Bioaccumulation of the pharmaceutical 17α-ethinylestradiol in shorthead redhorse suckers (Moxostoma macrolepidotum) from the St. Clair River, Canada

17α-ethynylestradiol (EE2), a synthetic estrogen prescribed as a contraceptive, was measured in Shorthead Redhorse Suckers (ShRHSs) (Moxostoma macrolepidotum) collected near a wastewater treatment plant (WWTP) in the St. Clair River (Ontario, Canada). We detected EE2 in 50% of the fish samples caught near the WWTP (Stag Island), which averaged 1.6 ± 0.6 ng/g (wet weight) in males and 1.43 ± 0.96 ng/g in females. No EE2 was detected in the samples from the reference site (Port Lambton) which was 26 km further downstream of the Stag Island site. Only males from Stag Island had VTG induction, suggesting the Corunna WWTP effluent as a likely source of environmental estrogen. EE2 concentrations were correlated with total body lipid content (R² = 0.512, p < 0.01, n = 10). Lipid normalized EE2 concentrations were correlated with δ¹⁵N (R² = 0.436, p < 0.05, n = 10), suggesting higher EE2 exposures in carnivores. Our data support the hypothesis of EE2 bioaccumulation in wild fish.     

Solar light–driven photocatalytic degradation and mineralization of beta blockers propranolol and atenolol by carbon dot/TiO2 composite

Herein improved solar light–driven photocatalytic degradation and mineralization of two emerging pollutants as well as recalcitrant beta blockers propranolol (PR) and atenolol (AT) have been demonstrated by metal-free carbon dot/TiO₂ (CDT) composite. Hydrothermally synthesized TiO₂ has been decorated with electrochemically synthesized carbon dots (CDs) and was well characterized by various analytical techniques viz. XRD, FTIR, Raman, XPS, UV–visible DRS, FESEM, and TEM. The optimized CDT composite, 2CDT (2 mL carbon dot/TiO₂), showed?~?3.45- and?~?1.75-fold enhancement in the photodegradation rate as compared to pristine TiO₂ for PR and AT respectively in 1 hour of irradiation along with complete degradation of PR and AT after 3 hours of irradiation. 2CDT exhibited 76% and 80% mineralization of PR and AT in contrast with 62% and 47% observed by pristine TiO₂. Further, the major reaction intermediates formed after degradation have been identified by HPLC/MS analysis, confirming more than 99% reduction of the parent compound for both PR and AT. Reusability of the optimized catalyst also showed successful degradation up to 3 cycles, showing reduction abilities of 97%, 95%, and 94% for 1st, 2nd, and 3rd cycle respectively. The enhanced degradation and mineralization efficiency of the 2CDT composite could be attributed to the excellent photosensitizer and electron reservoir properties of the CD along with upconverted photoluminescence behavior. The present study unlocks the possibility of using metal-free, facile CDT composite for effective degradation and mineralization of widely used beta blockers and other pharmaceuticals.

     

No bioavailability of 17α-ethinylestradiol when associated with nC60 aggregates during dietary exposure in adult male zebrafish (Danio rerio)

The C(60) fullerene is a manufactured carbon nanoparticle (CNP) that could pose a risk to humans and other organisms after release into the environment. In surface waters, C(60) is likely to be present as aggregates of nC(60) and these aggregates can associate with other substances that are toxic. Our goal was to evaluate the association of a model contaminant [17α-ethinylestradiol (EE2)] with nC(60) and determine bioavailability of EE2 after accumulation by a filter feeding organism [Brine shrimp (BS) Artemia sp.] and subsequent dietary exposure in zebrafish. Aqueous suspensions of nC(60) were prepared (600 mg C(60)/900 mL, 6-month water stirred method) with/without EE2 (1 μg/L) and BS were exposed to these preparations. Accumulation of nC(60) in gut of BS was assessed by light microscopy, and C(60) were extracted from BS and concentration analyzed by HPLC. Adult male zebrafish were fed (5d) live BS according to the following treatments: BS (control); BS containing nC(60); BS containing nC(60)+EE2; or BS containing EE2. Liver was excised from exposed fish and total RNA was extracted for assessment of vitellogenin gene (vtg1A/B) expression. The vtg1A/B was highly up-regulated in fish exposed to BS containing EE2, but expression of vtg1A/B did not differ from controls in other treatments. The EE2 associated with nC(60) did not become bioavailable in zebrafish during passage through the intestinal tract of zebrafish. Results have implications on the effect of nC(60) on the bioavailability of co-contaminants in organisms during dietary exposure.     

Effectiveness of UV/SO32− advanced reduction process for degradation and mineralization of trichlorfon pesticide in water: identification of intermediates and toxicity assessment

Environmental Science and Pollution Research - This study aimed to investigate the degradability, mineralization, proposed decomposition pathway, intermediate products, and toxicity of effluent...     

Development of zerovalent iron and titania (Fe0/TiO2) composite for oxidative degradation of dichlorophene in aqueous solution: synergistic role of peroxymonosulfate (HSO5−)

Environmental Science and Pollution Research - Binary composite of zerovalent iron and titanium dioxide (Fe0/TiO2) was synthesized for the catalytic removal of dichlorophene (DCP) in the presence...     

Novel two-step vapor-phase synthesis of UV–Vis light active Fe2O3/WO3 nanocomposites for phenol degradation

Supported Fe₂O₃/WO₃ nanocomposites were fabricated by an original vapor phase approach, involving the chemical vapor deposition (CVD) of Fe₂O₃ on Ti sheets and the subsequent radio frequency (RF)-sputtering of WO₃. Particular attention was dedicated to the control of the W/Fe ratio, in order to tailor the composition of the resulting materials. The target systems were analyzed by the joint use of complementary techniques, that is, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and optical absorption spectroscopy. The results showed the uniform decoration of α-Fe₂O₃ (hematite) globular particles by tiny WO₃ aggregates, whose content could be controlled by modulations of the sole sputtering time. The photocatalytic degradation of phenol in the liquid phase was selected as a test reaction for a preliminary investigation of the system behavior in wastewater treatment applications. The system activity under both UV and Vis light illumination may open doors for further material optimization in view of real-world end-uses.

     

Titanium dioxide and graphitic carbon nitride–based nanocomposites and nanofibres for the degradation of organic pollutants in water: a review

Environmental Science and Pollution Research - The paper reviews graphitic carbon nitride–based nanostructured photocatalytic materials and nanofibres for applications in water purification....     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.