Nicola Mastroianni

Spatial differences and temporal changes in illicit drug use in Europe quantified by wastewater analysis

Aims To perform wastewater analyses to assess spatial differences and temporal changes of illicit drug use in a large European population. Design Analyses of raw wastewater over a 1-week period in 2012 and 2013. Setting and Participants Catchment areas of wastewater treatment plants (WWTPs) across Europe, as follows: 2012: 25 WWTPs in 11 countries (23 cities, total population 11.50 million); 2013: 47 WWTPs in 21 countries (42 cities, total population 24.74 million). Measurements Excretion products of five illicit drugs (cocaine, amphetamine, ecstasy, methamphetamine, cannabis) were quantified in wastewater samples using methods based on liquid chromatography coupled to mass spectrometry. Findings Spatial differences were assessed and confirmed to vary greatly across European metropolitan areas. In general, results were in agreement with traditional surveillance data, where available. While temporal changes were substantial in individual cities and years (P ranging from insignificant to <10−3), overall means were relatively stable. The overall mean of methamphetamine was an exception (apparent decline in 2012), as it was influenced mainly by four cities. Conclusions Wastewater analysis performed across Europe provides complementary evidence on illicit drug consumption and generally concurs with traditional surveillance data. Wastewater analysis can measure total illicit drug use more quickly and regularly than is the current norm for national surveys, and creates estimates where such data does not exist.

Fully automated determination of nine ultraviolet filters and transformation products in natural waters and wastewaters by on-line solid phase extraction–liquid chromatography–tandem mass spectrometry

This paper describes the development and validation of the first fully automated method, based on on-line solid phase extraction-liquid chromatography-tandem mass spectrometry (on line-SPE-LC-MS/MS), for the determination of UV filters (UV F) and transformation products, with a wide range of physicochemical properties. The developed method was validated and applied to the analysis of the selected compounds in river water (RW), groundwater (GW), influent and effluent wastewater (IWW and EWW). Comparing with the off-line methodologies published so far the presented method provides several advantages including a shorter extraction time, lower sample volume and minimum manipulation. Low limits of detection were achieved for all the studied matrices, <3ng/L (GW), <3.5ng/L (RW), <4ng/L (EWW) and <10ng/L (IWW), allowing a reliable and accurate quantification of the analytes at trace level. SPE optimization and critical aspects associated with the trace level determination of the target compounds (e.g. matrix effects) have been also considered and discussed. The method was successfully applied to the analysis of the UV F in five real water samples of each considered matrix, being the first time that these compounds were determined in GW.

Drugs of abuse in surface and tap waters of the Tagus River basin: Heterogeneous photo-Fenton process is effective in their degradation

This work investigates for the first time the occurrence of drugs of abuse and metabolites in surface waters from the Tagus River on its way through the province of Toledo (downstream Madrid metropolitan area) and in drinking waters in two nearby cities. Some of the studied drugs are used for therapeutic purposes but they can also be consumed as illicit drugs. The results of this preliminary study have revealed the presence of 12 out of 22 drugs of abuse analyzed in fluvial water at concentrations ranging from 1.14 to 40.9 ng/L. The largest concentrations corresponded to the anxiolytics diazepam and lorazepam, the cocaine metabolite benzoilecgonine, the amphetamine-like compound ephedrine, and the methadone metabolite EDDP. All these substances, except for lorazepam, were detected in all the sampling points. Traces of methadone and ephedrine were detected in some samples of tap water. Despite the low concentrations of these pollutants, effects on wildlife or human health cannot be disregarded, especially on vulnerable population. Thus, the treatment of these substances using a heterogeneous photo-Fenton process has been evaluated, rendering a remarkable effectiveness for their degradation.

Drugs of abuse in urban groundwater. A case study: Barcelona

This study is concerned with drugs of abuse (DAs) and their metabolites in urban groundwater at field scale in relation to (1) the spatial distribution of DAs in Barcelonas groundwater, (2) the depth of the groundwater samples, (3) the presence of DAs in recharge sources, and (4) the assessment of the fate of DAs in Barcelona aquifers. To this end, 37 urban groundwater samples were collected in the city of Barcelona and a total of 21 drugs were analyzed including cocainics, amphetamine-like compounds, opioids, lysergics and cannabinoids and the prescribed drugs benzodiazepines. Overall, the highest groundwater concentrations (around 200 ng/L in SAP-4) and the largest number of detected DAs were found in zones basically recharged by a river that receives large amounts of effluents from waste water treatment plants (WWTPs). In contrast, the urbanized areas yielded not only lower concentrations but also a much smaller number of drugs, which suggests a local origin. In fact, cocaine and its metabolite were dominant in more prosperous neighborhoods, whereas the cheaper MDMA was the dominant DA in poorer districts. Measured concentrations were consistently smaller than those estimated from the waste water fraction in groundwater samples, suggesting that DAs undergo removal processes in both reducing and oxidizing conditions.

