Analysis and Sorption of Psychoactive Drugs onto Sediment

Abstract

An analytical method was developed to analyze eight psychoactive pharmaceuticals--including the antiepileptic carbamazepine, the opiates morphine, codeine, dihydrocodeine, the opiode tramadol, and the tranquilizers diazepam, oxazepam, temazepam--and the antibiotic sulfamethoxazole as well as three metabolites (10,11-dihydrocarbamazepine (DHC), 10,11-dihydroxy-10, 11-dihydrocarbamazepine, and N4-acetylsulfamethoxazole) in river sediments. Relative recoveries of all analytes exceeded 97% using either deuterated or 13C15N-labeled surrogate standards. Sorption isotherms of all analytes were constructed at pH 6.5-6.6 on two natural river sediments (Burgen and Dausenau) that differed in organic carbon contents and particle size distributions. Affinities of all analytes were up to an order of magnitude higher for the Dausenau sediment in comparison to the Burgen sediment. Isotherms were well described by the Freundlich model. Sorption of all analytes was linear on the Burgen sediment except for structurally similar carbamazepine (n = 0.90) and DHC (n = 0.88). Conversely, most analytes showed pronounced nonlinear sorption to the Dausenau sediment (n = 0.77-0.92) except for positively charged codeine, dihydrocodeine, and tramadol. Linear sorption of the latter was taken to arise from concentration-independent electrostatic interactions of the organocations with negatively charged surfaces on clay minerals or in the sediment organic matter. Desorption gave rise to hysteresis in 13 out of 16 investigated analyte-sorbent systems. Hysteresis was likely due to slow desorption kinetics beyond 24 h used in the experiment.