Determination of multiple pharmaceutical classes in surface and ground waters by liquid chromatography–ion trap–tandem mass spectrometry

• Published in: Journal of Chromatography A Vol. 1216; no. 25; pp. 4989 - 5000
• Main Authors: GRUJIC, Svetlana, VASILJEVIC, Tatjana, LAUSEVIC, Mila
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 19.06.2009; Amsterdam; New York: Elsevier; Elsevier
• Subjects: Analgesics - isolation & purification; Analgesics, Non-Narcotic - isolation & purification; Analysis methods; Analytical chemistry; Anti-Bacterial Agents - isolation & purification; Antibiotics; Anticonvulsants - isolation & purification; Applied sciences; Benzodiazepines - isolation & purification; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, Liquid - methods; drug residues; drugs; Exact sciences and technology; False Positive Reactions; groundwater contamination; Hydrogen-Ion Concentration; Ion trap; liquid chromatography; Liquid chromatography–tandem mass spectrometry; mass spectrometry; Multiclass pharmaceuticals; Natural water pollution; Other chromatographic methods; Pharmaceutical Preparations - isolation & purification; Pollution; Reproducibility of Results; Sensitivity and Specificity; Soil Pollutants - classification; Solid Phase Extraction; surface water; tandem mass spectrometry; Tandem Mass Spectrometry - methods; Water analysis; Water Pollutants, Chemical - classification; water pollution; Water treatment and pollution; Ion trap; Antibiotics; Water analysis; Solid-phase extraction; Multiclass pharmaceuticals; Liquid chromatography–tandem mass spectrometry; Solid phase extraction; Tandem mass spectrometry; Chemical analysis; Psychotropic; Lactam; HPLC chromatography; Liquid chromatography-tandem mass spectrometry; Anticonvulsant; Electrospray; Chemical enrichment; Sample preparation; Benzodiazepine derivatives; Antiinfectious; Ground water; Trace analysis; Sulfonamide; Coupled method; Tetracycline derivatives; Antiinflammatory agent; Macrolide; Antibiotic; Reversed phase chromatography; Cephalosporin derivatives; Analgesic; Multicomponent analysis; Tranquillizer; Sulfonamides; Surface water; Water quality; Antipyretic; Water pollution; Antibacterial agent; Mass spectrometry
• ISSN: 0021-9673; 1873-3778
• DOI: 10.1016/j.chroma.2009.04.059

This paper describes development, optimization and application of analytical method for determination and reliable confirmation of nineteen pharmaceuticals from different therapeutic classes (antibiotics—β-lactams, cephalosporines, sulfonamides, macrolides and tetracyclines; benzodiazepines; antiepileptics and analgoantipyretics) in surface and ground waters at ng l −1 levels. Water samples were prepared using solid-phase extraction and extracts were analyzed by liquid chromatography–ion trap–tandem mass spectrometry with electrospray ionization in both positive and negative ionization mode. The efficiency of ten different SPE cartridges to extract diverse compounds from water was tested. The pH-value of the water sample, the volume of elution solvent and the sample volume were optimized. Matrix effect, especially pronounced for cephalexin and metamizole, was eliminated using matrix-matched standards. It was determined that extraction should be performed at pH ∼ 7.5, i.e. without pH adjustment, and at pH 3, depending on the analyte. Azithromycin, doxycycline and acetylsalicylic acid must be extracted in acidic environment, whereas extraction of paracetamol, ampicillin, erythromycin and metamizole should be performed without pH adjustment. Repeatability of the method was generally lower than 20%. The estimated limits of detection were in the range from 0.15 to 12.46 ng l −1. The method was applied to 26 water samples for monitoring of selected drug residues. Results revealed the presence of carbamazepine (80% of water samples), azithromycin (23%), as well as trimethoprim and paracetamol (both 15%). The most striking was the false positive signal of diclofenac in every analyzed water sample. Confirmation of the positive results was performed by repeated injection of the positive sample extracts using confirmatory method with additional transitions.