Photodegradation of sulfasalazine and its human metabolites in water by UV and UV/peroxydisulfate processes

Abstract

The widespread occurrence of pharmaceuticals and their metabolites in natural waters has raised great concerns about their potential risks on human health and ecological systems. This study systematically investigates the degradation of sulfasalazine (SSZ) and its two human metabolites, sulfapyridine (SPD) and 5-aminosalicylic acid (5-ASA), by UV and UV/peroxydisulfate (UV/PDS) processes. Experimental results show that SPD and 5-ASA were readily degraded upon UV 254 nm direct photolysis, with quantum yields measured to be (8.6 ± 0.8) × 10^-3 and (2.4 ± 0.1) × 10^-2 mol Einstein^-1, respectively. Although SSZ was resistant to direct UV photolysis, it could be effectively removed by both UV/H₂O₂ and UV/PDS processes, with fluence-based pseudo-first-order rate constants determined to be 0.0030 and 0.0038 cm² mJ^-1, respectively. Second-order rate constant between SO₄^•- and SSZ was measured as (1.33 ± 0.01) × 10⁹ M^-1s^-1 by competition kinetic method. A kinetic model was established for predicting the degradation rate of SSZ in the UV/PDS process. Increasing the dosage of PDS significantly enhanced the degradation of SSZ in the UV/PDS process, which can be well predicted by the developed kinetic model. Natural water constituents, such as natural organic matter (NOM) and bicarbonate (HCO₃^-), influenced the degradation of SSZ differently. The azo functional group of SSZ molecule was predicted as the reactive site susceptible to electrophilic attack by SO₄^•- by frontier electron densities (FEDs) calculations. Four intermediate products arising from azo bond cleavage and SO₂ extrusion were identified by solid phase extraction-liquid chromatography-triple quadrupole mass spectrometry (SPE-LC-MS/MS). Based on the products identified, detailed transformation pathways for SSZ degradation in the UV/PDS system were proposed. Results reveal that UV/PDS could be an efficient approach for remediation of water contaminated by SSZ and its metabolites.

Keywords: Peroxydisulfate; Photolysis; Sulfasalazine; Sulfate radical; UV 254 nm.