title: Popular pharmaceutical residues in hospital wastewater: quantification and qualification of degradation products by mass spectroscopy after treatment with membrane bioreactor.
abstract: The occurrence of drugs in wastewater has been considered an imminent risk to the population, for the treatments used are usually ineffective. The presence of four popular drug residues (metformin, paracetamol, tetracycline, and enalapril) in hospital effluents, by using ultra-fast liquid chromatography tandem mass spectrometry (UFLC-MS/MS) with electrospray (ESI) ionization, and removal/degradation by membrane bioreactor (MBR) system are investigated in this study. For analysis method, all standard calibration curves showed satisfactory linearity (R (2) ≥ 0.993) within a relatively wide range. The recovery was between 70.4 and 105.0 %, and the relative standard deviation (RSD) values were within the ranges of 8.2 and 13.5 %. The effluent samples were collected at the end of the process treated in a bench-scale MBR treatment system and preconcentrated on solid-phase extraction (SPE) cartridges. Following that procedure, the chemical analysis demonstrated that the MBR system was effective in enalapril 94.3 ± 7.63 %, tetracycline 99.4 ± 0.02 %, and paracetamol 98.8 ± 0.86 % removal. However, the polar metformin was less effectively removed (35.4 ± 12.49 %). Moreover, the degradation products were investigated using high-resolution mass spectrometry (HRMS) by quadrupole-time of flight (Q-TOF), which has been indicated a tetracycline metabolite. In order to investigate the environmental impact, the wastewater potential risk was evaluated. The risk quotient (RQ) by measure environmental concentration (MEC) and its predicted no effect concentration (PNEC) ratio (RQ = MEC/PNEC) was between 0.003 (enalapril) to 0.815 (paracetamol). Finally, this work demonstrates that UFLC-MS/MS (ESI-Q) is a sensitive and selective method for drug analysis in wastewater and with ESI-Q-TOF has the accuracy required for determining the degradation products of these compounds. Also, it indicated that membrane bioreactor systems represent a new generation of processes that have proved to outperform conventional treatment showing better effluent quality. The removal capacity studied in this work demonstrates the efficiency of this process.
authors.affiliation: LBIOP-Laboratory of Biotechnology of Natural and Synthetics Products, Technology Department, Biotechnology Institute, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.|LATAM-Laboratory of Environmental Technology, Technology Department, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.
authors.forename: M
authors.initials: M
authors.lastname: Chiarello
authors.affiliation: LBIOP-Laboratory of Biotechnology of Natural and Synthetics Products, Technology Department, Biotechnology Institute, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.
authors.forename: L
authors.initials: L
authors.lastname: Minetto
authors.affiliation: LATAM-Laboratory of Environmental Technology, Technology Department, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.
authors.forename: S V Della
authors.initials: SV
authors.lastname: Giustina
authors.affiliation: LATAM-Laboratory of Environmental Technology, Technology Department, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil.
authors.forename: L L
authors.initials: LL
authors.lastname: Beal
authors.affiliation: LBIOP-Laboratory of Biotechnology of Natural and Synthetics Products, Technology Department, Biotechnology Institute, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil. sidnei.moura@ucs.br.
authors.forename: S
authors.initials: S
authors.lastname: Moura
mesh_terms: D019149:Bioreactors; D002853:Chromatography, Liquid; D006761:Hospitals; D004364:Pharmaceutical Preparations / Q000032:analysis* / Q000378:metabolism*; D018570:Risk Assessment; D052616:Solid Phase Extraction / Q000379:methods; D053719:Tandem Mass Spectrometry; D014865:Waste Disposal, Fluid / Q000379:methods; D062065:Wastewater / Q000032:analysis*; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000378:metabolism*
chemical_list: D004364:Pharmaceutical Preparations; D062065:Wastewater; D014874:Water Pollutants, Chemical
keywords: Degradation product; Hospital effluent; Mass spectrometry; Membrane bioreactor; Pharmaceutical residues