[Show abstract][Hide abstract] ABSTRACT: An isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was successfully developed and applied for analysis of 15 pharmaceuticals and 2 pharmaceutically active metabolites in fish tissues. This method relied on electrospray ionization (ESI), for which the influence of sample matrix on analyte ionization efficiencies remains a persistent challenge to environmental analysis. Statistically derived method detection limits (MDLs) for most analytes ranged from 1 to 10 ng/g, independent of sample matrix, and were as low as 0.04 ng/g for the most sensitive compounds in fillet tissue. MDLs for fish fillets were determined for both 10 μL and 100 μL injection volumes; however, results showed that detection limits did not scale linearly with injection volume. Direct comparison of spike recoveries from fish liver demonstrated that isotope dilution was superior to matrix-matched calibration in compensating for matrix interference. Spike recoveries for the isotope dilution approach generally ranged from 91 to 112%, independent of tissue (i.e., fillet or liver). The developed method was applied to examine target analytes in brown trout (Salmo trutta), collected upstream and downstream from a municipal effluent discharge to East Canyon Creek, Park City, UT, USA. Though no pharmaceuticals were detected in fish samples from the upstream location, 3 and 10 compounds (out of 17 target analytes) were detected in fish fillet and liver samples, respectively, from the downstream sampling site. Pharmaceuticals in fish fillets were observed at concentrations ranging from 0.14 to 12 ng/g, while levels were markedly higher in liver tissues (range: 0.27-600 ng/g).
Full-text · Article · Jul 2012 · Journal of Chromatography A
[Show abstract][Hide abstract] ABSTRACT: Researchers recognize that ionization state may influence the biological activity of weak acids and bases. Dissociation in aqueous solutions is controlled by the pKa of a compound and the pH of the matrix. Because many pharmaceuticals are implicitly designed as ionizable compounds, site-specific variability in pH of receiving waters may introduce uncertainty to ecological risk assessments. The present study employed 48-h and 7-d toxicity tests with Pimephales promelas exposed to the model weak base pharmaceutical sertraline over a gradient of environmentally relevant surface water pHs. The 48-h experiments were completed in triplicate, and the average lethal concentration values were 647, 205, and 72 microL sertraline at pH 6.5, 7.5, and 8.5, respectively. Survivorship, growth, and feeding rate (a nontraditional endpoint linked by other researchers to sertraline's specific mode of action) were monitored during the 7-d experiment. Adverse effects were more pronounced when individuals were exposed to sertraline at pH 8.5 compared to pH 7.5 and 6.5. The pH-dependent toxicological relationships from these studies were related to in-stream pH data for two streams in the Brazos River basin of central Texas, USA. This predictive approach was taken because of the scarcity of environmental analytical data for sertraline. The results of this study emphasized temporal variability associated with in-stream pH linked to seasonal differences within and between these spatially related systems. Relating site-specific pH variability of surface waters to ionization state may allow researchers to reduce uncertainty during ecological risk assessment of pharmaceuticals by improving estimates of biological effects associated with exposure.
[Show abstract][Hide abstract] ABSTRACT: Pharmaceuticals and personal care products are being increasingly reported in a variety of biological matrices, including fish tissue; however, screening studies have presently not encompassed broad geographical areas. A national pilot study was initiated in the United States to assess the accumulation of pharmaceuticals and personal care products in fish sampled from five effluent-dominated rivers that receive direct discharge from wastewater treatment facilities in Chicago, Illinois; Dallas, Texas; Orlando, Florida; Phoenix, Arizona; and West Chester, Pennsylvania, USA. Fish were also collected from the Gila River, New Mexico, USA, as a reference condition expected to be minimally impacted by anthropogenic influence. High performance liquid chromatography-tandem mass spectrometry analysis of pharmaceuticals revealed the presence of norfluoxetine, sertraline, diphenhydramine, diltiazem, and carbamazepine at nanogram-per-gram concentrations in fillet composites from effluent-dominated sampling locations; the additional presence of fluoxetine and gemfibrozil was confirmed in liver tissue. Sertraline was detected at concentrations as high as 19 and 545 ng/g in fillet and liver tissue, respectively. Gas chromatography-tandem mass spectrometry analysis of personal care products in fillet composites revealed the presence of galaxolide and tonalide at maximum concentrations of 2,100 and 290 ng/g, respectively, and trace levels of triclosan. In general, more pharmaceuticals were detected at higher concentrations and with greater frequency in liver than in fillet tissues. Higher lipid content in liver tissue could not account for this discrepancy as no significant positive correlations were found between accumulated pharmaceutical concentrations and lipid content for either tissue type from any sampling site. In contrast, accumulation of the personal care products galaxolide and tonalide was significantly related to lipid content. Results suggest that the detection of pharmaceuticals and personal care products was dependent on the degree of wastewater treatment employed.