Sorption of acetaminophen, 17α-ethynyl estradiol, nalidixic acid, and norfloxacin to silica, alumina, and a hydrophobic medium

Two pure minerals and a hydrophobic medium were selected to study sorption of pharmaceuticals. The sorption of four pharmaceuticals, acetaminophen (analgesic), 17 alpha-ethynyl estradiol (synthetic hormone), nalidixic acid (antibiotic), and norfloxacin (antibiotic), was evaluated with silica, alumina, and Porapak P (a hydrophobic medium). Alumina and silica were selected to represent positively charged and negatively charged aquifer mineral surfaces at neutral pH, respectively, while Porapak P was selected to represent the hydrophobic organic content of an aquifer medium. At neutral pH, acetaminophen, the least hydrophobic pharmaceutical, showed no significant sorption to any of the media, while 17 alpha-ethynyl estradiol, the most hydrophobic pharmaceutical, showed significant sorption to Porapak P. Nalidixic acid, which has a carboxyl functional group that is anionic at neutral pH, showed significant adsorption to the positively charged alumina. Norfloxacin, with both a carboxyl (anionic) and a piperazynyl (cationic) group, can exist in four forms (neutral, cationic, anionic, and zwitterionic) depending on the aqueous pH. Norfloxacin also showed significant adsorption to alumina at neutral pH, albeit a lower adsorption than nalidixic acid. Both nalidixic acid and norfloxacin adsorbed to silica and Porapak P to a much lower extent. The pH dependence of nalidixic acid and norfloxacin adsorption to silica and alumina was also studied by varying the pH between 4 and 11. The maximum adsorption of nalidixic acid to alumina occurred near its pKa (pH similar to 6), where the combination of cationic alumina and anionic nalidixic produced maximum adsorption. The maximum adsorption of norfloxacin to alumina was observed at pH similar to 7, which was the region where the zwitterionic form dominated. This research demonstrates that the adsorption of ionizable pharmaceuticals is strongly dependent on the system pH, the pharmaceutical properties (pKa and hydrophobicity), and the nature of the surface charge (point of zero charge). For pharmaceuticals that are uncharged at environmentally relevant pH values, the main sorption factor is their solubility or hydrophobicity; for charged forms, ion exchange is also an important adsorption mechanism. (c) 2006 Elsevier Ltd. All rights reserved.