Abstract
Pharmaceutical wastewater treatment plants (PWWTPs) receive industrial effluents from the plant that contain extremely high levels of antibiotics and are regarded as one of the major sources of antibiotics in the environment. Two PWWTPs have been selected in Zhejiang Province, China, to assess the removal mechanisms of fluoroquinolone antibiotics (FQs). PWWTP A uses activated sludge with biocarriers in a moving bed biofilm reactor in anoxic and aerobic units, and PWWTP B uses biological units under anaerobic, aerobic, and anoxic conditions. The wastewater samples and solid samples (sludge and suspended solid matter) were analyzed using solid-phase extraction and ultra-performance liquid chromatography-mass spectrometry. Ofloxacin (OFX) was detected in each stage of PWWTP A, and enrofloxacin and ciprofloxacin were detected in PWWTP B. The concentrations of FQs ranged from 0.32 μg/L to 5.7 mg/L. Although the FQs were largely removed in the biological units (94.5 to 99.9%), large amounts were still discharged in the final effluent (up to 88.0 ± 7.0 μg/L) and dewatered sludge (up to 0.85 ± 0.24 mg/kg). Mass balance analyses of samples from PWWTP A indicated that biodegradation (93.8%) was the major mechanism responsible for the removal of OFX, whereas the contribution of sorption by sludge (0.79%) was less significant, deviating from the findings of most similar studies. Using linear analysis and correlation analysis, we found that the log10 values of the FQ concentration in the sludge were positively related with the log10 values of the equilibrium concentration in water (C w ). These relationships can be described by a Freundlich-like equation. However, these relationships were negative when the C w values were high. Our preliminary explanation is that the equilibrium C w plays an important role in controlling the sorption behavior of FQs in activated sludge.
Similar content being viewed by others
References
Castiglioni S, Bagnati R, Fanelli R, Pomati F, Calamari D, Zuccato E (2006) Removal of pharmaceuticals in sewage treatment plants in Italy. Environ. Sci. Technol 40:357–363
Cesare A, Maria LS, Mariangela M, Alberto V (2012) Application of bioplastic moving bed biofilm carriers for the removal of synthetic pollutants from wastewater. Bioresour Technol 120:180–186
Christian T, Schneider RJ, Farber HA, Skutlarek D, Meyer MT, Goldbach HE (2003) Determination of antibiotic residues in manure, soil, and surface waters. Acta Hydrochim Hydrobiol 31:36–44
Costanzo SD, Murby J, Bates J (2005) Ecosystem response to antibiotics entering the aquatic environment. Mar Pollut Bull 51:218–223
Delnavaz M, Ayati B, Ganjidoust H (2010) Prediction of moving bed biofilm reactor (MBBR) performance for the treatment of aniline using artificial neural networks (ANN). J Hazard Mater 179(1-3):769–775
Fabio P, Kai L, Wolfgang D, Stefan T, Kevin V, Thomas B, Plósz G (2015) Factors influencing sorption of ciprofloxacin onto activated sludge: experimental assessment and modelling implications. Chemosphere 119:105–111
Focazio MJ, Kolpin DW, Barnes KK, Furlong ET, Meyer MT, Zaugg SD (2008) A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States-II untreated drinking water sources. Sci Total Environ 402:201–216
Franco A, Ferranti A, Davidsen C, Trapp S (2010) An unexpected challenge: ionizable compounds in the REACH chemical space. Int J Life Cycle Assess 15:321–325
Gao L, Shi Y, Li W, Niu H, Liu J, Cai Y (2012) Occurrence of antibiotics in eight sewage treatment plants in Beijing, China. Chemosphere 86:665–671
Ghosh GC, Okuda T, Yamashita N, Tanaka H (2009) Occurrence and elimination of antibiotics at four sewage treatment plants in Japan and their effects on bacterial ammonia oxidation. Water Sci Technol 59:779–786
Golet EM, Xifra I, Siegrist H, Alder AC, Giger W (2003) Environmental exposure assessment of fluoroquinolone antibacterial agents from sewage to soil. Environ Sci Technol 37:3243–3249
