Resumen de Análisis cualitativo y cuantitativo de fármacos en peces por espectrometría de masas de alta resolución de cuadrupolo-tiempo de vuelo
In this doctoral thesis, analytical methods for the determination of pharmaceuticals for human use in fish muscle tissue were developed. For detection and quantification of pharmaceuticals, liquid chromatography (LC) coupled to high resolution mass spectrometry (HRMS) using a QTOF instrument in SWATH mode was used.
The validated analytical methodologies used QuEChERS extraction or ultrasound extraction. Purification of the extracts was aimed to remove the lipid material, by EMR-lipid removal and Z-Sep+.
The validated parameters included recovery, accuracy, matrix effect, reproducibility, sensitivity, robustness and linearity. The validated QuEChERS extraction method performed for freeze-dried fish muscle matrices, at 3 different levels of concentration, was applied to 16 samples collected from two European rivers. The quantitative analysis revealed the presence of seven pharmaceuticals in concentrations up to 80 ng/g dry weight of fish.
In the second methodology, samples of fresh fish (fw) were examined for the presence of 47 drugs in targeted mode validated up to 50 ng/g fish (fw). As a complement, more than 500 pharmaceuticals, drugs of abuse, metabolites and transformation products were included for the suspected screening analysis. Positive results were confirmed through HRMS databases: SCIEX All-In-One HR-MS/MS, NIST 2017 library, Chemspider. The application of this method to 32 fish samples from 4 European rivers resulted in the detection of ten pharmaceuticals at concentrations up to 69 ng/g fish (fw). By suspect screening analysis, benzoylecgonine, cocaine, nicotine and ofloxacin were successfully detected and confirmed in the analyzed samples.
Additionally, we performed a study of organ-specific accumulation of the pharmaceuticals in fish samples (and water) from the Llobregat River, Spain, using target and suspected screening analysis. The detection / quantification, was directed to tissues, organs and bio-fluids of fish.
While 53 substances were identified in the water samples by targeted analysis and/or suspected screening, up to 34 compounds were detected in the organs of each specie. The semi-quantitative evaluation indicated the preferential distribution of drugs, drugs of abuse, metabolites and transformation products in the kidney, skin, liver, brain and pancreas.
