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.

Organic micropollutants paracetamol and ibuprofen—toxicity, biodegradation, and genetic background of their utilization by bacteria

“…Pharmaceuticals occurred in the environment mainly through the domestic wastewater, hospital effluents, industrial wastewater from pharmaceuticals production, run-off from aquacultures and concentrated animals feeding operations, and fish farming as well as a rural run-off and manure (Luo et al 2014 ; Chiarello et al 2016 ; Wiest et al 2018 ). In recent years, intensified attention has been paid to the evaluation of consumer disposal patterns.…”

Paracetamol - A Contaminant of High Concern: Existence in Environment and Adverse Effect

“…Pharmaceuticals reach the environment mainly through the domestic wastewater, hospital effluents, industrial wastewater from pharmaceuticals production, run-off from aquacultures and concentrated animals feeding operations, fish farming as well as a rural run-off and manure, disposal and discharges from pharmaceutical production industries [18][19][20][21][22]. Prevalent occurrence of paracetamol and its degradation product (4-aminophenol) in the environment is partly associated with their use for manufacturing of azo dyes and photographic materials [23].…”

Determinação de agrotóxicos na água e sedimentos por HPLC-HRMS e sua relação com o uso e a ocupação do solo

“…Valores de RSD% de até 20% são aceitáveis em métodos que determinam agrotóxicos ao nível de traços. 20,26 A exatidão foi avaliada por meio de ensaios de fortificação e recuperação das amostras ensaiadas, utilizando o método QuEChERS modificado. Os ensaios de fortificação foram realizados a partir da solução analítica com concentração 10000 µg L -1 contendo todos os analitos, em três níveis diferentes de concentração: 10, 50 e 100 µg kg -1 .…”

“…20 Na Figura 3 é apresentado um cromatograma com os 70 padrões avaliados. Das 70 substâncias analisadas por cromatografia líquida de alta eficiência e espectrometria de massas, foram obtidas recuperações entre 78,0 a 117,0% com RSD < 20%.…”