Transformation products formation of ciprofloxacin in UVA/LED and UVA/LED/TiO systems: Impact of natural organic matter characteristics.

The role of natural organic matter (NOM) in contaminants removal by photolysis and photocatalysis has aroused increasing interest. However, evaluation of the influence of NOM characteristics on the transformation products (TPs) formation and transformation pathways of contaminants has rarely been performed. This study investigated the decomposition kinetics, mineralization, TPs formation and transformation pathways of antibiotic ciprofloxacin (CIP) during photolysis and photocatalysis in the presence of three commercial NOM isolates (Sigma-Aldrich humic acid (SAHA), Suwannee River humic acid (SRHA) and Suwannee River NOM (SRNOM)) by using UVA light emitting diode (UVA/LED) as an alternative light source. NOM isolates insignificantly affected CIP photolysis but strongly inhibited CIP photocatalysis due to competitive radical quenching. The inhibitory effect followed the order of SAHA (49.6%) > SRHA (29.9%) > SRNOM (21.2%), consistent with their •OH quenching abilities, SUVA values and orders of aromaticity. Mineralization rates as revealed by F release were negatively affected by NOM during CIP photocatalysis. TPs arising from hydroxylation and defluorination were generally suppressed by NOM isolates in UVA/LED and UVA/LED/TiO systems. In contrast, dealkylation and oxidation of piperazine ring were promoted by NOM. The enhancement in the apparent formation kinetics (k) of TP245, TP291, TP334a, TP334b and TP362 followed the order of SRNOM > SRHA > SAHA. k values were positively correlated with O/C ratio, carboxyl content, E2/E3 and fluorescence index (FI) of NOM and negatively related with SUVA values. The observed correlations indicate that NOM properties are important in determining the fate and transformation of organic contaminants during photolysis and photocatalysis.