Gottschall N, Topp E, Metcalfe C, Edwards M, Payne M, Kleywegt S, Russell P, Lapen DR (2012) Pharmaceutical and personal care products in groundwater, subsurface drainage, soil, and wheat grain, following a high single application of municipal biosolids to a field. Chemosphere 87:194–203
Gu C, Karthikeyan KG (2008) Sorption of the antibiotic tetracycline tohumic-mineral complexes. J Environ Qual 37:704–711
Guo XY, Wang N, Hao LJ, Zhi Y, Xu J, Wang ZC, Shan ZJ (2015) Simultaneous detection of 25 kinds of veterinary antibiotics in soil, manure and water samples using liquid chromatography-tandem mass spectrometry. Chin J Anal Chem 43:13–20
Hari KS, Ravi N, Karuna KN (2016) Understanding the ammonia sensing behavior of filter coffee powder derived N-doped carbon nanoparticles using the Freundlich-like isotherm. J Mater Chem A 4:8860–8865
Hou J, Wang C, Mao DQ, Luo Y (2015) The occurrence and fate of tetracyclines in two pharmaceutical wastewater treatment plants of Northern China. Environ Sci Pollut Res 2:1722–1731
Hu XG, Zhou QX, Luo Y (2010) Occurrence and source analysis of typical veterinary antibiotics in manure, soil, vegetables and groundwater from organic vegetable bases, northern China. Environ Pollut 158:2992–2998
Jia A, Wan Y, Xiao Y, Hu J (2012) Occurrence and fate of quinolone and fluoroquinolone antibiotics in a municipal sewage treatment plant. Water Res 46:387–394
Karthikeyan KG, Meyer MT (2006) Occurrence of antibiotics in wastewater treatment facilitiesin Wisconsin, USA. Sci Total Environ 361:196–207
Lapara TM, Burch TR, McNamara PJ, Tan DT, Yan M, Eichmiller JJ (2011) Tertiary-treated municipal wastewater is a significant point source of antibiotic resistance genes into Duluth-Superior Harbor. Environ Sci Technol 45:9543–9549
Leung HW, Minh TB, Murphy MB, Lam JCW, So MK, Martin M (2012) Distribution, fate and risk assessment of antibiotics in sewage treatment plants in Hong Kong, South China. Environ Int 42:1–9
Li B, Zhang T (2010) Biodegradation and adsorption of antibiotics in the activated sludgeprocess. Environ Sci Technol 44:3468–3473
Li JZ, Ying GG, Liu S, Zhao JL, Yang B, Chen ZF, Lai HJ (2013) Occurrence and fate of eleven classes of antibiotics in two typical wastewater treatment plants in South China. Sci Total Environ 452-453:365–376
Lia WH, Shi YL, Gao LH, Liu JM, Cai YQ (2013) Occurrence and removal of antibiotics in a municipal wastewater reclamation plant in Beijing, China. Chemosphere 92:435–444
Lillenberg M, Roasto M, Püssa T (2003) Drug residues in environment. Estimation of fluoroquinolones in soil and food plants. J Agr Sci 14(1):13–26
Lindberg RH, Wennberg P, Johansson MI, Tysklind M, Andersson BAV (2005) Screeningof human antibiotic substances and determination of weekly mass flows in five sewage treatment plants in Sweden. Environ Sci Technol 39:3421–3429
Lindberg RH, Olofsson U, Rendahl P, Johansson MI, Tysklind M, Andersson B (2006) Behavior of fluoroquinolones and trimethoprim during mechanical, chemical, and active sludge treatment of sewage water and digestion of sludge. Environ. Sci. Technol 40:1042–1048
Ma YP, Li M, Wu MM, Li Z, Liu X (2015) Occurrences and regional distributions of 20 antibiotics in water bodies during groundwater recharge. Sci Total Environ 518-519:498–506
MacKay AA, Vasudevan D (2012) Polyfunctionalionogenic compound sorption: challenges and new approaches to advance predictive models. Environ. Sci. Technol 46:9209–9223
Manallack DT (2009) The acid–base profile of a contemporary set of drugs: implications for drug discovery. SAR QSAR Environ Res 20:611–655
Manfred C, Strenn B, Ernis S, Norbert K (2004) Adsorption of bisphenol-A, 17β-estradiole and 17α-ethinylestradiole to sewage sludge. Chemosphere 56:843–851
Miao XS, Bishay F, Chen M, Metcalfe CD (2004) Occurrence of antimicrobials in the final effluents of wastewater treatment plants in Canada. Environ Sci Technol 38:3533–3541
Ødegaard H (2000) Advanced compact wastewater treatment based on coagulation and moving bed biofilm processes. Water Science & Technology 42(12):33–48
