Identification of cocaine and its metabolites in urban wastewater and comparison with the human excretion profile in urine.

The most relevant human urinary metabolites of cocaine (nine metabolites) were measured in urban wastewater in Italy and USA. A novel analytical method based on liquid chromatography tandem mass spectrometry allowed the identification of ecgonine, ecgonine methyl ester and the pyrolytic derivatives of cocaine in untreated wastewater. The aim of this study was to verify whether the pattern of cocaine metabolites in wastewater reflected the human excretion profile in urine. The performance of the method was good, with recoveries higher than 60% and limits of quantifications in the low ng/L range. The stability in untreated wastewater was assessed for all metabolites and the best storage condition resulted freezing samples immediately after collection and keep them frozen until analysis. All the selected compounds were measured in wastewater at concentrations up to 1.5 μg/L and their weekly loads were calculated during a five weeks monitoring campaign in Milan (Italy). The profiles of cocaine metabolites in wastewater matched with those in human urine reported in the literature, suggesting that measures in wastewater reflect the real human excretion and that wastewater analysis is suitable for assessing drug consumption. Benzoylecgonine was confirmed as the best target for estimating cocaine use by wastewater analysis, while cocaine itself should not be considered because its amount in wastewater is affected by other environmental sources such as transport, handling and consumption. Results suggested that the measurement of other metabolites in combination with benzoylecgonine might reflect 60% of an administered dose of cocaine providing also information on different patterns of use.

[1]  C. Banta-Green,et al.  Eliminating solid phase extraction with large-volume injection LC/MS/MS: analysis of illicit and legal drugs and human urine indicators in U.S. wastewaters. , 2008, Environmental science & technology.

[2]  Ronny Blust,et al.  Spatial and temporal variations in the occurrence of cocaine and benzoylecgonine in waste- and surface water from Belgium and removal during wastewater treatment. , 2009, Water research.

[3]  S. Castiglioni,et al.  Illicit drugs in the environment , 2009, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[4]  Ettore Zuccato,et al.  Estimating Community Drug Abuse by Wastewater Analysis , 2008, Environmental health perspectives.

[5]  E. Cone,et al.  Cocaine metabolism and urinary excretion after different routes of administration. , 1998, Therapeutic drug monitoring.

[6]  D. Alvarez,et al.  Polar Organic Chemical Integrative Sampling and Liquid Chromatography–Electrospray/Ion-Trap Mass Spectrometry for Assessing Selected Prescription and Illicit Drugs in Treated Sewage Effluents , 2004, Archives of environmental contamination and toxicology.

[7]  G. Skopp,et al.  Analysis of cocaine, benzoylecgonine, ecogonine methyl ester, and ecgonine by high-pressure liquid chromatography-API mass spectrometry and application to a short-term degradation study of cocaine in plasma. , 2001, Journal of analytical toxicology.

[8]  S. Belknap,et al.  Urinary excretion of cocaine, benzoylecgonine, and ecgonine methyl ester in humans. , 1988, Journal of analytical toxicology.

[9]  Yunsheng Hsieh,et al.  Potential of HILIC-MS in quantitative bioanalysis of drugs and drug metabolites. , 2008, Journal of separation science.

[10]  Randall C. Baselt,et al.  Disposition of toxic drugs and chemicals in man , 1982 .

[11]  D. Barceló,et al.  Analysis of drugs of abuse and their human metabolites in water by LC-MS2: A non-intrusive tool for drug abuse estimation at the community level , 2008 .

[12]  A. Hogenboom,et al.  Accurate mass screening and identification of emerging contaminants in environmental samples by liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. , 2009, Journal of chromatography. A.

[13]  Ettore Zuccato,et al.  Identification and measurement of illicit drugs and their metabolites in urban wastewater by liquid chromatography-tandem mass spectrometry. , 2006, Analytical chemistry.

[14]  Odd Hordvin,et al.  The Drug Situation in Norway 2011 : Annual report to the European Monitoring Centre for Drugs and Drug Addiction - EMCDDA , 2009 .

[15]  M. Huestis,et al.  Urinary excretion of ecgonine and five other cocaine metabolites following controlled oral, intravenous, intranasal, and smoked administration of cocaine. , 2010, Journal of analytical toxicology.

[16]  A. Cecinato,et al.  Occurrence of cocaine in the air of the World's cities. An emerging problem? A new tool to investigate the social incidence of drugs? , 2009, The Science of the total environment.

[17]  H. Hamilton,et al.  Cocaine and benzoylecgonine excretion in humans. , 1977, Journal of forensic sciences.

[18]  W. D. Wilson,et al.  Excretion of cocaine and its metabolites in man , 1969, The Journal of pharmacy and pharmacology.

[19]  M. Huestis,et al.  Concentration profiles of cocaine, pyrolytic methyl ecgonidine and thirteen metabolites in human blood and urine: determination by gas chromatography-mass spectrometry. , 2005, Biomedical chromotography.

[20]  F. Ventura,et al.  Stimulatory drugs of abuse in surface waters and their removal in a conventional drinking water treatment plant. , 2008, Environmental science & technology.

[21]  M. Lebeau,et al.  An automated SPE/LC/MS/MS method for the analysis of cocaine and metabolites in whole blood. , 2008, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[22]  P. Reuter World drug report , 1998 .

[23]  C. Daughton Illicit drugs: contaminants in the environment and utility in forensic epidemiology. , 2011, Reviews of environmental contamination and toxicology.

[24]  M. Guardia,et al.  Analytical methods to determine cocaine contamination of banknotes from around the world , 2008 .

[25]  I. Senta,et al.  Illicit drugs in wastewater of the city of Zagreb (Croatia)--estimation of drug abuse in a transition country. , 2010, Environmental pollution.

[26]  I. González-Mariño,et al.  Determination of drugs of abuse in water by solid-phase extraction, derivatisation and gas chromatography-ion trap-tandem mass spectrometry. , 2010, Journal of chromatography. A.

[27]  Adrian Covaci,et al.  Illicit drug consumption estimations derived from wastewater analysis: a critical review. , 2011, The Science of the total environment.

[28]  H. Maurer,et al.  Toxicokinetics of Drugs of Abuse: Current Knowledge of the Isoenzymes Involved in the Human Metabolism of Tetrahydrocannabinol, Cocaine, Heroin, Morphine, and Codeine , 2006, Therapeutic drug monitoring.

[29]  M. Fischman,et al.  Urinary excretion of ecgonine methyl ester, a major metabolite of cocaine in humans. , 1984, Journal of analytical toxicology.

[30]  M. Huestis,et al.  Cocaine and metabolites urinary excretion after controlled smoked administration. , 2007, Journal of analytical toxicology.

[31]  R. Fanelli,et al.  Mass spectrometric analysis of illicit drugs in wastewater and surface water. , 2008, Mass spectrometry reviews.

[32]  A. L. Roberts,et al.  Quantification of drugs of abuse in municipal wastewater via SPE and direct injection liquid chromatography mass spectrometry , 2010, Analytical and bioanalytical chemistry.

[33]  D. Barceló,et al.  Determination of drugs of abuse in airborne particles by pressurized liquid extraction and liquid chromatography-electrospray-tandem mass spectrometry. , 2009, Analytical chemistry.