Desenvolvimento e validação de metodologia por UPLC-MS/MS para determinação de produtos farmacêuticos, produtos de cuidados pessoais e desreguladores endócrinos na bacia hidrográfica do rio Guandu - RJ

Abstract

Pharmaceuticals and personal care products (PPCPs) and endocrine disruptors (EDs) are micropollutants present in tests using µg L-1 and ng L-1, which are potentially dangerous for the environment as well as for humans. Among the PPCPs, widely consumed in themselves: Trimethoprim (TMP), Bromazepam (BZP), Clonazepam (CZP), Diazepam (DZP), Ibuprofen (IBP) and Benzophenone (BEN). EDs, in turn, are substances that impair the normal functioning of the endocrine system. Among them are 4-Nonylphenol (4NP), Bisphenol A (BPA) and Diethylphthalatee (DEP). The analytical method used for Solid Phase Extraction (SPE) as sample preparation and determination by Ultra Efficiency Liquid Chromatography coupled to Mass Spectrometry tandem (UPLC-MS/MS). For an SPE, use C18 - 500 mg cartridges and elution in two steps of 2.50 mL of methanol. After the optimization of the extraction and chromatographic separation, the analytical method was validated, using the validation parameters of United States Environmental Protection Agency (USEPA) according 8000D guide. The method developed was, sensitive, robust and selected. The LODs and LOQs for the method, varying between 0.844 and 8.13 from L-1 for LOD and 10.0 and 50.0 ng L-1 for LOQ; The precision values (% RSD) and the accuracy remain within the values recommended by the USEPA 8000D guide (RSD <20%) and accuracy between 50 and 120%. All analytical curves show values of R2> 0.990. For the 4NP, BPA, CZP, DEP, IBP and TMP, matrix effect was evidenced. The method was applied to surface water bottles collected in Nova Iguaçu (NIG), Paracambi (PBI), Rio de Janeiro (RIO) and Seropédica (SER), between April/2018 and March/2019. It was possible to detect all analytes in all collected samples. In the SER, DEP and BPA were quantified in 100% of the specifications. In PBI, SER and RIO, DEP and BZP were quantified in 100% of the colors. However, other analytes showed a high percentage of quantification, for example, IBP 91% in NIG, BPA 91% in PBI, DZP 82% in RIO and 82% in BPA in SER. A risk assessment evidenced by the BPA and DZP micropollutants shows high high risk coefficient (RQ > 1) in the Guandu River basin. For Minimum Environmental Concentration (MEC), BPA presented an RQ of 0.92. All samples showed an acute toxicity effect, through the Dunnett test, all samples were considered toxic, except for one sample (PBI - Oct / 2018). All samples collected showed estrogenic activity. A PBI sample showed an equivalent value of 17β-Estradiol (EQ-E2) approximately 6 times higher than the reference value (1.00 ng L-1).