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.
Structural modification of steroids through whole-cell biocatalysis is an invaluable procedure for the production of active pharmaceutical ingredients (APIs) and key intermediates. Modifications could be carried out with regio- and stereospecificity at positions hardly available for chemical agents. Much attention has been focused recently on the biotransformation of 17α-ethynyl substituted steroidal drugs using fungi, bacteria and plant cell cultures in order to obtained novel biologically active compounds with diverse structure features. Present article includes studies on biotransformation on 17α-ethynyl substituted steroidal drugs using microorganisms and plant cell cultures. Various experimental and structural elucidation methods used in biotransformational processes are also highlighted.
The 17 α-ethinylestradiol (EE2) adsorption from aqueous solution was examined using a novel adsorbent made from rice husk powder coated with CuO nanoparticles (CRH). Advanced analyses of FTIR, XRD, SEM, and EDSwere used to identify the classification parameters of a CRH-like surface morphology, configuration, and functional groups. The rice husk was coated with CuO nanoparticles, allowing it to create large surface area materials with significantly improved textural qualities with regard to functional use and adsorption performance, according to a detailed characterization of the synthesized materials. The adsorption process was applied successfully with elimination effectiveness of 100% which can be kept up to 61.3%. The parameters of adsorption were affecting the adsorption process significantly. Thermodynamic data stated that the process of adsorption was endothermic, spontaneous, chemisorption and the molecules of EE2 show affinity with the CRH. It was discovered that the adsorption process controlled by a pseudo-second-order kinetic model demonstrates that the chemisorption process was controlling EE2 removal. The Sips model is regarded as optimal for representing this practice, exhibiting a significantly high determination coefficient of 0.948. This coefficient implies that the adsorption mechanism indicates the occurrence of both heterogeneous and homogeneous adsorption. According to the findings, biomass can serve as a cheap, operative sorbent to remove estrogen from liquified solutions.
17α-ethynylestradiol (EE2) is a synthetic hormone, which is a derivative of the natural hormone, estradiol (E2). EE2 is an orally bio-active estrogen, and is one of the most commonly used medications for humans as well as livestock and aquaculture activity. EE2 has become a widespread problem in the environment due to its high resistance to the process of degradation and its tendency to (i) absorb organic matter, (ii) accumulate in sediment and (iii) concentrate in biota. Numerous studies have reported the ability of EE2 to alter sex determination, delay sexual maturity, and decrease the secondary sexual characteristics of exposed organisms even at a low concentration (ng/L) by mimicking its natural analogue, 17β-estradiol (E2). Thus, the aim of this review is to provide an overview of the science regarding EE2, the concentration levels in the environment (water, sediment and biota) and summarize the effects of this compound on exposed biota at various concentrations, stage life, sex, and species. The challenges in respect of EE2 include the extension of the limited database on the EE2 pollution profile in the environment, its fate and transport mechanism, as well as the exposure level of EE2 for better prediction and definition revision of EE2 toxicity end points, notably for the purpose of environmental risk assessment.
Steroid estrogens such as 17β-Estradiol (E2) and 17α-Ethynylestradiol (EE2) are highly potent estrogens that widely detected in environmental samples. Mathematical modelling such as concentration addition (CA) and estradiol equivalent concentration (EEQ) models are usually associated with measuring techniques to assess risk, predict the mixture response and evaluate the estrogenic activity of mixture. Wastewater has played a crucial role because wastewater treatment plant (WWTP) is the major sources of estrogenic activity in aquatic environment. The aims of this is to determine E2 and EE2 concentrations in six WWTPs effluent, to predict the estrogenic activity of the WWTPs effluent using CA and EEQ models where lastly the effectiveness of two models is evaluated. Results showed that all the six WWTPs effluent had relative high E2 concentration (35.1-85.2 ng/L) compared to EE2 (0.02-1.0 ng/L). The estrogenic activity predicted by CA model was similar among the six WWTPs (105.4 ng/L), due to the similarity of individual dose potency ratio calculated by respective WWTPs. The predicted total EEQ was ranged from 35.1 EEQ-ng/L to 85.3 EEQ-ng/L, explained by high E2 concentration in WWTPs effluent and E2 EEF value that standardized to 1.0 μg/L. The CA model is more effective than EEQ model in estrogenic activity prediction because EEQ model used less data and causes disassociation from the predicted behavior. Although both models predicted relative high estrogenic activity in WWTPs effluent, dilution effects in receiving river may lower the estrogenic response to aquatic inhabitants.
