Determination of Endocrine Disrupting Chemicals in Water and Wastewater Samples by Liquid Chromatography-Negative Ion Electrospray Ionization-Tandem Mass Spectrometry
MOLECULES
Authors: Aborkhees, Ghada; Raina-Fulton, Renata; Thirunavokkarasu, Ondiveerapan
Abstract
A liquid chromatography-negative ion electrospray ionization-tandem mass spectrometry method was developed for the simultaneous analysis of bisphenol A, 4-octylphenol, 4-nonylphenol, diethylstilbestrol, 17 beta-estradiol, estriol, estrone, 17 alpha-ethinylestradiol, prednisone, and prednisolone. This method used solid-phase extraction with an elution solvent of acetonitrile to improve the stability of the analytes. To maintain the stability of analytes analyses were completed within five days. The recoveries ranged from 84 to 112% and the relative standard deviation of analysis of duplicate samples was <10%. The limits of quantitation were 1-10 ng/L. Surface water and wastewater were obtained from five wastewater treatment plants in Saskatchewan. Matrix effects were moderate to severe. Using standard addition calibration, all analytes except diethylstilbestrol and 17 alpha-ethinyl estradiol were detected. There was a low frequency of detection of the target analytes in upstream and downstream water, indicating good removal efficiency during the wastewater treatment process. Bisphenol A and 4-nonylphenol were the only analytes detected downstream. Bisphenol A was the most frequently detected in raw wastewater (133 to 403 ng/L). Estriol was detected more often in raw wastewater than estrone or 17 beta-estradiol. This is the first Canadian study with the detection of prednisone and prednisolone with concentrations at 198-350 ng/L in raw wastewater at 60% of the wastewater treatment plants.
Degradation of estriol (E3) and transformation pathways after applying photochemical removal processes in natural surface water
WATER SCIENCE AND TECHNOLOGY
Authors: Perondi, T.; Michelon, W.; Basso, A.; Bohrer, J. K.; Viancelli, A.; Fonseca, T. G.; Treichel, H.; Moreira, R. F. P. M.; Peralta, R. A.; Dusman, E.; Pokrywiecki, T. S.
Abstract
Steroidal hormones such as estriol (E3), are resistant to biodegradation; hence their removal by conventional treatment systems (aerobic and anaerobic) facilities is limited. These substances are detected in surface water, and present risks to the aquatic ecosystem and humans via potential biological activity. Photochemical treatments can be used to remove E3; however, just a few studies have analyzed the kinetics, intermediates, and E3 degradation pathways in natural surface water. In this study, the behavior of E3 under ultraviolet irradiation associated with H2O2, O(3)or TiO(2)was investigated to determine the degradation potential and the transformation pathways in reactions performed with a natural surface water sample. E3 degradation kinetics (200 ppb) fitted well to the pseudo-first-order kinetics model, with kinetic constantkin the following order:k(UV/O3)>k(UV/TiO2)>k(UV/H2O2)>k(UV). The mechanism of degradation using different advanced oxidative processes seemed to be similar and 12 transformation byproducts were identified, with 11 of them being reported here for the first time. The byproducts could be formed by the opening of the aromatic ring and addition of a hydroxyl radical. A possible route of E3 degradation was proposed based on the byproducts identified, and some of the byproducts presented chronic toxicity to aquatic organisms, demonstrating the risks of exposure.