title: Method development for measuring trace levels of penicillins in aqueous environmental samples.
abstract: A method based on liquid chromatography/mass spectrometry with an electrospray ion source and a single quadrupole instrument (LC/ES-MS) has been developed for determining trace levels of eight widely used penicillins in aqueous environmental samples. Analyte extraction was performed from 4 L tap water, 2 L groundwater, 1 L river water, 0.2 L treated sewage and 0.1 L raw sewage, by using a Carbograph 4 cartridge. During removal of the solvent, penicillins were purposely allowed to convert into their penicilloyl methyl esters. This 'in situ' derivatization step resulted in a dramatic enhancement of the response of the ES-MS system for non-amphoteric penicillins. Analyte recoveries were better than 80% irrespective of the type of aqueous sample, with the exception of amoxicillin (76%) and ampicillin (77%) in tap water. At the level of 50 ng/L of each analyte in ground water, the within-day precision was in the range 6-10%. Calibration curves were linear for injected amounts up to 800 ng, with R(2) in the range 0.9952-0.9995. When injecting large equivalent volumes of the aqueous samples, the electrospray matrix effect altered in-source collision-induced dissociation (CID) spectra of the analytes by severely weakening signals for fragment ions, as compared to spectra of reference standards. Remedies to obviate this anomalous unwelcome effect are suggested. On the basis of a signal-to-noise ratio of 10, limits of quantification were estimated to range between 2 (cloxacillin) and 24 ng/L (amoxicillin) in river water.
authors.affiliation: Dipartimento di Chimica, Università "La Sapienza", Piazza Aldo Moro 5, 00185 Roma, Italy.
authors.forename: F
authors.initials: F
authors.lastname: Bruno
authors.forename: R
authors.initials: R
authors.lastname: Curini
authors.forename: A
authors.initials: A
authors.lastname: Di Corcia
authors.forename: M
authors.initials: M
authors.lastname: Nazzari
authors.forename: R
authors.initials: R
authors.lastname: Samperi
mesh_terms: D002853:Chromatography, Liquid / Q000295:instrumentation / Q000379:methods; D005618:Fresh Water / Q000032:analysis; D007202:Indicators and Reagents; D010406:Penicillins / Q000032:analysis*; D012680:Sensitivity and Specificity; D012722:Sewage / Q000032:analysis; D021241:Spectrometry, Mass, Electrospray Ionization / Q000295:instrumentation / Q000379:methods; D014874:Water Pollutants, Chemical / Q000032:analysis*; D018508:Water Purification; D014881:Water Supply / Q000032:analysis
chemical_list: D007202:Indicators and Reagents; D010406:Penicillins; D012722:Sewage; D014874:Water Pollutants, Chemical