The effects of treatment processes on estrogenicity were evaluated by examining estradiol equivalent (EEQ) concentrations in influents and effluents of sewage treatment plants (STPs) located along Yeongsan and Seomjin rivers in Korea. The occurrence and distribution of estrogenic chemicals were also estimated for surface water in Korea and compared with seven other Asian countries including Laos, Cambodia, Vietnam, China, Indonesia, Thailand and Malaysia. Target compounds were nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), estrone (E1), 17beta-estradiol (E2), 17alpha-ethynylestradiol (EE2) and genistein (Gen). Water samples were pretreated and analyzed by liquid-liquid extraction (LLE) and gas chromatography/mass spectrometry (GC/MS). The results showed that the treatment processes of Korean STPs were sufficient to reduce the estrogenic activity of municipal wastewater. The concentrations of phenolic xenoestrogens (i.e., NP, OP and BPA) in samples of Yeongsan and Seomjin rivers were smaller than those reported by previous studies in Korea. In most samples taken from the seven Asian countries, the presence of E2 and EE2 was a major contributor toward estrogenic activity. The EEQ concentrations in surface water samples of the seven Asian countries were at a higher level in comparison to that reported in European countries, America and Japan. However, further studies with more sampling frequencies and sampling areas should be carried out for better evaluation of the occurrence and distribution of estrogenic compounds in these Asian countries.
Since the inception of global industrialization, the growth of steroid estrogens becomes a matter of emerging serious concern for the rapid population. Steroidal estrogens are potent endocrine-upsetting chemicals that are excreted naturally by vertebrates (e.g., humans and fish) and can enter natural waters through the discharge of treated and raw sewage. Steroidal estrogens in plants may enter the food web and become a serious threat to human health. We evaluated the uptake and accumulation of ethinylestradiol (EE2) and 17β-estradiol (17β-E2) in lettuce plants (Lactuca sativa) grown under controlled environmental condition over 21 days growth period. An effective analytical method based on ultrasonic liquid extraction (ULE) for solid samples and solid phase extraction (SPE) for liquid samples with gas chromatography-mass spectrometry (GC/MS) has been developed to determine the steroid estrogens in lettuce plants. The extent of uptake and accumulation was observed in a dose-dependent manner and roots were major organs for estrogen deposition. Unlike the 17β-E2, EE2 was less accumulated and translocated from root to leaves. For 17β-E2, the distribution in lettuce was primarily to roots after the second week (13%), whereas in leaves it was (10%) over the entire study period. The distribution of EE2 at 2000 μg L-1 in roots and leaves was very low (3.07% and 0.54%) during the first week and then was highest (12% in roots and 8% in leaves) in last week. Bioaccumulation factor values of 17β-E2 and EE2 in roots were 0.33 and 0.29 at 50 μg L-1 concentration as maximum values were found at 50 μg L-1 rather than 500 and 2000 in all observed plant tissues. Similar trend was noticed in roots than leaves for bioconcentration factor as the highest bioconcentration values were observed at 50 μg L-1 concentration instead of 500 and 2000 μg L-1 spiked concentration. These findings mainly indicate the potential for uptake and bioaccumulation of estrogens in lettuce plants. Overall, the estrogen contents in lettuce were compared to the FAO/WHO recommended toxic level and were found to be higher than the toxic level which is of serious concern to the public health. This analytical procedure may aid in future studies on risks associated with uptake of endocrine-disrupting chemicals in lettuce plants.
A comparative multicenter clinical trial of two low-dose combined oral contraceptives (OCs) was conducted in Malaysia, Egypt, Thailand, and Mexico. Efficacy, safety and acceptability were investigated in women taking either a norgestrel-based (NG) OC or a norethindrone acetate-based (NA) OC. This paper includes analysis of 892 women, all of whom were at least 42 days but within 26 weeks postpartum and randomly allocated to one of the above OCs. Follow-up visits were scheduled at 1, 4, 8 and 12 months after admission. Baseline sociodemographic characteristics were similar for both groups, as well as compliance. There were nine unintended pregnancies reported; eight of these occurring in the NA group. Adverse experiences were minor with headaches and dizziness being the most common complaints; frequency of reports was similar in both groups. The group taking the NG-based OC had significantly (p < .05) fewer menstrual-related complaints. Discontinuations due to menstrual problems were significantly more common among NA users (primarily amenorrhea). Discontinuations in the NG group were primarily for other personal reasons, e.g. unable to return to the clinic. There was also a significant difference between the two groups for the 11-month gross cumulative life table discontinuation rates due to menstrual problems (p < .01); the NA group had the higher rate.
