Removal of sulfamethoxazol and trimethoprim using horizontal-flow anaerobic immobilized bioreactor

Martins, Giovana Silva; Luchiari, Natália da Costa; Lamarca, Rafaela Silva; Silva, Bianca Ferreira da; Gomes, Paulo Clairmont Feitosa de Lima

Palavras-chave: Horizontal-flow anaerobic immobilized bioreactor (HAIB), Liquid chromatography tandem-mass spectrometry (LC-MS/MS), sulfamethoxazol, trimethoprim.

ResumoSulfamethoxazole (SMTX) and trimethoprim (TMP) are antibiotics present in wastewater in a concentration range µg L−1 to ng L−1. The stability in aquatic environment characterizes them as potential risk to the environment which explains the interest of monitoring environmental matrices. The development of simple analytical method to monitor antibiotics in wastewater is essential to evaluate new treatment technologies. The aim of this paper is to evaluate the removal efficiency of sulfamethoxazol and trimethoprim using a horizontal-flow anaerobic immobilized bioreactor (HAIB). A liquid chromatography/tandem mass spectrometry (LC-MS/ MS) method was developed using column-switching online solid-phase extraction as sample preparation procedure to monitor influent and effluent samples. LC-MS /MS were performed in positive mode (ESI +) and selected-reaction monitoring mode (SRM). The total analysis time was 13 minutes integrating the sample preparation and chromatographic run. Injection volume of 100 μL was sufficient to sample extraction. This method presented precision, linearity, quantification and detection limit for simultaneous detection of very low concentrations (ng L-1) from HAIB bioreactor influent and effluent. The precision intra-days showed values lower than 5%, linearity (75-500 ng L-1) and quantification limit (LOQ) of 75 ng L -1 for both antibiotics to the influent and effluent samples from the bioreactor.

