Combining large-scale investigation and quantum chemical calculation of pharmaceuticals: Spatiotemporal patterns of occurrence and structural insights into removal.

This study investigated the spatiotemporal distribution of 17 pharmaceuticals in wastewater treatment plants (WWTPs) from 17 provinces across China, and explored structural insights into their removal in full-scale wastewater treatment processes by quantum chemistry. Briefly, 10 pharmaceuticals were detected in above 85 % of samples, of which ibuprofen and sulfamethoxazole dominated with concentrations up to the μg/L level. Seasonally, concentrations of psychoactive drugs (PDs) were 1.3-2.6 times higher in summer than in other seasons. Spatially, higher average concentrations were detected in northern WWTPs, and regions with similar economic levels exhibited similar contamination patterns. Pharmaceutical removal in WWTPs ranged from 41.4 % (carbamazepine) to 87.2 % (sulfamethizole), with the secondary treatment segment, especially aerobic treatment units, maintaining an important position. Molecular structural mechanisms behind these removal performances were further revealed. Firstly, we demonstrated a significant association of pharmaceutical overall removal with electrophilicity index (ωcubic) as well as the lowest unoccupied molecular orbital energy (ELUMO). Highly electrophilic pharmaceuticals may persist in WWTPs and their sensitivity to electron exchange reactions accounted for the discrepant removal. In terms of treatment segments, pharmaceuticals with reaction sites masked in molecular structure, such as ibuprofen and venlafaxine, showed a propensity for tertiary treatment suitability. Furthermore, enzymes of aerobic units exhibited excellent docking affinity to pharmaceutical molecules with an average affinity of -7.2 kcal/mol, and hydrogen-bond interactions played an important factor in promoting biodegradation. Our results emphasize the necessity of assessing pharmaceutical contamination on a larger spatiotemporal scale. Moreover, the structural insights into removal phenomena offer scientific molecular-level justification for the design and optimization of pharmaceutical treatment technologies in WWTPs.