The degradation of the pharmaceutical compound ibuprofen (IBP) in aqueous solution induced by direct photolysis (UV-A and UV-C radiation) and photocatalysis (TiO2 /UV-A and TiO2 /UV-C systems) was evaluated. Initially, we observed that whereas photocatalysis (both systems) and direct photolysis with UV-C radiation were able to cause an almost complete removal of IBP, the mineralization rates achieved for all the photodegradation processes were much smaller (the highest value being obtained for the TiO2 /UV-C system: 37.7%), even after an exposure time as long as 120 min. Chemical structures for the by-products formed under these oxidative conditions (11 of them were detected) were proposed based on the data from liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) analyses. Taking into account these results, an unprecedented route for the photodegradation of IBP could thus be proposed. Moreover, a fortunate result was achieved herein: tests against Artemia salina showed that the degradation products had no higher ecotoxicities than IBP, which possibly indicates that the photocatalytic (TiO2 /UV-A and TiO2 /UV-C systems) and photolytic (UV-C radiation) processes can be conveniently employed to deplete IBP in aqueous media.
Some organic microcontaminants, known as endocrine-disrupting compounds (EDC), are frequently found in surface waters and are of concern because of their ability to alter the normal functioning of the endocrine system. In this study five of these EDCs (estradiol, ethynylestradiol, bisphenol A, nonylphenol and diethylphthalate) in surface water samples, collected at the upper part of Rio das Velhas river (located between Ouro Preto and Nova Lima, Minas Gerais state, Brazil) were analysed. The analytical methodology, which employed solid-phase extraction and high-performance liquid chromatography coupled to high resolution mass spectrometry (HPLC-MS/MS), was properly validated and resulted in limits of quantification (LOQ, S/N = 10) of 4.3 ng/L for diethylphtalate, 3.9 ng/L for nonylphenol, 3.6 ng/L for estradiol, 4.7 ng/L for ethynylestradiol and 2.5 ng/L for bisphenol. The five compounds were monitored for eight months, from sites where the hormones were occasionally found. Ethynylestradiol and estradiol concentrations varied from 5.6 to 63.8 ng/L. Bisphenol was present in all samples in a concentration that ranged from 8.6 to 168.3 ng/L. The other two compounds were at quantifiable levels in all collected samples, with nonylphenol varying from 25.9 to 1435.3 ng/L and diethylphthalate from 5.0 to 410.9 ng/L. The study showed that nonylphenol pollution seemed to originate from agricultural run-off, while diethylphthalate pollution originated from the discharge of domestic sewage. Risk analysis studies showed that the environmental concentrations of nonylphenol and dicthylphthalate do not present risks to human health; however, the concentrations found for bisphenol and ethinylestradiol could be toxic to humans, especially infants, if such compounds are not effectively removed at water treatment plants.
Endocrine disrupting compounds (EDCs) have attracted the attention of the scientific community because of the effects of EDCs on aquatic fauna and the potential threat they pose to human health. There are a handful of papers on the monitoring of EDCs in Brazilian surface waters, hence this research was aimed at assessing, by using liquid chromatography coupled to mass spectrometry (LC-MS), the presence of 17 beta-estradiol, 17 alpha-ethynylestradiol and 4-nonylphenol in surface waters used for supplying the Belo Horizonte Metropolitan Area, Minas Gerais state, Brazil. The one-year monitoring period of three water sources showed that 4-nonylphenol was detected in all samples in a concentration range of 44 to 1918 ng L(-1), whilst the natural and synthetic estradiols were hardly detected (only in approximately 15% of samples) and always in low concentrations (2 to 54 ng L(-1)). Samples of partially treated water, collected in three water treatment plants before the chlorination step, showed that the steps of prechlorination, flocculation-sedimentation and sand filtration did not efficiently remove the EDCs studied.
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