Referências Bibliográficas

[1] DU, J. et al. Antibiotics in the coastal water of the South Yellow Sea in China: Occurrence, distribution and ecological risks. Science of the Total Environment, 2017, 595, 521-527.
[2] GUIMARÃES, D.O.; MOMESSO, L.S.; PUPO, M.T. Antibióticos: importância terapêutica e perspectivas para a descoberta e desenvolvimento de anovos agentes. Quim. Nova, 2010, 33 (3), 667–679.
[3] CARVALHO, I. T.; SANTOS, L. Antibiotics in the aquatic environments: A review of the European scenarioEnvironment International, 2016, 94, 736-757.
[4] BRANDT, E. M. F. et al. Behaviour of pharmaceuticals and endocrine disrupting chemicals in simplified sewage treatment systems. Journal of Environmental Management, 2013, 128, 718–726.
[5] LOCATELLI, M. A. F.; SODRÉ, F. F.; JARDIM, W. F. Determination of Antibiotics in Brazilian Surface Waters Using Liquid Chromatography–Electrospray Tandem Mass Spectrometry. Archives of Environmental Contamination and Toxicology, 2011, 60 (3), 385–393.
[6] DE ARAUJO, C.A.V. et al. Simultaneous Removal of the Antimicrobial Activity and Toxicity of Sulfamethoxazole and Trimethoprim by White Rot Fungi. Water, air, & soil pollut, 2017, 228-341.
[7] MOKH, S. et al. Innovative SPE-LC-MS/MS technique for the assessment of 63 pharmaceuticals and the detection of antibiotic-resistant-bacteria: A case study natural water sources in Lebanon. Science of the Total Environment, 2017, 609, 830-841.
[8] DIMPE, K. M.; MPUPA, A.; NOMNGONGO, P. N. Microwave assisted solid phase extraction for separation preconcentration sulfamethoxazole in wastewater using tyre based activated carbon as solid phase material prior to spectrophotometric determination. Spectrochimica Acta – Part A: Molecular and Biomolecular Spectroscopy, 2018, 188, 341-348.
[9] LE-MINH, N.; STUETZ, R. M.; KHAN, S. J. Determination of six sulfonamide antibiotics, two metabolites and trimethoprim in wastewater by isotope dilution liquid chromatography/tandem mass spectrometry. Talanta, 2012, 89, 407-416.
[10] BOXALL, A. B. A. et al. Pharmaceuticals and personal care products in the environment: What are the big questions? Environmental Health Perspectives, 2012, 120, 1221-1229.
[11] INGERSLEV, F.; HALLING-SORENSEN, B. Biodegradability properties of sulfonamides in activated sludge. Environmental Toxicology and Chemistry, 2000, v. 19, (10), 2467–2473.
[12] GOBEL, A. et al. Occurrence and Sorption Behaviour of Sulfonamides, Macrolides, and Trimethoprim in Activated Sludge Treatment. Environ. Sci. Technol, 2005, v. 39, 3981-3989.
[13] CARBALLA, M. et al. Behaviour of pharmaceuticals, cosmetics and hormones in a sewage treatment plant. Water Research, 2004, v. 38, 2918-2926.
[14] QI, W. et al. Elimination of polar micropollutants and anthropogenic markers by wastewater treatment in Beijing, China. Chemosphere, 2015, v. 119, 1054-1061.
[15] RIBEIRO, R. et al. BTEX removal in a horizontal-flow anaerobic immobilized biomass reactor under denitrifying conditions. Biodegradation, v. 24, p. 269-278, 2013.
[16] CHATILA, S. et al. Sulfamethoxazole and ciprofloxacin removal using a horizontal-flow anaerobic immobilized biomass reactor. Environmental Technology, v. 27, n. 7, p. 847-853, 2016.
[17] DAMIANOVIC, M. H. R. Z.; MORAES, E. M.; ZAIAT, M.; FORESTI, E. Pentachlorophenol (PCP) dechlorination in horizontal-flow anaerobic immobilized biomass (HAIB) reactors. Bioresource Technology, v. 100, p. 4361-4367, 2009.
[18] OLIVEIRA, S. V. W. B. et al. Formaldehyde degradation in an anaerobic packed-bed bioreactor. Water Research, v. 38, p. 1685-1694, 2004.
[19] GOMES, P. C. F. L. et al. Rapid determination of 12 antibiotics and caffeine in sewage and bioreactor effluent by online column-switching liquid chromatography/tandem mass spectrometry. Analytical and Bioanalytical Chemistry, v. 407, n. 29, p. 8787-8801, 2015.
[20] BRASIL, Resolução RE n° 27 de 2012. “Dispõe sobre os requisitos mínimos para a validação de métodos bioanalíticos empregados em estudos com fins de registro e pós-registro de medicamentos.”. Órgão emissor: ANVISA – Agência Nacional de Vigilância Sanitária.
[21] THOMPSON, M.; ELISSON, S. L. R.; WOOD, R. Harmonized guidelines for single-laboratory validation of methods of analysis. Pureand Applied Chemistry, 2002, 74 (5), 835-85.
[22] FDA. U.S. Food and Drug Administration, Bioanalytical method validation, in: Guidance for Industry, 2001.
[23] APHA. Standard Methods for the Examination of Water and Wastewater. 21st ed. Washington (DC): American Public Health Association; 2005.
[24] LEITAO, R. C. et al. The effects of operational and environmental variations on anaerobic wastewater treatment systems: A review. Bioresource Technology, v. 97, 1105-1118, 2006.
[25] METCALF, L.; EDDY, H. P. Tratamento de Efluentes e Recuperação de Recursos, 5ª ed. Porto Alegre: AMGH, 2016. 2008 p.
[26] AYDIN, S. et al. Inhibitory effects of antibiotic combination on syntrophic bacteria, homoacetogens and methanogens. Chemosphere, v. 120, p. 515-520, 2015.
[27] FENG, L. et al. Removal of antibiotics during the anaerobic digestion of pig manure. Science of the Total Environment, v. 603-603, p. 219-225, 2017.