The catalytic properties of nanoparticles (e.g., nano zero valent iron, nZVI) have been used to effectively treat a wide range of environmental contaminants. Emerging contaminants such as endocrine disrupting chemicals (EDCs) are susceptible to degradation by nanoparticles. Despite extensive investigations, questions remain on the transformation mechanism on the nZVI surface under different environmental conditions (redox and pH). Furthermore, in terms of the large-scale requirement for nanomaterials in field applications, the effect of polymer-stabilization used by commercial vendors on the above processes is unclear. To address these factors, we investigated the degradation of a model EDC, the steroidal estrogen 17α-ethinylestradiol (EE2), by commercially sourced nZVI at pH 3, 5 and 7 under different oxygen conditions. Following the use of radical scavengers, an assessment of the EE2 transformation products shows that under nitrogen purging direct reduction of EE2 by nZVI occurred at all pHs. The radicals transforming EE2 in the absence of purging and upon air purging were similar for a given pH, but the dominant radical varied with pH. Upon air purging, EE2 was transformed by the same radical species as the non-purged system at the same respective pH, but the degradation rate was lower with more oxygen - most likely due to faster nZVI oxidation upon aeration, coupled with radical scavenging. The dominant radicals were OH at pH 3 and O2- at pH 5, and while neither radical was involved at pH 7, no conclusive inferences could be made on the actual radical involved at pH 7. Similar transformation products were observed without purging and upon air purging.
The occurrence and estrogenic activities of steroid estrogens, such as the natural estrone (E1), 17β estradiol (E2), and estriol (E3), as well as the synthetic 17α-ethynylestradiol (EE2), were investigated in eight sampling points along the Langat River (Malaysia). Surface water samples were collected at 0.5 m and surface sediment 0-5 cm from the river surface. Instrument analysis of steroid estrogens was determined by UPLC-ESI-MS with an ultra-performance liquid chromatograph (Perkin Elmer FX15) coupled to a Q Trap function mass spectrophotometer (model 3200: AB Sciex). Steroid estrogen concentrations were higher in the Langat River sediments than those in its surface water. In surface water, E1 was not detected in any sampling point, E2 was only detected in two midstream sampling points (range 0-0.004 ng/L), E3 in three sampling points (range 0-0.002 ng/L), and EE2 in four sampling points (range 0-0.02 ng/L). E1 and E2 were detected in sediments from all sampling points, E3 in five sampling points, while EE2 only in one midstream sample (3.29E-4 ng/g). Sewage treatment plants, farming waste, and agricultural activities particularly present midstream and downstream were identified as potential sources of estrogens. Estrogenic activity expressed as estradiol equivalents (EEQs) was below 1 ng/L in all samples for both surface water and sediment, indicating therefore a low potential estrogenic risk to the aquatic environment. Although the health risks are still uncertain for drinking water consumers exposed to low levels of steroid estrogen concentrations, Langat River water is unacceptable for direct drinking purposes without treatment. Further studies of endocrine disruptors in Malaysian waters are highly recommended.
A cross-sectional study looking at the coagulation system was carried out involving 175 women attending the National Population and Family Development Board's Clinic at the Maternity Clinic, General Hospital, Kuala Lumpur. Study subjects comprise of 50 combined low-dose estrogen/progestrogen oral contraceptive (DC) pill users and 75 non-DC users, acting as controls. The subjects were on the pill for a period of one year or more. There were significant shortening of the prothrombin time (PT) and partial thromboplastin time (PIT) in the DC group as compared to the control group. However, the activities of factors II, Vand VIII assayed were not significantly different between the two groups, suggesting that the changes in the PT and PIT were not significant clinically. The effect of long term usage of combined 10w..cJose DC pills does not seem to indicate changes in the coagulation profile of the women in our study.
PIP: The effect of low dose combined oral contraceptives containing 30 mcg ethinyl estradiol and either 150 mcg levonorgestrel or 150 mcg desogestrel on coagulation indices in Malaysian women was examined. 50 women who had been using the pills for 1 year or more, were compared to 75 non-users. All were attending the Maternity Clinic of the General Hospital, Kuala Lumpur. Pill users registered shorter prothrombin time, 11.5 vs. 11.1 seconds (p=0.016), and partial thromboplastin time, 40.1 vs 35.1 seconds (p=0.000). Since there were no significant differences in Factors II, V, VII, or VIII, the overall effects of low-dose pills on coagulation is probably not clinically significant.
