Fixed-bed adsorption studies of endocrine-disrupting compounds from water by using novel calcium-based metal-organic frameworks.

The presence of emerging water pollutants such as endocrine-disrupting compounds (EDCs), including 17-ethynylestradiol (EE2), bisphenol A (BPA), and perfluorooctanoic acid (PFOA), in contaminated water sources poses significant environmental and health challenges. This study aims to address this issue by investigating the efficiency of novel calcium-based metal-organic frameworks, known as mixed-linker calcium-based metal-organic frameworks (Ca-MIX), in adsorbing these endocrine-disrupting compounds. This study analyzed the influence of influent concentration, bed height, and flow rate on pollutant removal, with bed height emerging as a crucial factor. From the breakthrough curves, it was determined that the column maximum adsorption capacities followed the order of 17-ethynylestradiol (101.52 µg/g; 40%) > bisphenol A (99.07 µg/g; 39%) > perfluorooctanoic acid (81.28 µg/g; 32%). Three models were used to predict the adsorption process, with the Yan model outperforming the other models. This suggests the potential of mixed-linker calcium-based metal-organic frameworks for removing endocrine-disrupting compounds from water, using the Yan model as an effective predictor. Overall, this study provides valuable insights for the development of effective water treatment methods using mixed-linker calcium-based metal-organic frameworks to remove endocrine-disrupting compounds from contaminated water sources.

Unveiling the presence of endocrine disrupting chemicals in northern French soils: Land cover variability and implications.

Endocrine disrupting chemicals (EDCs) are chemicals that can be found in the environment and have adverse effects on human health by mimicking, perturbing and blocking the function of hormones. They are commonly studied in water surfaces, rarely in soils, although it can be an important source of their presence in the environment. Their detection in soils is analytically challenging to quantify, hence the lack of known background concentrations found in the literature. This scientific research aimed to detect EDCs in soils by analyzing 240 soil samples using an optimized protocol of double extraction and analysis using liquid chromatography coupled to mass spectrometry. The optimized protocol allowed for very sensitive detection of the targeted compounds. The results showed a high concentration of 29.391 ng/g of 17ß-estradiol in soils and 47.16 ng/g for 17α-ethinylestradiol. Testosterone and Progesterone were detected at a highest of 1.02 and 6.58 ng/g, respectively. The ∑EDCs which included estrogens, progesterone, testosterone and Bisphenol A was found at an average of 22.72 ± 35.46 ng/g in the study area. The results of this campaign showed a heterogeneous geographic distribution of the EDCs compounds in the different zones of study. Additionally, the study conducted a comparison of the concentration of EDCs in different land covers including urban areas, agricultural lands, grasslands and forests. We observed a significant difference between forests and other land covers (p < 0.0001) for 17α-ethinylestradiol, estriol, and progesterone. This presence of EDCs in forest lands is not yet understood and requires further studies concerning its origins, its fate and its effect on human health. This study is the first large-scale sampling campaign targeting EDCs in soils in Europe and the second in the world. It is also the first to assess the concentrations of these compounds based on different land covers.

Dissolved organic matter accelerates microbial degradation of 17 alpha-ethinylestradiol in the presence of iron mineral.

Dissolved organic matter (DOM) and iron minerals widely existing in the natural aquatic environment can mediate the migration and transformation of organic pollutants. However, the mechanism of interaction between DOM and iron minerals in the microbial degradation of pollutants deserves further investigation. In this study, the mechanism of 17 alpha-ethinylestradiol (EE2) biodegradation mediated by humic acid (HA) and three kinds of iron minerals (goethite, magnetite, and pyrite) was investigated. The results found that HA and iron minerals significantly accelerated the biodegradation process of EE2, and the highest degradation efficiency of EE2 (48%) was observed in the HA-mediated microbial system with pyrite under aerobic conditions. Furthermore, it had been demonstrated that hydroxyl radicals (HO•) was the main active substance responsible for the microbial degradation of EE2. HO• is primarily generated through the reaction between hydrogen peroxide secreted by microorganisms and Fe(II), with aerobic conditions being more conducive. The presence of iron minerals and HA could change the microbial communities in the EE2 biodegradation system. These findings provide new information for exploring the migration and transformation of pollutants by microorganisms in iron-rich environments.

Removal of estrogens from primary settled sewage by repeated culture of Selenastrum capricornutum.

