title: Challenge of high polarity and low concentrations in analysis of cytostatics and metabolites in wastewater by hydrophilic interaction chromatography/tandem mass spectrometry.
abstract: A method for solid phase extraction and HPLC-MS/MS of the cytostatics 5-fluorouracil, cytarabine, and gemcitabine and human metabolites uracil 1-beta-d-arabinofuranoside and 2',2'-difluorodeoxyuridine in wastewater was established. Wastewater samples from a Swiss hospital were analyzed for 5-fluorouracil, gemcitabine and 2',2'-difluorodeoxyuridine. The limits of quantification were 5.0, 0.9, and 9.0ng/L and the maximum concentrations detected were 27, 38, and 840ng/L, respectively. Along with the method development, retention mechanisms on the hydrophilic interaction chromatography (HILIC) stationary phase were studied. Both partitioning and adsorption play a role in the retention on the tested sulfoalkylbetaine modified silica HILIC column material. The contribution of these two processes is changing over the 1.6-40% range water in the mobile phase. Although the specific break point is difficult to determine, adsorption becomes more significant as the fraction of water in the mobile phase decreases below approximately 16%.
authors.affiliation: Eawag, Swiss Federal Institute of Aquatic Science and Technology, Environmental Chemistry, Uberlandstrasse 133, CH-8600 Dübendorf, Switzerland.
authors.forename: Lubomira
authors.initials: L
authors.lastname: Kovalova
authors.forename: Christa S
authors.initials: CS
authors.lastname: McArdell
authors.forename: Juliane
authors.initials: J
authors.lastname: Hollender
mesh_terms: D000327:Adsorption; D002853:Chromatography, Liquid / Q000379:methods*; D054697:Cytostatic Agents / Q000032:analysis*; D003841:Deoxycytidine / Q000031:analogs & derivatives / Q000032:analysis; D004350:Drug Residues / Q000032:analysis*; D005467:Floxuridine / Q000031:analogs & derivatives / Q000032:analysis; D005472:Fluorouracil / Q000032:analysis; D057927:Hydrophobic and Hydrophilic Interactions; D016014:Linear Models; D008958:Models, Molecular; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D052616:Solid Phase Extraction / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014867:Water / Q000032:analysis; D014874:Water Pollutants, Chemical / Q000032:analysis*; D000093542:Gemcitabine
chemical_list: D054697:Cytostatic Agents; D014874:Water Pollutants, Chemical; D005467:Floxuridine; D014867:Water; D003841:Deoxycytidine; D005472:Fluorouracil; C084565:2',2'-difluoro-2'-deoxyuridine; D000093542:Gemcitabine