The environmental fate of non-steroidal anti-inflammatory drugs (NSAIDs) in the urban water cycle is still uncertain and their status is mainly assessed based on specific water components and information on human risk assessments. This study (a) explores the environmental fate of NSAIDs (ibuprofen, IBU; naproxen, NAP; ketoprofen, KET; diazepam, DIA; and diclofenac, DIC) in the urban water cycle, including wastewater, river, and treated water via gas chromatography-mass spectrophotometry (GCMS), (b) assesses the efficiency of reducing the targeted NSAIDs in sewage treatment plant (STP) using analysis of variance (ANOVA), and (c) evaluates the ecological risk assessment of these drugs in the urban water cycle via teratogenic index (TI) and risk quotient (RQ). The primary receptor of contaminants comes from urban areas, as a high concentration of NSAIDs is detected (ranging from 5.87 × 103 to 7.18 × 104 ng/L). The percentage of NSAIDs removal in STP ranged from 25.6% to 92.3%. The NAP and KET were still detected at trace levels in treated water, indicating the persistent presence in the water cycle. The TI values for NAP and DIA (influent and effluent) were more than 1, showing a risk of a teratogenic effect. The IBU, KET, and DIC had values of less than 1, indicating the risk of lethal embryo effects. The NAP and DIA can be classified as Human Pregnancy Category C (2.1 > TI ≥ 0.76). This work proved that these drugs exist in the current urban water cycle, which could induce adverse effects on humans and the environment (RQ in high and low-risk categories). Therefore, they should be minimized, if not eliminated, from the primary sources of the pollutant (i.e., STPs). These pollutants should be considered a priority to be monitored, given focus to, and listed in the guideline due to their persistent presence in the urban water cycle.
A facile dispersive-micro-solid phase extraction (D-μ-SPE) method coupled with HPLC for the analysis of selected non-steroidal anti-inflammatory drugs (NSAIDs) in water samples was developed using a newly prepared magnetic sporopollenin-cyanopropyltriethoxysilane (MS-CNPrTEOS) sorbent. Sporopollenin homogenous microparticles of Lycopodium clavatum spores possessed accessible functional groups that facilitated surface modification. Simple modification was performed by functionalization with 3-cyanopropyltriethoxysilane (CNPrTEOS) and magnetite was introduced onto the biopolymer to simplify the extraction process. MS-CNPrTEOS was identified by infrared spectrometrywhile the morphology and the magnetic property were confirmed by scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), respectively. To maximize the extraction performance of ketoprofen, ibuprofen, diclofenac and mefenamic acid using the proposed MS-CNPrTEOS, important D-μ-SPE parameters were comprehensively optimized. The optimum extraction conditions were sorbent amount, 40 mg; extraction time, 5 min; desorption time; 5 min; sample volume, 15 mL; sample pH 2.0; and salt addition, 2.5% (w/v). The feasibility of the developed method was evaluated using spiked tap water, lake water, river water and waste water samples. Results showed that ketoprofen and ibuprofen were linear in the range of 1.0-1000 μg L-1whilst diclofenac and mefenamic acid were linear in the range 0.8-500 μg L-1. The results also showed good detection limits for the studied NSAIDs in the range of 0.21-0.51 μg L-1and good recoveries for spiked water samples in the range of 85.1-106.4%. The MS-CNPrTEOS proved a promising dispersive sorbent and applicable to facile and rapid assay of NSAIDs in water samples.