Biotransformation and biodegradation of estrogenic compounds by bacteria and even fungi have been reported widely, but the role of microalgae in the elimination of estrogens from municipal wastewater treatment plants and their interaction with other microorganisms in wastewater are not clear. This study reported the feasibility of repeatedly removing a mixture of 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2), each was 100 µg L-1, from primary settled municipal sewage by Selenastrum capricornutum (SC), a ubiquitous microalga, in four exposure cycles, each lasted 7 days, and how they interacted with the microbial consortium in sewage. Mixed estrogen in sewage stimulated the growth of SC, and the indigenous microorganisms in sewage also affected the microalgal growth. The indigenous microorganisms, particularly bacteria, could easily remove E2 (with 99.5% removal), so the role of SC was insignificant. On the contrary, EE2 was difficult to remove by indigenous microorganisms but the removal was significantly enhanced by SC, with almost all spiked EE2 being removed, even at the end of the fourth cycle (with 99.0% removal). These results indicated that SC, together with the indigenous microorganisms in wastewater, could be repeatedly used for simultaneous removal of E2 and EE2 from municipal sewage.

4-Azido-7-nitrobenzoxadiazole as innovative clickable fluorescence probe for trace and selective quantification of ethinylestradiol in human plasma.

Quantification of ethinylestradiol (EE) in biological matrices is challenging as it is a very potent drug with a very low Cmax (75 pg.ml-1 ). Despite the high sensitivity of fluorometric methods, the detection of EE was confined because its structure exhibited very limited fluorescence. Therefore, it must be derivatized first using a fluorogenic agent to produce a more potent fluorescence derivative to achieve the desired ultrasensitive bioanalysis. Here, for the first time, we proposed a promising click fluorescent probe, 4-azido-7-nitrobenzoxadiazole (NBD-AZ) to react with the alkyne group of EE, with the help of copper sulphate and l-ascorbic acid to give a highly fluorescent and stable 1,2,3-triazole derivative. Density functional theory calculation revealed how the triazole formation affects the quantum yield and fluorescence of click reaction product when compared with NBD-AZ. The resulting triazole exhibited a strong signal at a wavelength of 540 nm after excitation at 470 nm. Reaction parameters impacting the intensity of fluorescence were cautiously studied and optimized. The suggested approach has shown outstanding performance, high linearity (25-300 pg.ml-1 ) and a low detection limit of 7.5 pg.ml-1 . The enhanced sensitivity and selectivity were exploited for analyzing EE in plasma using liquid-liquid extraction for samples cleaning up without interference from any biological components and with a mean % recovery of 100.13 ± 0.39. Accuracy, sensitivity, selectivity, simplicity, and cost-effectiveness make this approach a convincing, promising, and appealing alternative to the reported analytical methods for EE bioanalysis in different matrices.

Efficient removal of endocrine disrupting compounds 17 α-ethynyl estradiol and 17 ß-estradiol by Enterobacter sp. strain BHUBP7 and elucidation of the degradation pathway by HRAMS analysis.

Owing to the increased population and their overuse, estrogens are being detected in the environment at alarming levels. They act as endocrine disrupting compounds (EDC's) posing adverse effects on animals and humans. In this study, a strain belonging to Enterobacter sp. strain BHUBP7 was recovered from a Sewage Treatment Plant (STP) situated in Varanasi city, U.P., India, and was capable of metabolizing both 17 α-Ethynylestradiol (EE2) and 17 ß-Estradiol (E2) separately as a sole carbon source. The strain BHUBP7 exhibited high rates of E2 degradation as compared to EE2 degradation. The degradation of E2 (10 mg/L) was 94.3% after four days of incubation, whereas the degradation of EE2 (10 mg/L) under similar conditions was 98% after seven days of incubation. The kinetics of EE2 and E2 degradation fitted well with the first-order reaction rate. FTIR analysis revealed the involvement of functional groups like C = O, C-C, C-OH during the degradation process. The metabolites generated during degradation of EE2 and E2 were identified using HRAMS and a plausible pathway was elucidated. It was observed that metabolism of both E2 and EE2 proceeded with the formation of estrone, which was then hydroxylated to 4-hydroxy estrone, followed by ring opening at the C4-C5 position, and was further metabolized by the 4,5 seco pathway leading to the formation of 3-(7a-methyl-1,5-dioxooctahydro-1H-inden-4-yl) propanoic acid (HIP). It is the first report on the complete pathway of EE2 and E2 degradation in Enterobacter sp. strain BHUBP7. Moreover, the formation of Reactive Oxygen Species (ROS) during the degradation of EE2 and E2 was observed. It was concluded that both hormones elicited the generation of oxidative stress in the bacterium during the degradation process.