Pan B, Wang P, Wu M, Li J, Zhang D, Xiao D (2012) Sorption kinetics of ofloxacin in soils and mineral particles. Environ Pollut 171:185–190
Robert JU, Sarah CB, Miguel B, John KBJ, Ripal NS, Ken DS (2001) Application of the Freundlich adsorption isotherm in the characterization of molecularly imprinted polymers. Anal Chim Acta 435:35–42
Ruan YF, Chen JM, Guo CS, Chen SS, Wang ST, Wang YQ (2011) Distribution characteristics of typical antibiotics in surface water and sediments from freshwater aquaculture water in Tianjin suburban areas, China. Journal of Agro-environment Science 30(12):2586–2593 (In Chinese)
Rusten B, Eikebrokk B, Ulgenes Y, Lygren E (2006) Design and operations of the kaldnes moving bed biofilm reactors. Aquac Eng 34:322–323
Shi L, Zhou XF, Zhang YL, Gu GW (2009) Simultaneous determination of 8 fluoroquinolone antibiotics in sewage treatment plants by solid-phase extraction and liquid chromatography with fluorescence detection. Water Sci Technol 59:805–813
Snip L, Flores-Alsina X, Plósz BG, Gernaey KV, Jeppsson U. submitted for publication. Extending the BSM platform with occurrence, transport and fate of micropollutants using the ASM-X framework.Environ. Modell.Softw
Suárez S, Lema JM, Omil F (2010) Removal of pharmaceutical and personal care products (PPCPs) under nitrifying and denitrifying conditions. Water Res 44:3214–3224
Tong L, Li P, Wang YX, Zhu KZ (2009) Analysis of veterinary antibiotic residues in swine wastewater and environmental water samples using optimized SPE-LC/MS/MS. Chemosphere 74:1090–1097
Verlicchi P, Aukidy M, Zambello E (2012) Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after a secondary treatment—a review. Sci Total Environ 429:123–155
Wang XJ, Xia SQ, Chen L, Zhao JF, Renault NJ, Chovelon JM (2006) Nutrients removal from municipal wastewater by chemical precipitation in a moving bed biofilm reactor. Process Biochem 41:824–828
Wang N, Guo XY, Xu J, Kong XJ, Gao SX, Shan ZJ (2014) Pollution characteristics and environmental risk assessment of typical veterinary antibiotics in livestock farms in Southeastern China. J Environ Sci Health B 49:1–12
Watkinson AJ, Murby EJ, Costanzo SD (2007) Removal of antibiotics in conventional and advanced wastewater treatment: implications for environmental discharge and wastewater recycling. Water Res 41:4164–4176
Xu WH, Zhang G, Li XD, Zou SC, Li P, Hu ZH (2007) Occurrence and elimination of antibiotics at four sewage treatment plants in the Pearl River Delta (PRD), South China. Water Res 41:4526–4534
Yang JF, Ying GG, Zhao JL, Tao R, Su HC, Liu YS (2011) Spatial and seasonal distribution of selected antibiotics in surface waters of the Pearl Rivers, China. J Environ Sci Health B 46:272–280
Zhou LJ, Ying GG, Zhao JL, Yang JF, Wang L, Yang B (2011) Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China. Environ Pollut 159:1877–1885
Zhou XF, Zhang YL, Shi L, Chen JB, Qiang ZM, Zhang TC (2013) Partitioning of fluoroquinolones on wastewater sludge. Clean-Soil, Air, Water 41(8):820–827
Acknowledgments
The authors would like to acknowledge the financial support from the Natural Science Foundation of China (No. 21507037), the Fundamental Research Funds for NIES in 2016 “Source Apportionment Research of antibiotics pollution in typical drinking water resource” as well as Commonwealth and Environmental Protection Project granted by the MEP (No. 201309031), and the Major Science and Technology Program for Water Pollution Control and Treatment (2015ZX07203-007).
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Angeles Blanco
Electronic supplementary material
ESM 1
(DOCX 33 kb)
Rights and permissions
About this article
Cite this article
Guo, X., Yan, Z., Zhang, Y. et al. Removal mechanisms for extremely high-level fluoroquinolone antibiotics in pharmaceutical wastewater treatment plants. Environ Sci Pollut Res 24, 8769–8777 (2017). https://doi.org/10.1007/s11356-017-8587-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-017-8587-3