A gas chromatographic method with flame ionization detection (GC/FID) was developed for the determination of cocaine and its metabolites in blood and urine samples from cocaine users in Northwestern Spain. After a solid-phase extraction with Bond Elut Certify cartridges and a derivatization with bistrimethyisilyltrifluoroacetamide-trimethylchlorosilane (1%), calibration curves were constructed over 0.4-4 mug ml(-1) for urine and 0.1-2 mug ml(-1) for blood, using proadifen as the reference compound. The average extraction recoveries were 75% for urine and 78% for blood. The limits of detection and quantitation were 0.071 and 0.24 mug ml(-1), respectively. Coefficients of variation were <10% and accuracy was within 12%. The average blood concentrations of cocaine, benzoylecgonine and ecgonine methyl ester in 42 living patients were 0.22, 1.43 and 0.16 mug ml(-1), respectively. Urine samples were collected from individuals in the criminal justice system (70 cases), from drug abusers admitted to emergency rooms (36 cases) and from patients under detoxification treatment (36 cases). The second group exhibited the highest average concentrations (e.g. 0.97 mug ml(-1) for cocaine, 5.23 mug ml(-1) for benzoylecgonine and 0.39 mug ml(-1) for ecgonine methyl ester). Sixty-five fatal intoxications due to cocaine alone or in combination with other drugs were studied, and average blood levels were found to be higher in the deaths related to cocaine alone (e.g. 0.40 mug ml(-1) for cocaine, 2.38 mug ml(-1) for benzoylecgonine and 0.38 mug ml(-1) for ecgonine methyl ester). Copyright (C) 2004 John Wiley Sons, Ltd.