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.

A robust multi-residue method for the monitoring of 25 endocrine disruptors at ultra-trace levels in surface waters by SPE-LC-MS/MS.

Estrogenic endocrine disruptors are one of the biggest ecotoxicological threats in water that pose a significant ecological burden and health-risk for humans due to their high biological activity and proven additive effects. Therefore, we have developed and validated the most comprehensive and ultra-sensitive analytical method published to date, for reliable quantification of 25 high-risk endocrine disruptors at their ecologically relevant concentrations: naturally excreted hormones (estradiol, estrone, estriol, testosterone, corticosterone, and progesterone), synthetic hormones used for contraception and menopausal symptoms (ethinylestradiol, drospirenone, chlormadinone acetate, norgestrel, gestodene, tibolone, norethindrone, dienogest, and cyproterone) and bisphenols (BPS, BPA, BPF, BPE, BPAF, BPB, BPC, and BPZ). It is based on a solid-phase extraction of water samples, followed by a robust dansyl chloride derivatization with detection by liquid chromatography-tandem mass spectrometry with a single sample preparation and two analytical methods using the same analytical column and mobile phases. The achieved limits of quantitation are in the sub-ng L-1 range, and detection limits as low as 0.02 ng L-1, meeting the newest proposal for environmental quality standards (EQS) by the EU water framework directive for estradiol and ethinylestradiol. The method was extensively validated and applied to seven representative Slovenian water samples, where we detected 21 out of 25 analytes; 13 were quantified in at least one sample. Estrone and progesterone were quantified in all samples, reaching levels up to 50 ng L-1; ethinylestradiol was higher than the current EQS (0.035 ng L-1) in three samples, and estradiol was above its EQS (0.4 ng L-1) in one sample, proving the method's applicability and the necessity for monitoring these pollutants.

Occurrence, bioconcentration, and human health risks of pharmaceuticals in biota in the Sea of Marmara, Türkiye.

The presence, bioconcentration, and health risk via seafood consumption of 11 pharmaceutical compounds belonging to different therapeutic groups (anti-inflammatory, antiepileptic, lipid regulators, and hormones) were investigated in the muscle tissues of fish and the meat of shrimp in the Sea of Marmara. Six biota species (Merlangius merlangus, Trachurus meditterraneus, Serranus hepatus, Pomatomus saltatrix, Parapenaeus longirostris, Spratus sprattus) were collected from the five stations in October and April 2019. Ultrasonic extraction method followed by solid phase extraction was used for extraction of pharmaceutical compounds from biota samples and then analyzed using high-performance liquid chromatography. Of the 11 compounds, 10 were detected in biota species. Ibuprofen was the most frequently detected pharmaceutical in the biota tissues at high concentrations (<3.0-1225 ng/g, dw). The other widely detected compounds were fenoprofen (<3.6-323 ng/g, dw), gemfibrozil (<3.2-480 ng/g, dw), 17α-ethynylestradiol (<2.0-462 ng/g, dw), and carbamazepine (<7.6-222 ng/g, dw). The bioconcentration factors of the selected pharmaceuticals calculated in various aquatic organisms ranged from 9 to 2324 L/kg. The estimated daily intakes of anti-inflammatories, antiepileptics, lipid regulators, and hormones via seafood consumption were 0.37-568, 1.1-324, 8.5-197, 3-340 ng/kg bw. Day, respectively. Based on hazard quotients, estrone, 17ß-estradiol, and 17α-ethynylestradiol may pose a health risk to humans through the consumption of this seafood.

Bioaugmentation removal and microbiome analysis of the synthetic estrogen 17α-ethynylestradiol from hostile conditions and environmental samples by Pseudomonas citronellolis SJTE-3.

