RESUMEN
This study explores the application of a tyrosinase cantilever nanobiosensor for detecting 17ß-estradiol and estrone in typical water systems. The physical-chemical parameters of water were evaluated within the Tigre River micro-basin in Erechim, RS, to determine water potability for urban populations. Water clarity, conductivity, and pH levels were essential markers, adhering to recognized standards for water quality and human consumption. The cantilever nanobiosensor demonstrated strong sensitivity and a broad linear range, with a limit of detection (<0.00051 ppb) surpassing other enzymatic biosensors and covering a range of 0.0001-100 ppb. The real water sample quality investigated in relation to contamination with 17ß-estradiol and estrone by nanobiosensor showed values below the LOD for both compounds. Recovery studies demonstrated the reliability of the nanobiosensor. Selectivity tests indicated minimal interference from structurally similar substances. This study validates the nanobiosensor's potential for environmental monitoring and hormone detection, aligning with standard practices.
Asunto(s)
Técnicas Biosensibles , Monitoreo del Ambiente , Monofenol Monooxigenasa , Ríos , Contaminantes Químicos del Agua , Monitoreo del Ambiente/métodos , Monitoreo del Ambiente/instrumentación , Ríos/química , Técnicas Biosensibles/instrumentación , Técnicas Biosensibles/métodos , Contaminantes Químicos del Agua/análisis , Estradiol/análisis , Estrona/análisis , Límite de DetecciónRESUMEN
A novel magnetic dispersive solid phase extraction (MDSPE) procedure based on the deep eutectic solvent (DES) modified magnetic graphene oxide/metal organic frameworks nanocomposites (MGO@ZIF-8@DES) was established and used for the efficient enrichment of estradiol, estrone, and diethylstilbestrol in cosmetics (toner, lotion, and cream) for the first time. Then, the three estrogens were separated and determined by UHPLC-UV analysis method. In order to study the features and morphology of the synthesized adsorbents, various techniques such as FT-IR, SEM, and VSM measurements were executed. The MGO@ZIF-8@DES nanocomposites combine the advantages of high adsorption capacity, adequate stability in aqueous solution, and convenient separation from the sample solution. To achieve high extraction recoveries, the Box-Behnken design and single factor experiment were applied in the experimental design. Under the optimum conditions, the method detection limits for three estrogens were 20-30 ng g-1. This approach showed a good correlation coefficient (r more than 0.9998) and reasonable linearity in the range 70-10000 ng g-1. The relative standard deviations for intra-day and inter-day were beneath 7.5% and 8.9%, respectively. The developed MDSPE-UHPLC-UV method was successfully used to determine three estrogens in cosmetics, and acceptable recoveries in the intervals of 83.5-95.9% were obtained. Finally, three estrogens were not detected in some cosmetic samples. In addition, the Complex GAPI tool was used to evaluate the greenness of the developed pretreatment method. The developed MDSPE-UHPLC-UV method is sensitive, accurate, rapid, and eco-friendly, which provides a promising strategy for determining hormones in different complex samples.
Asunto(s)
Cosméticos , Disolventes Eutécticos Profundos , Estrógenos , Grafito , Estructuras Metalorgánicas , Nanocompuestos , Extracción en Fase Sólida , Grafito/química , Cosméticos/química , Cosméticos/análisis , Nanocompuestos/química , Estructuras Metalorgánicas/química , Extracción en Fase Sólida/métodos , Estrógenos/análisis , Estrógenos/aislamiento & purificación , Estrógenos/química , Disolventes Eutécticos Profundos/química , Límite de Detección , Estradiol/química , Estradiol/análisis , Estradiol/aislamiento & purificación , Estrona/análisis , Estrona/química , Estrona/aislamiento & purificación , Adsorción , Dietilestilbestrol/análisis , Dietilestilbestrol/química , Dietilestilbestrol/aislamiento & purificación , Cromatografía Líquida de Alta Presión/métodosRESUMEN
Progesterone (PROG) and estrone (E1) are typical reproductive hormones in dairy cows. Assessing the levels of these hormones in vivo can aid in estrus identification. In the present work, the feasibility of the qualitative and quantitative detection of PROG and E1 using terahertz time-domain spectroscopy (THz-TDS) and metamaterial technology was preliminarily investigated. First, the time domain spectra, frequency domain spectra, and absorption coefficients of PROG and E1 samples were collected and analyzed. A vibration analysis was conducted using density functional theory (DFT). Subsequently, a double-ring (DR) metamaterial structure was designed and simulated using the frequency domain solution algorithm in CST Studio Suite (CST) software. This aimed to ensure that the double resonance peaks of DR were similar to the absorption peaks of PROG and E1. Finally, the response of DR to different concentrations of PROG/E1 was analyzed and quantitatively modeled. The results show that a qualitative analysis can be conducted by comparing the corresponding DR resonance peak changes in PROG and E1 samples at various concentrations. The best R2 for the PROG quantitative model was 0.9872, while for E1, it was 0.9828. This indicates that terahertz spectral-metamaterial technology for the qualitative and quantitative detection of the typical reproductive hormones PROG and E1 in dairy cows is feasible and worthy of in-depth exploration. This study provides a reference for the identification of dairy cow estrus.
