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Calcium ion is an important cation influencing the binding of recalcitrant organic contaminants with activated sludge during wastewater treatment process, but there is still unknown about its role in amphoteric fluoroquinolones binding. Binding experiments show that Ca 2+ markedly inhibited binding of ciprofloxacin (CIP) onto sludge, causing 7-203 times of CIP release. Multi-spectroscopic examinations indicate that tryptophan-like and tyrosine-like proteins in extracellular polymeric substances (EPS) were dominant components for CIP binding by static quenching and forming CIP-proteins complexes. Addition of Ca 2+ into EPS and CIP binding systems induced increase of association constants (from 0.024-0.064 to 0.027-0.084 L/μmol) and binding constants (from 0.002-0.039 to 0.012-0.107) and decrease of binding sites number (from 0.893-2.007 to 0.721-1.386). Functional groups of EPS and secondary structure of proteins were remarkably changed upon reactions with CIP and Ca 2+ . Calcium ion interacted with EPS and CIP binding system in two distinct ways: Ca 2+ shielded CO in amide I in EPS for CIP binding, whereas strengthened binding between CIP and functional groups including CO in carboxyl groups in extra-microcolony polymers and OH in extra-cellular polymers by forming ternary complexes. Cation competition for CO in amide I is responsible for Ca 2+ induced CIP release from the sludge. Results suggest the highly potential release of CIP from high saline wastewater and cation-conditioned sludge which needs further monitoring and evaluation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)