Synthetic estrogens are emerging environmental contaminants with great estrogenic activities and stable structures that are widespread in various ecological systems and significantly threaten the health of organisms. Pseudomonas citronellolis SJTE-3 is reported to degrade the synthetic estrogen 17α-ethynylestradiol (EE2) efficiently in laboratory conditions. In this work, the environmental adaptability, the EE2-degrading properties, and the ecological effects of P. citronellolis SJTE-3 under different hostile conditions (heavy metals and surfactants) and various natural environment samples (solid soil, lake water, and pig manure) were studied. Strain SJTE-3 can tolerate high concentrations of Zn2+ and Cr3+, but is relatively sensitive to Cu2+. Tween 80 of low concentration can significantly promote EE2 degradation by strain SJTE-3, different from the repressing effect of Triton X-100. High concentration of Tween 80 prolonged the lagging phase of EE2-degrading process, while the final EE2 removal efficiency was improved. More importantly, strain SJTE-3 can grow normally and degrade estrogen stably in various environmental samples. Inoculation of strain SJTE-3 removed the intrinsic synthetic and natural estrogens (EE2 and estrone) in lake water samples in 4 days, and eliminated over 90% of the amended 1 mg/L EE2 in 2 days. Bioaugmentation of strain SJTE-3 in EE2-supplied solid soil and pig manure samples achieved a removal rate of over 55% and 70% of 1 mg/kg EE2 within 2 weeks. Notably, the bioaugmentation of extrinsic strain SJTE-3 had a slight influence on indigenous bacterial community in pig manure samples, and its relative abundance decreased significantly after EE2 removal. Amendment of EE2 or strain SJTE-3 in manure samples enhanced the abundance of Proteobacteria and Actinobacteria, implying their potential in utilizing EE2 or its metabolites. These findings not only shed a light on the environment adaptability and degradation efficiency of strain SJTE-3, but also provide insights for bioremediation application in complex and synthetic estrogen polluted environments.

Combined reverse osmosis and UV/H2O2 treatment of aqueous solutions of bisphenol A and 17α-ethinylestradiol: assessment of estrogenic activity.

Bisphenol-A (BPA) and 17α-ethinylestradiol (EE2) are considered endocrine disrupting compounds (EDC) and they may be harmful to the normal functioning of endocrine systems of humans and animals. Moreover, the presence of these compounds in superficial and groundwater may represent serious risks, even in low concentrations like ng·L-1. The objectives of this study were to remove BPA and EE2 from solutions containing a mixture of these compounds in ultrapure water at low concentrations through reverse osmosis (RO) membrane combined with a UV/H2O2 process. Furthermore, to assess the estrogenic activity reduction after such treatments, in vitro recombinant yeast-estrogen screen (YES) assay was used. The removal efficiencies of target micropollutants increased with the increase of H2O2 dosage. For RO permeate stream, they enhanced from 91% to 96% for EE2 and from 76% to 90% for BPA while, for the concentrate stream, from 70% to 81% for EE2 and 41% to 84% for BPA as the H2O2 concentration were increased from 100 to 1000 µg·L-1. The OH radicals' generation was the dominant factor in the degradation of EDC during the UV/H2O2 treatment since the photolysis itself was not enough to degrade BPA or EE2. The estrogenic activity reduction after UV/H2O2 treatment was high, ranging from 92% to 98% for the permeate stream and from 50% to 93% for the concentrate stream. The EE2 was responsible for the whole observed estrogenic activity since BPA does not present estrogenicity, by in vitro YES assay, in the concentrations observed.

The influence of aeration rate on the sorption of emerging pharmaceuticals in activated sludge.

The sorption of pharmaceuticals on activated sludge during the wastewater treatment process has been widely studied and considered one of the main mechanisms for the removal of these micropollutants from domestic sewage. Understanding the removal mechanism is important to reduce the environmental risk associated with these compounds. To the best of our knowledge, no data are reporting the influence of the aeration rate and, consequently, of the physicochemical properties of the sludge flocs, on the sorption of pharmaceutical compounds. In this context, the influence of the aeration rate (2, 5, and 8 L min-1) on the physical properties of the sludge and the sorption of two emerging pharmaceuticals, 17-alpha-ethynylestradiol (EE2) and diclofenac (DCF), was evaluated. The pharmaceuticals were analyzed by Solid Phase Extraction and Liquid Chromatography, and the sludge by Laser Particle Size Analyzer and Settling Curves. As a result, higher sorption for 17-alpha-ethinylestradiol (78-96%) in comparison to diclofenac (23-43%) was observed, corroborating the greater hydrophobicity of EE2. Higher pharmaceuticals removal rates were observed for the highest aeration (10.02 µgEE2 gSST-1 and 3.99 µgDCF gSST-1) in comparison to the lowest one (7.81 µgEE2 gSST-1 and 2.58 µgDCF gSST-1), what can be attributed to structural and surface changes in flocs. Smaller and more dispersed flocs were observed when aeration was increased (104.4 µm for 8 L min-1 and 63.8 µm for 2 L min-1). The results suggest that the increase in aeration seems to be promising for the removal of pharmaceuticals by sorption in sewage sludge, especially for the hydrophobic ones.