Asunto(s)
Estrona , Progesterona , Espectroscopía de Terahertz , Bovinos , Animales , Progesterona/análisis , Femenino , Espectroscopía de Terahertz/métodos , Estrona/análisis , Industria LecheraRESUMEN
Imidazoline-linked cationic covalent triazine framework (IM-iCTF) was facilely prepared through the Debus-Radziszewski reaction, involving 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline, formaldehyde and methylglyoxal. The IM-iCTF was applied as a sorbent for cartridge solid-phase extraction (SPE). It provided good adsorption performance for estrogen and estrogen mimics including bisphenol F, bisphenol A, 7ß-estradiol, bisphenol B and estrone. The adsorption isotherm, adsorption kinetic model, thermodynamic calculations and adsorption mechanism were investigated to reveal the adsorption behavior. The IM-iCTF was employed for the extraction of the estrogens and estrogen mimics from water, fish and shrimp (fish and shrimp samples were extracted with acetonitrile before the SPE). The analytes were then determined by high-performance liquid chromatography with diode array detection. The limits of detection were 0.008-0.05 ng mL-1 for water, 0.015-0.11 µg g-1 for fish, and 0.012-0.10 µg g-1 for shrimp samples. This research not only offers a new approach to construct cationic covalent triazine framework, but also provides a reliable strategy for the adsorption/enrichment trace level of organic pollutants.
Asunto(s)
Estrógenos , Triazinas , Animales , Triazinas/análisis , Estrógenos/análisis , Estradiol/análisis , Estrona/análisis , Cromatografía Líquida de Alta Presión/métodos , Extracción en Fase Sólida/métodos , Agua/química , Adsorción , Límite de DetecciónRESUMEN
Steroid hormones (SHs) are among the important classes of Contaminants of Emerging Concern (CECs) whose detection in aquatic environments is vital due to their potential adverse health impacts. Their detection is challenging because of their lower stability in natural conditions and low concentrations. This study reports the presence of steroid hormones in a major river system, the Periyar River, in Kerala (India). Water samples were collected from thirty different river locations in the case of SHs and five locations within these in the case of other CECs. These were subjected to LC-MS/MS and LC-Q-ToF/MS analyses. Five SHs, estriol, estrone, 17 ß estradiol, progesterone, and hydroxy progesterone, were separated and targeted using MS techniques. The studies of the water samples confirmed the presence of the first three estrogens in different sampling sites, with estrone present in all the sampling sites. The concentration of estrone was detected in the range from 2 to 15 ng/L. Estriol and estradiol concentrations ranged from 1.0 to 5 ng/L and 1-6 ng/L, respectively. The hormones at some selected sites were continuously monitored for seven months. The chosen areas include the feed water sites for the drinking water treatment plants across the river. The monthly data revealed that estrone is the only SHs detected in all the samples in the selected months. The highest concentration of SH was found in August. Twelve CECs belonging to pharmaceuticals and personal care products were identified and quantified. In addition, 31 other CECs were also identified using non-target analysis. A detailed study of the hormone mapping reported here is the first from any South Indian River.