Drugs of abuse and benzodiazepines in the Madrid Region (Central Spain): seasonal variation in river waters, occurrence in tap water and potential environmental and human risk.

This work analyzes the seasonal variation (winter and summer) of ten drugs of abuse, six metabolites and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain. The occurrence of these compounds in tap water in this region is also investigated and a preliminary human health risk characterization performed for those substances found in tap water. Finally, a screening level risk assessment that combines the measured environmental concentrations (MECs) with dose-response data to estimate Hazard Quotients (HQs) for the compounds studied is also presented. The results of this study show the presence of fourteen out of the nineteen compounds analyzed in winter and twelve of them in summer. The most ubiquitous compounds, with a frequency of detection of 100% in both seasons, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-type stimulant (ATS) ephedrine (EPH), the opioid methadone (METH), the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three benzodiazepines investigated, namely alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). The highest concentrations observed corresponded to EPH (1020ngL(-1) in winter and 250ngL(-1) in summer). The only compounds not detected in both seasons were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (O-H-LSD), and Δ(9)-tetrahydrocannabinol (THC). In terms of overall concentration, all sampling points presented higher concentrations in winter than in summer. Statistical analyses performed to gather evidence concerning occasional seasonal differences in the concentrations of individual substances between summer and winter showed statistically significantly higher concentrations (p<0.05) of BE, EPH and the opioid morphine (MOR) in winter than in summer. Two out of the nineteen compounds studied, namely cocaine (CO) and EPH, were detected in tap water from one sampling point at concentrations of 1.61 and 0.29ngL(-1), respectively. The preliminary human health risk characterization showed that no toxic effects could be expected at the detected concentration level in tap water. The screening level risk assessment showed that MOR, EDDP and the THC metabolite 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol (THC-COOH) were present in at least one of the sampling sites in a concentration leading to a Hazard Quotient (HQ) value between 1.0 and 10.0, thus indicating some possible adverse effects. The cumulative HQ or Toxic units (TUs) calculated for each of the groups studied showed that opioids and cannabinoids were present at concentrations high enough to potentially generate some adverse effects on at least one sampling point.

Occurrence of drugs of abuse and benzodiazepines in river waters from the Madrid Region (Central Spain)

This work investigates, for the first time, the occurrence of 10 drugs of abuse, six metabolites, and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain and one of the most densely populated in Europe. The results of this study have shown the presence of 14 out of the 19 compounds analyzed at concentrations ranging from 1.45 to 1020 ng L(-1). The most ubiquitous compounds, found in 100% of the samples, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-like compound ephedrine (EPH), the opioids morphine (MOR), methadone (METH), and the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three investigated benzodiazepines alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). Meanwhile, the largest concentrations observed corresponded to EPH (up to 1020 ng L(-1)), BE (823 ng L(-1)), EDDP (151 ng L(-1)), and LOR (167 ng L(-1)). The only not detected compounds were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (OH-LSD), and Δ(9)-tetrahydrocannabinol (THC). Overall, the levels measured are comparatively higher than those previously reported in Europe. Comparison of the results obtained for samples collected on different days (Thursday and Sunday) did not show meaningful differences between weekdays and weekends. The lack of (eco)toxicological data does not permit to predict or disregard potential adverse effects on wildlife. Risk assessment in humans would require further knowledge, not currently available, on exposure to these compounds through other routes like drinking water and/or food.

Elimination of drugs of abuse and their toxicity from natural waters by photo-Fenton treatment

This paper investigates the elimination of drugs of abuse from six different chemical classes and their metabolites in natural fluvial waters (nearby the output of a sewage system). Mineralization of these substances and toxicological characterization before and after treatment by a heterogeneous photo-Fenton system has been evaluated. This advanced oxidation technology was able to significantly reduce the concentration of the drugs of abuse in all the tested conditions (different hydrogen peroxide and catalyst loadings). However, toxicological analyses measured as inhibition of fern spore mitochondrial activity, showed only a complete elimination of acute and chronic toxicity when a higher solid catalyst loading was used (0.6 g/L). A lower catalyst loading of 0.2 g/L was not enough for toxicity elimination. These results evidence the need for combining toxicological tests and chemical analyses in order to establish the effectiveness of the water treatment technologies based on advanced oxidation processes.

Analysis of ethyl sulfate in raw wastewater for estimation of alcohol consumption and its correlation with drugs of abuse in the city of Barcelona.