Capture-SELEX of DNA Aptamers for Estradiol Specifically and Estrogenic Compounds Collectively.

Estrogenic compounds such as estrone (E1), 17ß-estradiol (E2), and 17α-ethynylestradiol (EE2) are serious environmental contaminants due to their potent biological activities. At least six selections were previously reported to obtain DNA aptamers for E2, highlighting its environmental importance. A careful analysis revealed that the previous aptamers either are too long or do not bind optimally. Herein, a series of new aptamers were obtained from the capture-SELEX method with dissociation constants down to 30 nM as determined by isothermal titration calorimetry (ITC). Two aptamers were converted to structure-switching fluorescent biosensors, which achieved a limit of detection down to 3.3 and 9.1 nM E2, respectively. One aptamer showed similar binding affinities to all the three estrogens, while the other aptamer is more selective for E2. Both aptamers required Mg2+ for binding. The proposed sensors were successfully applied in the determination of E2 in wastewater. Moreover, comparisons were made with previous aptamers based on primary sequence alignment and secondary structures. Among previously reported truncated aptamers, ITC showed binding only in one of them. The newly selected aptamers have the combined advantages of small size and high affinities.

Distribution, ecological fate, and risks of steroid estrogens in environmental matrices.

Over the past two decades, steroidal estrogens (SEs) such as 17α-ethylestradiol (EE2), 17ß-estradiol (E2),17α-estradiol (17α-E2), estriol (E3) and estrone (E1) have elicited worldwide attention due to their potentially harmful effects on human health and aquatic organisms even at low concentration ng/L. Natural steroidal estrogens exhibit greater endocrine disruption potency due to their high binding effect on nuclear estrogen receptors (ER). However, less has been explored regarding their associated environmental risks and fate. A comprehensive bibliometric study of the current research status of SEs was conducted using the Web of Science to assess the development trends and current knowledge of SEs in the last two decades, from 2001 to 2021 October. The number of publications has tremendously increased from 2003 to 2021. We summarized the contamination status and the associated ecological risks of SEs in different environmental compartments. The results revealed that SEs are ubiquitous in surface waters and natural SEs are most studied. We further carried out an in-depth evaluation and synthesis of major research hotspots and the dominant SEs in the matrices were E1, 17ß-E2, 17α-E2, E3 and EE2. Nonetheless, investigations of SEs in soils, groundwater, and sediments remain scarce. This study elucidates SEs distribution, toxicological risks, ecological fate and mitigation measures, which will be beneficial for future monitoring, management, and risk assessment. Further studies are recommended to assess the toxicological risks of different SEs in complex environmental matrices to pursue a more precise and holistic quantitative estimation of estrogenic risk.

The impact of sewage sludge processing on the safety of its use.

Particular attention is devoted to pharmaceutical residues in sewage sludge caused by their potential ecotoxicological effects. Diclofenac, ibuprofen and carbamazepine, 17-α-ethinylestradiol, ß-estradiol, were analysed in four types of fertilizers, based on sewage sludge commercial products, in compliance with Polish requirements. The release of active pharmaceutical compounds from fertilizers to water the phase after 24 h and 27 days was analysed. Solid-water partition coefficients (Kd) and partitioning coefficient values normalized on organic carbon content (log KOC) were evaluated. The environmental risk to terrestrial ecosystems, due to the application of fertilizers onto soils, was estimated. Cumulative mass of pharmaceuticals emitted to water from fertilizers ranged from 0.4 to 30.8 µg/kg after 24 h contact. The greatest amount of the material that was released, over 70%, was observed for carbamazepine. No presence of compounds except ibuprofen was observed after 27 days of testing. The highest environmental risk in fertilizers is due to carbamazepine, risk quotation, RQ = 0.93 and diclofenac RQ = 0.17. The values of risk quotation estimated for soil were below RQ = 0.01. This fact means that no risk to terrestrial ecosystems is expected to occur. The important decrease of the concentrations of active compounds after passing from sewage sludge to fertilizers [and] to fertilized soil could be observed.

Occurrence and removal of drugs and endocrine disruptors in water supply systems in the metropolitan region of Belo Horizonte (Minas Gerais State, Brazil).

