Removal of ecotoxicity of 17α-ethinylestradiol using TAML/peroxide water treatment

17α -ethinylestradiol (EE2), a synthetic oestrogen in oral contraceptives, is one of many pharmaceuticals found in inland waterways worldwide as a result of human consumption and excretion into wastewater treatment systems. At low parts per trillion (ppt), EE2 induces feminisation of male fish, diminishing reproductive success and causing fish population collapse. Intended water quality standards for EE2 set a much needed global precedent. Ozone and activated carbon provide effective wastewater treatments, but their energy intensities and capital/operating costs are formidable barriers to adoption. Here we describe the technical and environmental performance of a fast- developing contender for mitigation of EE2 contamination of wastewater based upon smallmolecule, full-functional peroxidase enzyme replicas called “TAML activators”. From neutral to basic pH, TAML activators with H2O2 efficiently degrade EE2 in pure lab water, municipal effluents and EE2-spiked synthetic urine. TAML/H2O2 treatment curtails estrogenicity in vitro and substantially diminishes fish feminization in vivo. Our results provide a starting point for a future process in which tens of thousands of tonnes of wastewater could be treated per kilogram of catalyst. We suggest TAML/H2O2 is a worthy candidate for exploration as an environmentally compatible, versatile, method for removing EE2 and other pharmaceuticals from municipal wastewaters.Heinz Endowments, the Swiss National Science Foundation, the Steinbrenner Institute for a Steinbrenner Doctoral Fellowship. NMR instrumentation at CMU was partially supported by NSF (CHE-0130903 and CHE-1039870)

Simultaneous determination of natural and synthetic steroid estrogens and their conjugates in aqueous matrices by liquid chromatography / mass spectrometry

An analytical method for the simultaneous determination of nine free and conjugated steroid estrogens was developed with application to environmental aqueous matrices. Solid phase extraction (SPE) was employed for isolation and concentration, with detection by liquid chromatography/mass spectrometry (LC/MS) using electrospray ionisation (ESI) in the negative mode. Method recoveries for various aqueous matrices (wastewater, lake and drinking water) were determined, recoveries proving to be sample dependent. When spiked at 50 ng/l concentrations in sewage influent, recoveries ranged from 62-89 % with relative standard deviations (RSD) < 8.1 %. In comparison, drinking water spiked at the same concentrations had recoveries between 82-100 % with an RSD < 5%. Ion suppression is a known phenomenon when using ESI; hence its impact on method recovery was elucidated for raw sewage. Both ion suppression from matrix interferences and the extraction procedure has bearing on the overall method recovery. Analysis of municipal raw sewage identified several of the analytes of interest at ng/l concentrations, estriol (E3) being the most abundant. Only one conjugate, estrone 3-sulphate (E1-3S) was observe

The simpler the better: Highly sensitive 17α-ethinylestradiol sensor based on an unmodified carbon paper transducer

The remarkable features of a carbon fiber paper sensor (CP) were employed for detection of the estrogenic hormone 17α-ethinylestradiol (EE2), considered a contaminant of emerging concern due to its potential ecotoxicity and widespread in the aquatic ecosystems. In this work, an unpreceded CP pre-treatment study was conducted with the (Il)-hexacyanoferrate(III) ion pair, however a bare sensor without pre-treatment revealed higher efficiency on the oxidation of EE2 compared to a chemical and electrochemical pre-treated CP and a gold nanoparticles modified CP, being thus selected for EE2 determinations. The analytical conditions were thoroughly optimized in terms of electrolyte pH (pH 7), differential pulse voltammetry parameters (modulation time 0.003 s, amplitude 0.09 V, interval time 0.1 s and step potential 0.01 V), and analyte preconcentration potential (0.4 V) and time (180 s). The hormone can be determined by the CP in a wide linear range from 0.1 to 1000 nM, achieving a detection limit of 0.14 ± 0.005 nM and an outstanding sensitivity of 1636 ± 232 μA μM−1 cm−2 in the lowest linear zone (0.1–1 nM). The sensor was validated in river water and fish reaching good recoveries (91.2 ± 4.6 to 109.0 ± 7.1%), reproducibility and repeatability. Moreover, the sensor showed high selectivity to EE2 in the presence of several potential interfering compounds and frequently prescribed drugs, though it could not discriminate the similar hormone, 17β-estradiol, being the total concentration obtained in this case. CP-based sensors emerge as efficient electroanalytical tools, suggesting that modification of the surface may not always be beneficial in terms of sensitivityThe authors are grateful for the financial support by the project PTDC/ASP-PES/29547/2017 (POCI-01-0145-FEDER-029547) funded by FEDER funds through the POCI and by National Funds through Fundação para a Ciência e a Tecnologia (FCT), Ministério da Ciência, Tecnologia e Ensino Superior (MCTES). This work received support by UIDB/50006/2020, UIDP/50006/2020 and LA/P/0008/2020 by the Fundação para a Ciência e a Tecnologia (FCT), Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national fundsinfo:eu-repo/semantics/publishedVersio

