Identification and Measurement of Illicit Drugs and Their Metabolites in Urban Wastewater by Liquid Chromatography−Tandem Mass Spectrometry

Abstract

Residues of illicit drugs and their metabolites that are excreted by humans may flow into and through wastewater treatment plants. The aim of this study was to develop a method for the determination of cocaine, amphetamines, morphine, cannabinoids, methadone, and some of their metabolites in wastewater. Composite 24-h samples from urban treatment plants were enriched with deuterated internal standards before solid-phase extraction. High-pressure liquid chromatography tandem mass spectrometry with multiple reaction monitoring was used for quantitation. Recoveries were generally higher than 80%, and limits of quantifications were in the low nanograms-per-liter range for untreated and treated wastewater. The overall variability of the method was lower than 10% for untreated and 5% for treated wastewater. The method was applied to wastewater samples coming from two treatment plants in Italy and Switzerland. Quantification ranges were found to be 0.2-1 microg/L for cocaine and its metabolite benzoylecgonine, 80-200 ng/L for morphine, 10 ng/L for 6-acetylmorphine, 60-90 ng/L for 11-nor-9-carboxy-Delta9-tetrahydrocannabinol, 10-90 ng/L for methadone and its main metabolite 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine, and lower than 20 ng/L for amphetamines. As previously reported for cocaine, this method could be useful to estimate and monitor drug consumption in the population in real time, helping social scientists and authorities to combat drug abuse.

Illicit drugs in Canadian municipal wastewater and estimates of community drug use

“…In Europe, methamphetamine is generally present at lower concentrations (i.e. <10 ng/L) in untreated wastewater, but the concentrations of MDMA and amphetamine are comparable to the levels reported in the present study (Zuccato et al, 2005;Castiglioni et al, 2006;Postigo et al, 2010).…”

“…These concentrations are very similar to the range of concentrations of these compounds detected in untreated wastewater from WWTPs in the USA (Chiaia et al, 2008) and in Europe (Zuccato et al, 2005;Castiglioni et al, 2006;Mari et al, 2009;Postigo et al, 2010). Fig.…”

“…3 illustrates the estimates of community use of the illicit drugs within the Canadian cities served by the three WWTPs. Calculations from the data for BE indicate that cocaine is the most commonly used illicit drug in Canadian cities, which is consistent with consumption estimates for other cities in continental Europe, Wales and Ireland (Zuccato et al, 2008a(Zuccato et al, , 2005Castiglioni et al, 2006;Postigo et al, 2010;Kasprzyk-Hordern et al, 2009;Bones et al, 2007). The estimates for the number of doses of cocaine varied widely from a low of 8.1 per day per 1000 people on a week day in the city served by WWTP3 to a high of 56.7 per day per 1000 people on a Friday in the city served by WWTP1 (Fig.…”

“…1). These ratios are markedly different from the ratios observed in untreated wastewater from cities in continental Europe (Zuccato et al, 2008a(Zuccato et al, , 2005Castiglioni et al, 2006;Mari et al, 2009;Postigo et al, 2010) and in the USA (Chiaia et al, 2008), Table 2 Target compounds and stable isotope surrogates surveyed in this study, with chemical formulas, the chromatographic retention times, the mass spectrometric SRM ion transitions, de-clustering potential (DP) and collision energies for analysis, and the limits of detection (LODs) and limits of quantitation (LOQs) for the target analytes dissolved in wastewater (ng/L) and adsorbed to particulates (ng/g dry weight).…”

“…Drug consumption can be estimated from data on the concentrations of the target compounds in untreated wastewater, the flow rates into municipal wastewater treatment plants (WWTPs), the population served by the WWTP, human excretion rates for the target compounds in urine, and estimates of the drug dose. This method has been used to estimate use patterns for drugs of abuse in continental Europe (Zuccato et al, 2005;Castiglioni et al, 2006;Mari et al, 2009;Postigo et al, 2010), in Wales (KasprzykHordern et al, 2009) and in Ireland (Bones et al, 2007). Recently, the concentrations of illicit drugs were determined in wastewater from municipal wastewater treatment plants (WWTPs) in the USA (Chiaia et al, 2008;Bartelt-Hunt et al, 2009;Loganathan et al, 2009), although these studies did not include estimates of community drug consumption.…”