Occurrence of psychoactive stimulatory drugs in wastewaters in north-eastern Spain.

The occurrence of several psychoactive drugs in water resources from north-eastern Spain (NE-Spain) has been evaluated. The drugs were analyzed using ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-ESI-MS/MS) after enrichment by solid-phase extraction (SPE). Most of the studied controlled drugs (8 out of 11) were found in both influent and effluent samples from several wastewater treatment plants. Cocaine and its metabolite were detected in wastewaters at concentrations ranging from 4 ng/L to 4.7 mug/L and from 9 ng/L to 7.5 mug/L respectively while concentrations of amphetamine type stimulatory drugs ranged from 2 to 688 ng/L. Removal percentages were estimated by sampling eight WWTPs (n=4). Cocaine and benzoylecgonine removal percentages were higher than 88% while those of amphetamine type stimulants varied ranging from 40% to more than 99%. Daily variability was also evaluated by performing a sequential survey, which revealed important fluctuations in the concentrations of nicotine, paraxanthine, amphetamine and ecstasy during the week. From the total concentrations found in wastewater influents estimations of the cocaine and ecstasy consumption were performed. For cocaine the results were approximately 14 doses per 1000 inhabitants (15-64 years old) per day and for ecstasy, approximately 4 doses per 1000 young adults (15-34 years old) per day for ecstasy.

New chlorinated amphetamine-type-stimulants disinfection-by-products formed during drinking water treatment.

Previous studies have demonstrated high removal rates of amphetamine-type-stimulants (ATSs) through conventional drinking water treatments; however the behaviour of these compounds through disinfection steps and their transformation into disinfection-by-products (DBPs) is still unknown. In this work, for the first time, the reactivity of some ATSs such as amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA) with chlorine has been investigated under simulated and real drinking water treatment conditions in order to evaluate their ability to give rise to transformation products. Two new DBPs from these illicit drugs have been found. A common chlorinated-by-product (3-chlorobenzo)-1,3-dioxole, was identified for both MDA and MDEA while for MDMA, 3-chlorocatechol was found. The presence of these DBPs in water samples collected through drinking water treatment was studied in order to evaluate their formation under real conditions. Both compounds were generated through treatment from raw river water samples containing ATSs at concentration levels ranging from 1 to 15 ng/L for MDA and from 2.3 to 78 ng/L for MDMA. One of them, (3-chlorobenzo)-1,3-dioxole, found after the first chlorination step, was eliminated after ozone and GAC treatment while the MDMA DBP mainly generated after the postchlorination step, showed to be recalcitrant and it was found in final treated waters at concentrations ranging from 0.5 to 5.8 ng/L.

Occurrence and removal of pharmaceuticals and hormones through drinking water treatment.

The occurrence of fifty-five pharmaceuticals, hormones and metabolites in raw waters used for drinking water production and their removal through a drinking water treatment were studied. Thirty-five out of fifty-five drugs were detected in the raw water at the facility intake with concentrations up to 1200 ng/L. The behavior of the compounds was studied at each step: prechlorination, coagulation, sand filtration, ozonation, granular activated carbon filtration and post-chlorination; showing that the complete treatment accounted for the complete removal of all the compounds detected in raw waters except for five of them. Phenytoin, atenolol and hydrochlorothiazide were the three pharmaceuticals most frequently found in finished waters at concentrations about 10 ng/L. Sotalol and carbamazepine epoxide were found in less than a half of the samples at lower concentrations, above 2 ng/L. However despite their persistence, the removals of these five pharmaceuticals were higher than 95%.

Evaluation of the presence of drugs of abuse in tap waters.

A total of seventy samples of drinking water were tested for non-controlled and illicit drugs. Of these, 43 were from Spanish cities, 15 from seven other European countries, three from Japan and nine from seven different Latin American countries. The most frequently detected compounds were caffeine, nicotine, cotinine, cocaine and its metabolite benzoylecgonine, methadone and its metabolite EDDP. The mean concentrations of non-controlled drugs were: for caffeine 50 and 19 ng L(-1), in Spanish and worldwide drinking water respectively and for nicotine 13 and 19 ng L(-1). Illicit drugs were sparsely present and usually at ultratrace level (<1 ng L(-1)). For example, cocaine has mean values of 0.4 (Spain) and 0.3 ng L(-1) (worldwide), whereas for benzoylecgonine, these mean values were 0.4 and 1.8 ng L(-1), respectively. Higher concentrations of benzoylecgonine were found in Latin American samples (up to 15 ng L(-1)). No opiates were identified in any sample but the presence of methadone and EDDP was frequently detected. Total mean values for EDDP were 0.4 ng L(-1) (Spain) and 0.3 ng L(-1) (worldwide). Very few samples tested positive for amphetamines, in line with the reactivity of chlorine with these compounds. No cannabinoids, LSD, ketamine, fentanyl and PCP were detected.

Fast liquid chromatography-quadrupole-linear ion trap mass spectrometry for the analysis of pharmaceuticals and hormones in water resources.