This study evaluates both the occurrence and removal of 24 compounds, including drugs and endocrine disruptors, in 8 water treatment plants (WTP) located in the metropolitan region of Belo Horizonte (Minas Gerais State, Brazil). The compounds 4-nonylphenol, 4-octylphenol, 17α-ethinylestradiol, 17ß-estradiol, acyclovir, bisphenol A, bezafibrate, caffeine, dexamethasone, diclofenac sodium, diltiazem, estrone, estriol, gemfibrozil, ibuprofen, linezolid, loratadine, losartan, metformin, naproxen, paracetamol, promethazine, propranolol and sulfamethoxazole were monitored at 3 sampling points (raw water, filtered water, treated water) over 10 or 12 collection campaigns for each WTP. The results showed that bisphenol A occurred at higher concentrations during the dry period with a maximum concentration of 3257.1 ng L-1, while the compounds 4-nonylphenol and losartan exhibited higher concentrations in the rainy period with maximum concentrations of 8577.2 ng L-1 and 705.8 ng L-1, respectively. Regarding the removal of compounds in the monitored WTPs, the clarification step demonstrated better removals for 4-nonylphenol, bisphenol-A, paracetamol, and sulfamethoxazole, whereas the disinfection step mainly removed the compounds 4-octylphenol and estrone. Margin of exposure (ME) assessment results indicated that only dexamethasone, ethinyl estradiol, diclofenac, estradiol, and estrone were classified as imminent risk or alert considering the 95th percentile concentration found in the samples of treated water.

Photodegradation of free estrogens driven by UV light: Effects of operation mode and water matrix.

Estrogens are endocrine disrupting chemicals that have been frequently detected in diverse water matrices (e.g. surface water, wastewater and drinking water) and caused a series of health risks. This study was aimed at investigating the photochemical degradation of free estrogens estrone (E1), 17ß-estradiol (E2), estriol (E3), and 17α-ethyl estradiol (EE2) upon the monochromatic irradiation (253.7 nm). Concerning the practical installation of photolysis treatment, exposing the impacts of photoreactor operation mode (stationary or up-flow) and the water matrix (ultrapure water or natural surface water) on the photolytic behaviour of estrogens was of high importance. The pseudo-first-order rate constants showed that E1 was the most susceptible to UV radiation among chosen estrogens due to its high molar absorption coefficient of 402.4 M-1 cm-1 and quantum yield of 0.065 mol E-1 at λ = 253.7 nm. Moreover, the up-flow mode and the surface water matrix collected from a lake in Regent's Park (London) were found to favour the photodegradation of estrogens due to the introduction of more dissolved oxygens and promotion of reactive oxygen species (ROS) formation. These findings may shed light on the photochemical behaviour of estrogens in some specific scenarios.

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, 17ß-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 sensitivity.

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).

Sexual hormones in a coastal river adjacent to the Bohai Sea: Characteristic pollutants and dominantly influencing factors.

Characteristic sexual hormones (SHs) and the factors that dominantly influence their occurrence in coastal ecosystems are less understood. This study verified the relationships between SHs and environmental factors and further inferred the possible controlling mechanisms of SH distribution. A characteristic pollutant of SHs was first proposed by determining the contamination level and ecological risks of SHs (seven species) in a coastal river adjacent to the Bohai Sea. The results showed that the 17ß-oestradiol (17ß-E2), estriol (E3), and 17α-ethynylestradiol (EE2) had high mean concentrations of 11.20 (±1.31), 10.17 (±4.91), and 16.71 (±0.88) ng L-1, respectively, in the river water. The concentration of estrone (E1) was positively related to microbial substances of DOMs (p < 0.05). The humification index (HIX) had a negative relationship with E3 (p < 0.05). In water, the distribution of total SHs was regulated by the HIX and fluorescence index (FI), which might be related to photodegradation reactions. The 17α-oestradiol (17α-E2) and EE2 were related to humified organic matter, while E3 and androstenedione (ADD) were influenced by sewage input. The 17ß-E2, E1, and 17α-E2 may be derived from animal sources, while E3, ADD, EE2, and progesterone were from human activities. Oestrogens, including E1, 17α-E2, 17ß-E2, and EE2, displayed higher ecological risks than androgens and progesterone, with medium to high risk in most sites. The 17ß-E2 was regarded as a characteristic pollutant of SHs throughout the river system, which displayed the highest risk. This paper may provide a reference for SH risk management and control.