Fate of drugs during wastewater treatment

This is the post-print version of the final paper published in TrAC Trends in Analytical Chemistry. The published article is available from the link below. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. Copyright @ 2013 Elsevier B.V.Recent trends in the determination of pharmaceutical drugs in wastewaters focus on the development of rapid multi-residue methods. This review addresses recent analytical trends in drug determination in environmental matrices used to facilitate fate studies. Analytical requirements for further fate evaluation and tertiary process selection and optimization are also discussed.EPSRC, Northumbrian Water, Anglian Water, Severn Trent Water, Yorkshire Water, and United Utilities

Removal of steroid estrogens in carbonaceous and nitrifying activated sludge processes

This is the post-print version of the final paper published in Chemosphere. The published article is available from the link below. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. Copyright @ 2010 Elsevier B.V.A carbonaceous (heterotrophic) activated sludge process (ASP), nitrifying ASP and a nitrifying/denitrifying ASP have been studied to examine the role of process type in steroid estrogen removal. Biodegradation efficiencies for total steroid estrogens (ΣEST) of 80 and 91% were recorded for the nitrifying/denitrifying ASP and nitrifying ASP respectively. Total estrogen biodegradation (ΣEST) was only 51% at the carbonaceous ASP, however, the extent of biodegradation in the absence of nitrification clearly indicates the important role of heterotrophs in steroid estrogen removal. The low removal efficiency did not correlate with biomass activity for which the ASPcarbonaceous recorded 80 μg kg−1 biomass d−1 compared to 61 and 15 μg kg−1 biomass d−1 at the ASPnitrifying and ASPnitrifying/denitrifying respectively. This finding was explained by a moderate correlation (r2 = 0.55) between total estrogen loading (ΣEST mg m−3 d−1) and biomass activity (μg ΣEST degraded kg−1 d−1) and has established the impact of loading on steroid estrogen removal at full-scale. At higher solids retention time (SRT), steroid estrogen biodegradation of >80% was observed, as has previously been reported. It is postulated that hydraulic retention time (HRT) is as important as SRT as this governs both reaction time and loading. This observation is based on the high specific estrogen activity determined at the ASPcarbonaceous plant, the significance of estrogen loading and the positive linear correlation between SRT and HRT.Public Utilities Board of Singapore, Anglian Water Ltd., Severn Trent Water Ltd., Thames Water Utilities Ltd., United Utilities Plc., and Yorkshire Water Services Ltd

Effects of binary mixtures of xenoestrogens on gonadal development and zeproduction in zebrafish

