The Fenton process is used as a tertiary treatment to remove organic pollutants from the effluent of bio-treated pharmaceutical wastewater (EBPW). The optimal and most appropriate Fenton conditions were determined by an orthogonal array test and single-factor experiments. The removal of chemical oxygen demand (COD) was influenced by the following factors in a descending order: H2O2/Fe(II) molar ratio > H2O2 dosage > reaction time. Under the most appropriate Fenton conditions (H2O2/Fe(II) molar ratio of 1:1, H2O2 dosage of 120 mg L-1 and reaction time of 10 min), the COD and dissolved organic carbon (DOC) were removed with efficiencies of 62 and 53%, respectively, which met the national discharge standard (GB 21903-2008) for the Lake Tai Basin, China. However, the Fenton treatment was inadequate for removal of N compounds, and the removal of organic nitrogen led to an increment in N-NH3 from 3.28 to 19.71 mg L-1. Proteins and polysaccharides were completely removed, and humic acids (HAs) were partly removed with an efficiency of 55%. Three-dimensional excitation/emission matrix spectra (3DEEMs) indicated complete removal of fulvic acid-like substances and 90% reduction in the florescence intensity of humic acid-like substances. Organic pollutants with molecular weights (MW) > 10 kDa were completely removed, MW 5-10 kDa were degraded into smaller MW ones, and some low molecular weight acids (MW 0.1-1 kDa) were mineralized during the Fenton process. Some species, including pharmaceutical intermediates and solvents were detected by gas chromatography-mass spectrometry (GC-MS). The operational costs of the Fenton's treatment were estimated to be 0.58 yuan RMB/m3 EBPW based on reagent usage and iron sludge treatment and disposal.
Keywords: Bio-treated pharmaceutical wastewater; Effluent organic matter; Fenton process; Operational costs; Organic pollutants removal; Tertiary treatment.