Asunto(s)
Estrona , Contaminantes Químicos del Agua , Estrona/análisis , Cromatografía Liquida/métodos , Progesterona , Espectrometría de Masas en Tándem/métodos , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , Estrógenos/análisis , Estradiol/análisis , Estriol/análisis , RíosRESUMEN
Veterinary antibiotics and estrogens are excreted in livestock waste before being applied to agricultural lands as fertilizer, resulting in contamination of soil and adjacent waterways. The objectives of this study were to 1) investigate the degradation kinetics of the VAs sulfamethazine and lincomycin and the estrogens estrone and 17ß-estradiol in soil mesocosms, and 2) assess the effect of the phytochemical DIBOA-Glu, secreted in eastern gamagrass (Tripsacum dactyloides) roots, on antibiotic degradation due to the ability of DIBOA-Glu to facilitate hydrolysis of atrazine in solution assays. Mesocosm soil was a silt loam representing a typical claypan soil in portions of Missouri and the Central United States. Mesocosms (n = 133) were treated with a single target compound (antibiotic concentrations at 125 ng g-1 dw, estrogen concentrations at 1250 ng g-1 dw); a subset of mesocosms treated with antibiotics were also treated with DIBOA-Glu (12,500 ng g-1 dw); all mesocosms were kept at 60% water-filled pore space and incubated at 25 °C in darkness. Randomly chosen mesocosms were destructively sampled in triplicate for up to 96 days. All targeted compounds followed pseudo first-order degradation kinetics in soil. The soil half-life (t0.5) of sulfamethazine ranged between 17.8 and 30.1 d and ranged between 9.37 and 9.90 d for lincomycin. The antibiotics results showed no significant differences in degradation kinetics between treatments with or without DIBOA-Glu. For estrogens, degradation rates of estrone (t0.5 = 4.71-6.08 d) and 17ß-estradiol (t0.5 = 5.59-6.03 d) were very similar; however, results showed that estrone was present as a metabolite in the 17ß-estradiol treated mesocosms and vice-versa within 24 h. The antibiotics results suggest that sulfamethazine has a greater potential to persist in soil than lincomycin. The interconversion of 17ß-estradiol and estrone in soil increased their overall persistence and sustained soil estrogenicity. This study demonstrates the persistence of these compounds in a typical claypan soil representing portions of the Central United States.
Asunto(s)
Estrona , Contaminantes del Suelo , Estrona/análisis , Antibacterianos , Suelo , Sulfametazina , Contaminantes del Suelo/análisis , Estradiol/análisis , Estrógenos/metabolismo , LincomicinaRESUMEN
So far, little has been known about how the combined collection systems of sewage and rainfall runoff (CCSs) affect emerging contaminants in river water. To fill up the knowledge gap, this study was conducted to investigate the spatial distributions of three natural estrogens (NEs, i.e., estrone (E1), 17ß-estradiol (E2) and estriol (E3)) and their conjugates (C-NEs) in the Pearl River in the wet and dry seasons. Results showed that the respective average concentrations of NEs and C-NEs at different locations alongside the Pearl River in the wet season were 7.3 and 1.8 times those in the dry season. Based on estrogen equivalence (EEQ), the average estimated EEQ level in the Pearl River waters in the wet season was nearly 10 times that in the dry season. These seemed to imply that the CCSs in the wet season not only cause untreated sewage into the receiving water body, but greatly decrease the removal efficiency of NEs and C-NEs in wastewater treatment plant. Furthermore, the estimated annual loads of E1, E2, and E3 to the Pearl River in the wet season accounted for about 88.6 %, 100 %, and 99.3 % of the total annual loads. Consequently, this work for the first time demonstrated that the CCSs in cities with high precipitation are unfavorable for controlling of emerging contaminants.
Asunto(s)
Monitoreo del Ambiente , Estrógenos , Lluvia , Ríos , Aguas del Alcantarillado , Contaminantes Químicos del Agua , Ríos/química , China , Estrógenos/análisis , Aguas del Alcantarillado/química , Contaminantes Químicos del Agua/análisis , Estaciones del Año , Estrona/análisis , Estradiol/análisisRESUMEN
Investigou-se sintomatologia estrógeno-dependente em 97 mulheres, escolhidas ao acaso, com menopausa natural há mais de um ano, cuja idade variou entre 42 e 66 anos, em relaçäo à massa corpórea, dosagem de esteróides sexuais e tempo de pós-menopausa. Näo se constatou diferença significativa entre a referida sintomatologia e a massa corpórea e, nem desta em relaçäo aos níveis de estrona, estradiol e androstenediona. Também näo se evidenciou diferença entre as dosagens desses esteróides em relaçäo à presença ou näo de sintomas vasomotores e de dispareunia. O tempo de pós-menopausa, da mesma forma, näo apresentou influência na incidência dos sintomas estudados e nos níveis dos referidos hormônios. Assim, as investigaçöes hormonais parecem ser dispensáveis, sendo a sintomatologia o melhor indicador para uma terapêutica adequada