Previous studies exposing fish to xenoestrogens have demonstrated vitellogenin (VTG) induction, delayed gametogenesis, altered sex distribution, and decreased reproductive performance, with a majority of those studies focusing on exposure to single chemicals. The objective of this study was to determine the effects of binary mixtures of a weak estrogen receptor agonist, nonylphenol (NP) and a potent estrogen receptor agonist, 17&#945;-ethinylestradiol (EE) on sex distribution, gametogenesis, VTG induction, heat shock protein 70 (HSP70) expression and reproductive capacity in zebrafish (Danio rerio). Fish were exposed from 2 to 60 days post-hatch (dph) to nominal concentrations of 10 or 100 µg/l NP (NP10 or NP100, respectively), 1 or 10 ng/l EE (EE1 or EE10, respectively), 1 ng/l EE + 10 or 100 µg/l NP (EE1+NP10 or EE1+NP100, respectively), 10 ng/l EE + 10 or 100 µg/l NP (EE10+NP10 or EE10+NP100, respectively) or solvent control (0.01% acetone v/v) in a static-renewal system with replacement every 48h. At 60 dph, fish from each treatment were euthanized for histological examination of gonads, and whole body VTG and HSP70 levels. Remaining fish were reared in clean water until adulthood (240 dph) for breeding studies. In all EE10 exposure groups (EE10, EE10+NP10 and EE10+NP100), increasing NP concentration acted less than additively to the action of EE in terms of VTG induction at 60 dph. Similarly, a less than additivity of effect was observed with egg production, where EE1+NP100 exposure resulted in significantly more eggs produced per breeding trial than EE1 alone. Histological staging of oogenesis revealed suppressed gametogenesis in females at 60 dph. There were no differences among treatment groups in whole body HSP70 expression in 60 dph fish or in gonadal HSP70 expression in adult fish. Although there was no statistical evidence of non-additivity, breeding trials in adults revealed significant reductions in egg viability, egg hatchability and/or F1 swim-up success, suggesting that developmental exposures to xenoestrogens may cause irreversible effects on egg quality and progeny even after depuration. In conclusion, these results suggest that environmentally relevant mixtures of NP and EE can produce additive or non-additive effects depending on the particular response being determined and the respective exposure concentrations of each chemical. Thus, it is recommended that caution be exercised in ecological risk assessments when assuming additivity in piscine responses to xenoestrogen mixtures

Stability of polymeric membranes to UV exposure before and after coating with TiO2 nanoparticles

Acknowledgments: Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP, Nº 2019/ 04319-9), Associate Laboratory for Green Chemistry—LAQV, Unidade de Tecnologia de Células Animais do iBET e à Paula Alves, iNOVA4Health—UIDB/Multi/04462/2020, a program financially supported by Fundação para a Ciência e Tecnologia/Ministério da Educação e Ciência, through national funds is acknowledged. Funding from INTERFACE Program, through the Innovation, Technology and Circular Economy Fund (FITEC), is also gratefully acknowledged. Funding Information: Funding: Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP, Nº 2019/04319-9), Associate Laboratory for Green Chemistry—LAQV (through projects UIDB/50006/2020 and UIDP/ 50006/2020), Fundação para a Ciência e a Tecnologia through the project PTDC/EAM-AMB/30989/2017, Unidade de Tecnologia de Células Animais do iBET, iNOVA4Health—UIDB/Multi/04462/2020. Funding Information: Funda??o de Amparo ? Pesquisa do Estado de S?o Paulo (FAPESP, N? 2019/04319-9), Associate Laboratory for Green Chemistry?LAQV (through projects UIDB/50006/2020 and UIDP/ 50006/2020), Funda??o para a Ci?ncia e a Tecnologia through the project PTDC/EAM-AMB/30989/2017, Unidade de Tecnologia de C?lulas Animais do iBET, iNOVA4Health?UIDB/Multi/04462/2020. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.The combination of photocatalysis and membrane filtration in a single reactor has been proposed, since the photocatalytic treatment may degrade the pollutants retained by the membrane and reduce fouling. However, polymeric membranes can be susceptible to degradation by UV radiation and free radicals. In the present study, five commercial polymeric membranes were exposed to ultraviolet (UV) radiation before and after applying a sol–gel coating with TiO2 nanoparticles. Membrane stability was characterized by changes in hydrophilicity as well as analysis of soluble substances and nanoparticles detached into the aqueous medium, and by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectrometry (EDS) for structural, morphological, and elemental distribution analysis, respectively. The TiO2 coating conferred photocatalytic properties to the membranes and protected them during 6 h of UV radiation exposures, reducing or eliminating chemical and morphological changes, and in some cases, improving their mechanical resistance. A selected commercial nanofiltration membrane was coated with TiO2 and used in a hybrid reactor with a low-pressure UV lamp, promoting photocatalysis coupled with cross-flow filtration in order to remove 17α-ethinylestradiol spiked into an aqueous matrix, achieving an efficiency close to 100% after 180 min of combined filtration and photocatalysis, and almost 80% after 90 min.publishersversionpublishe

