Spatial and temporal analysis of pharmaceutical concentrations in the upper Tennessee River basin.

The behavior of pharmaceutical compounds in aquatic ecosystems is not well defined. In order to determine spatial and temporal variations in concentrations of pharmaceuticals in the Tennessee River, water samples were collected from multiple points along the river and at the inflow of major tributaries. Sampling structure was designed to investigate trends between surface and subsurface samples, seasonal trends (winter, spring, summer, and fall), the direct influence of sewage treatment plants (upstream versus downstream), and the effect of downstream distance on pharmaceutical concentrations. All samples were quantified via solid phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). This method yielded reproducible quantitation at low parts per trillion (ng L(-1)) levels for all 14 analytes (acetaminophen, atorvastatin, caffeine, carbamazepine, ciprofloxacin, diltiazem, fluoxetine, levofloxacin, lovastatin, norfluoxetine, ranitidine, sertraline, sulfamethoxazole, and trimethoprim). Correlation analyses (depth, distance) and repeated-measures ANOVAs (season, sewage treatment plant proximity) were used to determine statistically significant trends for frequently detected pharmaceuticals (caffeine, carbamazepine, sulfamethoxazole). Caffeine and sulfamethoxazole were found to vary by season in subsurface samples; spring exhibited the highest concentrations. Carbamazepine varied in proximity to sewage treatment plant outfall with subsurface samples yielding greater concentrations downstream than upstream. In addition, individual pharmaceuticals displayed positive correlation between surface and subsurface samples and negative correlation with downstream distance from the headwaters.