The increasing, generalized consumption of alcohol, especially among young people, generates great concern in our society due to its negative consequences on public health and safety. Besides the traditional, official methods employed for estimation of alcohol consumption, the monitoring of ethyl sulfate (EtS), a urinary biomarker of alcohol ingestion, in raw wastewater has been recently proposed as an additional tool to estimate alcohol use at community level through the so-called sewage epidemiology approach. In the presented study, a fast and reliable analytical method based on ion-pair liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been optimized and further applied to the analysis of EtS in seven 24h composite samples collected along one week at the inlet of a large sewage treatment plant (STP) located in the Barcelona area. EtS was measured in the entire set of analysed samples, with concentrations ranging from 5.5 to 33μg/L, which correspond to an absolute alcohol consumption of around 11,000 (Wednesday) to 25,000 (Sunday) kg/day. The average per capita absolute alcohol consumption calculated was 18mL/day/inhabitant. Moreover, the levels of EtS measured throughout the week showed high correlation with those of some recreational illicit drugs and metabolites, namely, cocaethylene (r(2)=0.9391, n=5), benzoylecgonine (r(2)=0.9252, n=7), ecstasy (r(2)=0.8950, n=7), amphetamine (r(2)=0.8707, n=7) and cocaine (r(2)=0.6425, n=7), measured in the same samples. This study confirms that the analysis of EtS in raw wastewater can be a useful tool for the estimation of alcohol consumption in an anonymous, fast and economic way, and indicates that consumption of alcohol and some illicit drugs occurs often together.

Drugs of abuse, cytostatic drugs and iodinated contrast media in tap water from the Madrid region (central Spain):A case study to analyse their occurrence and human health risk characterization.

This work analyses the presence of forty-eight emerging pollutants, including twenty-five drugs of abuse and metabolites, seventeen cytostatic drugs and six iodinated contrast media, in tap water from the Madrid Region. Analysis of the target compounds in the tap water was performed by means of (on-line or off-line) solid-phase extraction followed by analysis by liquid chromatography-tandem mass spectrometry. A preliminary human health risk characterization was undertaken for each individual compound and for different groups of compounds with a common mechanism of action found in tap water. The results of the study showed the presence of eight out of the twenty-five drugs of abuse and metabolites analysed, namely, the cocainics cocaine and benzoylecgonine, the amphetamine-type stimulants ephedrine, 3,4-methylenedioxymethamphetamine and methamphetamine, the opioid methadone and its metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine and, finally caffeine at concentrations ranging from 0.11 to 502 ng L(-1). Four out of the six analysed iodinated contrast media, namely, diatrizoate, iohexol, iomeprol and iopromide, were detected in at least one sample, with concentration values varying between 0.4 and 5 ng L(-1). Cytostatic compounds were not detected in any sample. Caffeine was the substance showing the highest concentrations, up to 502 ng L(-1), mainly in the drinking water sampling point located in Madrid city. Among the other drugs of abuse, the most abundant compounds were cocaine and benzoylecgonine, detected at concentrations ranging from 0.11 to 86 ng L(-1) and from 0.11 to 53 ng L(-1), respectively. Regarding iodinated contrast media, iohexol was the most ubiquitous and abundant compound, with a frequency of detection of 100% and concentrations from 0.5 to 5.0 ng L(-1) in basically the same range in all sampling points. Taking into account the results and types of treatment applied, ozonisation plus granular activated carbon filtration appears to be efficient in the removal of cocaine and benzoylecgonine. For the amphetamine-type stimulants, opioids and caffeine, ozonisation plus granular activated carbon filtration and ultrafiltration plus reverse osmosis showed higher removal efficiency than sand filtration. The human health risk characterization performed indicates that the lifetime consumption of the tap waters analysed has associated a negligible human health concern.

Comprehensive monitoring of the occurrence of 22 drugs of abuse and transformation products in airborne particulate matter in the city of Barcelona

In recent years monitoring the presence of psychotropic compounds in wastewater has been proposed as a tool to estimate community drug use. Measurement of drugs of abuse (DAs) in airborne particulate is currently being explored as an additional tool to evaluate drug use patterns in time and space, and identify potential emission sources. In this study, we comprehensively monitor the occurrence of 22 licit and illicit DAs and transformation products, belonging to 6 different chemical groups, in airborne particulate matter (PM10) in the city of Barcelona. In order to study spatial and temporal variations, samples were collected from 12 different selected locations on one weekday (Wednesday) and one weekend day (Saturday), during five consecutive weeks. A previously developed analytical methodology, based on pressurized liquid extraction (PLE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) determination, was adapted for analysis of the target compounds with satisfactory performance, ensuring reliability of results. Among the investigated compounds, cannabinol (CBN), cocaine (COC), and methamphetamine (MA) were found to be the most ubiquitous and abundant compounds in PM10 with concentrations ranging from 0.7pg/m(3) (MA) to 6020pg/m(3) (CBN). Significant differences in total DA concentrations in PM10 were observed across sampling days and locations. DA emissions were identified in highly densely populated areas, where popular commercial and nightlife zones are located. Psychoactive effects due to inhalation of measured concentrations are probably negligible; however, potential health effects due to chronic exposure have not been explored yet.