Steroid estrogens, such as 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) are potent and were categorized as "Watch List" in Directive 2013/39/EU because of their potential risks to aquatic environment. Commercialized enzyme-linked immunosorbent assay (ELISA) kits have been used to quantify steroid estrogens in wastewater samples due to their simplicity, rapid, cost-effectiveness, and validated assays. Hence, this study aims to determine the occurrence and removal of steroid hormones in Malaysian wastewater treatment plants (WWTPs) by ELISA, to identify the association of removal efficiency (E2 and EE2) with respect to WWTPs operating conditions, and to assess the potential risks of steroid estrogens to aquatic environment and human. Results showed E2 concentration ranged from 88.2 ± 7.0 ng/L to 93.9 ± 6.9 ng/L in influent and 35.1 ± 17.3 ng/L to 85.2 ± 7.6 ng/L in effluent, with removal of 6.4%-63.0%. The EE2 concentration ranged from 0.2 ± 0.2 ng/L to 4.9 ± 6.3 ng/L in influent and 0.02 ± 0.03 ng/L to 1.0 ± 0.8 ng/L in effluent, with removal of 28.3-99.3%. There is a correlation between EE2 removal with total suspended solid (TSS) and oxidation reduction potential (ORP), and was statistically significant. Despite the calculated estrogenic activity for E2 and EE2 was relatively high, dilution effects could lower estrogenic response to aquatic environment. Besides, these six selected WWTPs have cumulative RQ values below the allowable limit, except WWTP 1. Relatively high precipitation (129-218 mm) could further dilute estrogens concentration in the receiving river. These outputs can be used as quantitative information for evaluating the occurrence and removal of steroid estrogens in Malaysian WWTPs.
PIP: Marvelon, a monophasic oral contraceptive (OC) containing 30 mcg of ethinyl estradiol and 150 mcg of desogestrel, has been available to Malaysian women through the national family planning program since 1982. To assess the safety, effectiveness, and side effects associated with this OC, 247 women who requested the pill were enrolled in a multicenter prospective study that included follow-up after the first, third, and sixth cycles of use. 81% of participants had never used any form of contraception before Marvelon. 194 women (79%) completed the 6-month study. There were no pregnancies recorded. Although women reported a slightly increased incidence of nausea, breast tenderness, and headache in the first treatment cycle, these side effects had abated by the end of the third cycle. After six cycles, mean body weight had decreased by an average of 0.4 kg. Both systolic and diastolic blood pressure were unaffected. An unexpected finding was a decrease in the severity of acne with continuous use of Marvelon. Although both spotting and breakthrough bleeding increased slightly in the first two cycles, irregular bleeding returned to pretreatment levels by the third cycle. The length of the withdrawal bleed in the pill-free week was reduced. The incidence of irregular bleeding and other side effects was substantially lower in this sample of Malaysian women than in Asian and Caucasian Marvelon users surveyed in other studies.
Steroid estrogens, such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethinylestradiol (EE2), are natural and synthetic hormones released into the environment through incomplete sewage discharge. This review focuses on the sources of steroid estrogens in wastewater treatment plants (WWTPs). The mechanisms and fate of steroid estrogens throughout the entire wastewater treatment system are also discussed, and relevant information on regulatory aspects is given. Municipal, pharmaceutical industry, and hospitals are the main sources of steroid estrogens that enter WWTPs. A typical WWTP comprises primary, secondary, and tertiary treatment units. Sorption and biodegradation are the main mechanisms for removal of steroid estrogens from WWTPs. The fate of steroid estrogens in WWTPs depends on the types of wastewater treatment systems. Steroid estrogens in the primary treatment unit are removed by sorption onto primary sludge, followed by sorption onto micro-flocs and biodegradation by microbes in the secondary treatment unit. Tertiary treatment employs nitrification, chlorination, or UV disinfection to improve the quality of the secondary effluent. Activated sludge treatment systems for steroid estrogens exhibit a removal efficiency of up to 100%, which is higher than that of the trickling filter treatment system (up to 75%). Moreover, the removal efficiency of advance treatment systems exceeds 90%. Regulatory aspects related to steroid estrogens are established, especially in the European Union. Japan is the only Asian country that implements a screening program and is actively involved in endocrine disruptor testing and assessment. This review improves our understanding of steroid estrogens in WWTPs, proposes main areas to be improved, and provides current knowledge on steroid estrogens in WWTPs for sustainable development.
13 α,21-Dihydroeurycomanone (1), a known quassinoid of Eurycoma longifolia Jack was recrystallized from chloroform into a novel crystal structure in space group P2 (1). Its X-ray data were compared with those of eurycomanone ( 2). Following intraperioneal injections at similar doses of 2.44 µmol/kg/day for 3 consecutive days, 2 displayed comparable potency with tamoxifen but was more potent than 1 in the anti-estrogenic effect against 17 α-ethynylestradiol (EE)-induced uterotrophy of immature rats.