Roles of hydrophobic and hydrophilic fractions of dissolved organic matter in sorption of ketoprofen to biochars

Hydrophobic acid (HoA) and hydrophilic neutral (HiN) are two major fractions of dissolved organic matter (DOM). Their role in the sorption of ketoprofen (KTP) to wheat straw-derived biochars pyrolyzed at 300 degrees C (WS300) and 700 degrees C (WS700) was investigated to further probe the mechanisms responsible. WS700 has much higher pore volume and specific surface area (SSA) than WS300. Loading of HoA and HiN resulted in surface coverage of biochars. HoA with larger molecular size led to more pore blockage of biochars than HiN. Higher HoA binding affinity also caused a stronger competition with KTP on biochars. These factors reduced the accessibility of sorption sites for KTP, and significantly inhibited KTP sorption to biochar of lower SSA (i.e., WS300) by HoA. Water solubility (S-w) of KTP was slightly enhanced (3%) in the presence of HoA. In contrast, the presence of HiN reduced (22%) S-w of KTP. The decreased S-w of KTP by HiN exerted a more dominant influence than its competitive and loading effects, thus led to apparent enhanced sorption of KTP, especially to biochar of higher SSA (i.e., WS700). The results demonstrated the diverse effects of HoA and HiN on KTP sorption, which is helpful in understanding pharmaceutical-DOM-biochar interactions and environmental behaviors of pharmaceuticals.