In this study, an analytical methodology was validated to determine and quantify four estrogen hormones using high-performance liquid chromatography (HPLC) with detections by diode array detector (DAD) and by fluorescence detector (FLD). For validation of the method, the following parameters were evaluated: linearity, selectivity, precision, accuracy, limit of detection (LOD), limit of quantification (LOQ) and robustness. Environmental samples were preconcentrated using solid phase extractions and for that, an experimental design was planned to determine the best recovery conditions by varying cartridge types, flow of eluent, pH of the samples, and eluting solvent. Five surface water sampling campaigns were carried out in five different sites of Furnas Reservoir over the months of December 2015 and May 2016. Sample point 1 was located near the sewage treatment plant of the city of Alfenas - MG, while sample point 5 was the most distant from this location. All estrogens, except for E1, were found in all water samples of at least one of the sampling sites. The concentrations of E3, E2 and EE2 ranged from 11-366, 63-422 and 75-9998 ng L-1, respectively. These results are consistent with several studies published in the scientific literature.
This study describes the application of peanut shells, a biodegradable agroindustrial residue as a biosorbent, in the 17α-ethinylestradiol (EE2) removal in water matrices. An analytical method was developed and validated from the high-performance liquid chromatographic technique with fluorescence detection (HPLC-FLD) in a λEx= 230 nm and λEm= 310 nm in the determination of EE2. The evaluated parameters were: selectivity, linearity (R2 = 0.9984 and R = 0.9992), precision (Variation coefficient = 2.90% and 2.95% for the first and second analyst, respectively), accuracy (recovery rate = 100.2 – 110.4%), detection limit (3.4 – 5.0 μg L-1), quantification limit (10.0 – 11.3 μg L-1) and robustness (recovery rate = 98.7 – 115.5%). The chromatographic analysis conditions were: mobile phase (water 2:3 acetonitrile), mobile phase flow (0.5 mL min-1), injection volume (10 µL), column temperature (45ºC) and race time (10 min). An experiment planning (Box-Behnken Model) was carried out for the investigation and verification of the adsorptive capacity of the peanut shells, of which 3 parameters were evaluated (stirring rate, pH and adsorbent mass) on 3 levels. Optimum experimental condition (2 g of adsorbent, pH = 6 and stirring at 500 rpm) with a removal rate of 90% in 24 hours of the process.
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17α-ethinylestradiol (EE2), an endocrine disruptor (ED) excreted by women and is found in contraceptive and hormone replacement pills used at menopause. An increase in EDs requires alternative means of water and sewage treatment, since these compounds threaten human health and the environment, even at trace levels. Phytotechnology stands out from other processes because it is sustainable, given that plants are used to recover the contaminated environment. Thus, the objective of this study was to evaluate rice grass performance in the removal of 17α-ethinylestradiol (EE2), and determine the effect of this hormone on the root anatomy and chlorophyll content of the species. A completely randomized design was used with 4 replications: EE2 concentration composed of 4 study treatments (420, 300, 180 and 60 μg L-1 EE2) and 2 control treatments (positive and negative). The effect of the treatments was evaluated over time (1, 7 and 15 days). EE2 removal from the solution was analyzed by HPLC. Chlorophyll was analyzed by UVvis spectrophotometry, showing that EE2 does not interfere with the photosynthetic activity of rice grass. Aerenchyma was analyzed by microphotographs of root sections, revealing a higher proportion in plants exposed to the hormone, indicating morpho-anatomical adaptations to survive in this medium. Thus, it can be concluded that rice grass has significant phytoremediation potential after 7 days’ exposure, surviving and adapting to the contaminated environment, and can be used to complement water and sewage treatments.
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