This paper presents the development of a fast multi-residue method for the determination of 49 pharmaceuticals and 6 metabolites from different therapeutic classes in water resources by means of Ultra-performance liquid chromatography (UPLC) coupled to tandem mass spectrometry. The use of the UPLC technology enabled all the 55 compounds to be separated chromatographically in less than 9min (6.3min positive mode and 2.7min negative mode) and with a total analysis time of 18min when considering column conditioning. Improved resolution, sensitivity and a reduction of matrix effects were obtained under these conditions. Unequivocal identification and quantification of the target compounds was also performed by using the dual acquisition modes of the hybrid triple quadrupole-linear ion trap (QqLIT) system. Triple quadrupole mode by means of selected reaction monitoring (SRM) was used for quantification, whilst a second SRM transition together with information-dependent analysis (IDA) experiments was used for confirmation. Additionally, one general, single solid-phase extraction (SPE) method was developed by using Oasis HLB cartridges. Quality parameters of the method in wastewaters were established obtaining a fast, robust, reproducible and cost-effective method for all the target pharmaceuticals. Finally, the optimized SPE-UPLC/QqLIT method was used for the analysis of the target compounds in wastewaters from Spain. Thirty-one out of fifty-five compounds were identified in the samples collected.

Natural photodegradation of the cyanobacterial toxins microcystin and cylindrospermopsin.

Microcystins (MC) and cylindrospermopsin (CYN) are potent toxins produced by diverse cyanobacterial genera found in waterbodies throughout the world. In the present study, and in order to achieve a better understanding of the fate of cyanobacterial toxins in the environment, we assessed the photodegradation of MC and CYN along the water column and by different radiation bands of the natural solar spectrum: photosynthetic active radiation (PAR), UV-A, and UV-B. Photodegradation of CYN seemed to be highly dependent on UV-A and was very low under natural conditions. This fact could be one of the reasons explaining the high extracellular CYN concentration found in diverse waterbodies. Microcystin photodegradation was higher, all three radiation bands (PAR, UV-A, and UV-B) being responsible for its degradation, although PAR and UV-A were more efficient because of their high natural irradiance. Modeling of MC photodegradation along the watercolumn was performed, using specific MC breakdown rates for the different radiation bands and including calculated attenuation coefficients for these bands. As a result, we suggest that rapid and efficient MC photodegradation may be expected in shallow systems or thin mixed layers.

Stimulatory drugs of abuse in surface waters and their removal in a conventional drinking water treatment plant.

The presence of psychoactive stimulatory drugs in raw waters used for drinking water production and in finished drinking water was evaluated in a Spanish drinking water treatment plant (DWTP). Contamination of the river basin which provides raw water to this DWTP was also studied. In surface waters, illicit drugs such as cocaine, benzoylecgonine (cocaine metabolite), amphetamine, methamphetamine, MDMA (ecstasy), and MDA were detected at mean concentrations ranging from 4 to 350 ng/L. Nicotine, caffeine, and their metabolites were also found at the microg/L level. The elimination of these compounds during drinking water treatment was investigated in a real waterworks. Amphetamine-type stimulants (except MDMA) were completely removed during prechlorination, flocculation, and sand filtration steps, yielding concentrations lowerthan their limits of detection (LODs). Further, ozone treatment was shown to be effective in partially eliminating caffeine (76%), while subsequent granulated activated carbon (GAC) filtration removed cocaine (100%), MDMA(88%), benzoylecgonine (72%), and cotinine (63%). Postchlorination achieved the complete elimination of cocaine and nicotine and only one parent compound (caffeine) and two metabolites (cotinine and benzoylecgonine) persisted throughout treatment although reductions of 90% for caffeine and benzoylecgonine and 74% for cotinine were obtained.

Ultraperformance liquid chromatography-tandem mass spectrometry analysis of stimulatory drugs of abuse in wastewater and surface waters.

Ultraperformance liquid chromatography coupled to electrospray tandem mass spectrometry was used for the rapid and simultaneous analysis of 15 stimulatory drugs in water. Cocaine, amphetamine-related compounds, LSD, ketamine, PCP, fentanyl, and metabolites, among the controlled drugs, and nicotine, caffeine, and their metabolites, among the noncontrolled drugs, were studied. Chromatographic separation was achieved in less than 4.5 min, with improved peak resolution and sensitivity. Identification and quantification of the compounds of interest was performed by selected reaction monitoring, using an electrospray ionization source. Isotope dilution (except for paraxanthine) was used for quantitation. Quality parameters of the method were established, and limits of quantification were obtained for controlled drugs in surface waters from 0.1 to 3.1 ng/L and in wastewaters from 0.2 to 4.0 ng/L. Run-to-run and day-to-day precisions were evaluated in different water matrixes (Milli-Q water, surface water, wastewater). To assess the presence of these drugs in real water samples, the optimized method was applied to the analysis of wastewater and surface river water. The analysis of several samples from wastewater treatment plants in northeast Spain revealed the presence of drugs such as cocaine and amphetamine-related compounds, in both influent and effluent samples. Cocaine metabolite and MDMA (ecstasy) were also found in surface waters while nicotine and caffeine were detected in all the analyzed samples. The results obtained demonstrate that the presence of these drugs in the aquatic media must be considered a matter of environmental concern.