Environmental concentrations of anti-androgenic pharmaceuticals do not impact sexual disruption in fish alone or in combination with steroid oestrogens

This article has been made available through the Brunel Open Access Publishing Fund.Sexual disruption in wild fish has been linked to the contamination of river systems with steroid oestrogens, including the pharmaceutical 17α-ethinylestradiol, originating from domestic wastewaters. As analytical chemistry has advanced, more compounds derived from the human usage of pharmaceuticals have been identified in the environment and questions have arisen as to whether these additional pharmaceuticals may also impact sexual disruption in fish. Indeed, pharmaceutical anti-androgens have been shown to induce such effects under laboratory conditions. These are of particular interest since anti-androgenic biological activity has been identified in the aquatic environment and is potentially implicated in sexual disruption alone and in combination with steroid oestrogens. Consequently, predictive modelling was employed to determine the concentrations of two anti-androgenic human pharmaceuticals, bicalutamide and cyproterone acetate, in UK sewage effluents and river catchments and their combined impacts on sexual disruption were then assessed in two fish models. Crucially, fish were also exposed to the anti-androgens in combination with steroid oestrogens to determine whether they had any additional impact on oestrogen induced feminisation. Modelling predicted that the anti-androgenic pharmaceuticals were likely to be widespread in UK river catchments. However, their concentrations were not sufficient to induce significant responses in plasma vitellogenin concentrations, secondary sexual characteristics or gross indices in male fathead minnow or intersex in Japanese medaka alone or in combination with steroid oestrogens. However, environmentally relevant mixtures of oestrone, 17β-oestradiol and 17α-ethinylestradiol did induce vitellogenin and intersex, supporting their role in sexual disruption in wild fish populations. Unexpectedly, a male dominated sex ratio (100% in controls) was induced in medaka and the potential cause and implications are briefly discussed, highlighting the potential of non-chemical modes of action on this endpoint

Effects of 17α-Ethinylestradiol (EE\u3csub\u3e2\u3c/sub\u3e) on Reproductive Endocrine Status in Mummichog (\u3cem\u3eFundulus Heteroclitus\u3c/em\u3e) Under Differing Salinity and Temperature Conditions

Waterborne exposure to 17α-ethinylestradiol (EE2), a synthetic estrogen, has previously been shown to decrease reproductive endocrine status in the estuarine killifish or mummichog (Fundulus heteroclitus macrolepidotus; northern subspecies). To evaluate if variations in salinity or temperature holding conditions modify the effects of EE2 on gonad size, plasma reproductive steroid levels, and gonadal steroidogenesis, mummichog were exposed in vivo for 14 days to 0, 50 and 250 ng/L EE2 in 0, 16 and 32 ppt salinity at 18°C and to 0 and 250 ng/L EE2 at 10, 18 and 26°C at 16 ppt salinity. Effects due to salinity were limited; however, 250 ng/L EE2 decreased plasma 17β-estradiol (E2) levels and in vitro gonadal E2 production and plasma 11-ketotestosterone (11-KT) across all salinities. Higher temperatures triggered gonadal growth in both sexes as well as increased plasma E2 and gonadal E2 production in females, while 11-KT production was decreased in males. EE2 counteracted the effect of temperature as determined by depressed gonadal growth in males. In both exposures, the effects of EE2 on testosterone (T) production were variable. The use of steroidogenic precursors (25-OH cholesterol, and/or pregnenolone and/or testosterone) in the in vitro gonadal incubations indicated decreased E2 production in females and 11-KT production in males were predominately due to suppression of the terminal conversion step between T and E2 or 11-KT. Ovarian cyp19a gene expression was not affected by 250 ng/L EE2 compared to controls at 16 ppt and 18oC (the only treatment combinations tested). The lack of effects of salinity could be protective for a species spawning in such a variable environment. Gonadal growth at higher temperatures confirms previous work on northern mummichog while EE2 effects on gonadal growth could be due to temperature-related increases in EE2 uptake and/or increased susceptibility during gonadal maturation. In conclusion, the present work demonstrated that environmental conditions impact effects of EE2, including terminal steroid production in the gonads. These results should be considered in designing standardized estuarine fish reproductive bioassays and in understanding the potential effects of reproductive contaminants in estuarine environments