Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 38
Filter
1.
Sci Total Environ ; 953: 176108, 2024 Nov 25.
Article in English | MEDLINE | ID: mdl-39265683

ABSTRACT

Wastewater-based epidemiology (WBE) is a well-established approach that can provide objective and real-time data on the consumption of substances such as pharmaceuticals. However, most of the studies reported so far compares consumption data obtained using WBE with those derived from prescription data from public health systems, which is often incomplete and might represent a source of uncertainty. This study aims to compare the measured pharmaceutical consumption back calculated with the WBE approach with consumption derived from dispensed pharmaceuticals in two regions of Spain, managed by two different Health Systems. To do so, a group of 17 pharmaceuticals, including the most representative ones of every therapeutic family, were monitored in influent wastewater (IWW) samples collected over a week campaign in spring 2022 at four different wastewater treatment plants (WWTPs) in Spain: two WWTPs in Madrid city (center of Spain) and two WWTPs in Catalonia (Northeast of Spain). Population-normalized daily loads (PNDL) revealed that the patterns of pharmaceutical occurrence in the different WWTPs are very similar, being acetaminophen, 4-acetamidoantipyrine and valsartan the pharmaceuticals with the highest PNDL values: 17162 ± 1457 mg day-1 1000 inh-1 for acetaminophen, 2365 ± 696 and 2429 ± 263 mg day-1 1000 inh-1 for 4-acetamidoantipyrine, 2006 ± 541 and 2041 ± 352 mg day-1 1000 inh-1 for valsartan. Pharmaceutical PNLDs were then transformed into measured pharmaceutical consumption (MC) and compared with dispensed consumption (DC) data obtained from the pharmacies in the catchment area where the WWTPs are located. A ratio MC/DC within 0.8 to 1.2 was obtained for 11 out of the 17 studied pharmaceuticals. Highlighting a match in all the cardiovascular system pharmaceuticals, with the exception of losartan (1.29-1.39 ratio) and valsartan (1.35-1.43) in all WWTPs. In summary, the degree of correlation between MC/DC is higher than those previously reported comparing with the prescribed pharmaceutical consumption.


Subject(s)
Wastewater , Water Pollutants, Chemical , Spain , Wastewater/chemistry , Water Pollutants, Chemical/analysis , Pharmaceutical Preparations/analysis , Waste Disposal, Fluid
2.
Talanta ; 275: 126146, 2024 Aug 01.
Article in English | MEDLINE | ID: mdl-38678925

ABSTRACT

A novel and simple method combining in-situ acetylation, liquid-liquid extraction and gas chromatography-mass spectrometry (GC-MS) has been developed for the quantification of 10 bromophenols in urine, used as biomarkers of exposure to polybrominated diphenyl ethers. The analytical process involves an enzymatic hydrolysis of the bromophenol glucuronide fraction followed by an aqueous derivatization of the phenol group with acetic anhydride. A subsequent liquid-liquid extraction of the sample with hexane allows the injection of the organic layer, using a programmed temperature vaporizer, into a gas chromatograph coupled to a single quadrupole mass spectrometer. Quantification is performed by the standard addition method. Limits of detection are in the pg mL-1 range. Trueness, assessed in terms of percentages of recovery, varies between 100 % and 118 % in synthetic urine and between 79 % and 117 % in human urine. Precision, assessed at two different levels, 0.25 ng mL-1 and 2.5 ng mL-1, shows values of relative standard deviation below 14 % both in intra- and inter-day studies for both matrices. The method has been applied to the analysis of seven urine samples, measuring concentrations higher than the LOQ in three of them. These levels are in agreement with others found in literature, but they have been obtained by applying a much simpler and faster protocol. In addition, the replacement of silylating reagents by acetic anhydride, to derivatize the phenol moiety, provides a greener alternative to other GC-MS procedures published up to date.


Subject(s)
Gas Chromatography-Mass Spectrometry , Liquid-Liquid Extraction , Phenols , Gas Chromatography-Mass Spectrometry/methods , Liquid-Liquid Extraction/methods , Humans , Phenols/urine , Phenols/chemistry , Acetylation , Limit of Detection
3.
Molecules ; 28(13)2023 Jun 25.
Article in English | MEDLINE | ID: mdl-37446640

ABSTRACT

Contraceptive tablets typically contain a combination of two synthetic versions of an estrogen and a progestogen, which work together to inhibit the ovulation process. An accurate and precise quantification of these components is essential for contraceptive producers. In this study, we have developed the first gas chromatography-mass spectrometry (GC-MS) method for the simultaneous quantification of 17α-ethinyl estradiol (EE) and drospirenone (DP) in contraceptive formulations. Under the final working conditions, analytes were extracted from the solid by ultrasound-assisted extraction (15 min) in methanol. The resulting suspension was diluted in ethyl acetate, subjected to centrifugation and, finally, the supernatant was directly injected into the GC-MS system. No derivatization reagents were utilized. To correct for instrumental variations, calibration was performed using the internal standard method, with cholesterol as the internal standard. A good linearity was achieved throughout the calibration range for both EE (3-12 µg mL-1) and DP (300-1200 µg mL-1), with R2 values exceeding 0.99. Trueness, assessed in terms of percentages of recovery, was also found to be satisfactory for both analytes, with recovery rates of 106 ± 8% for EE and 93 ± 9% for DP. Furthermore, intra-day and inter-day precision studies yielded relative standard deviation values below 6% for both analytes. In terms of sensitivity, the instrumental limits of detection were 0.25 µg mL-1 for EE and 6.6 µg mL-1 for DP, and the instrumental limits of quantification 0.82 µg mL-1 for EE and 22 µg mL-1 for DP. The method was successfully applied to the analysis of contraceptive tablets from three different pharmaceutical companies. No differences were observed between the measured and the declared amount of active principle per tablet, demonstrating the applicability of the procedure. In addition, a stability study conducted on both the standards and sample extracts demonstrated that they can be stored at room temperature for a minimum period of seven days.


Subject(s)
Contraceptives, Oral, Combined , Ethinyl Estradiol , Female , Humans , Estradiol , Gas Chromatography-Mass Spectrometry , Tablets
4.
Sci Total Environ ; 892: 164547, 2023 Sep 20.
Article in English | MEDLINE | ID: mdl-37270014

ABSTRACT

The consumption patterns of five categories of psychoactive substances (PS), including "conventional" illicit drugs, new psychoactive substances (NPS), therapeutic opioids, alcohol and nicotine, were studied in the city of Split, Croatia, using wastewater-based epidemiology (WBE), with an emphasis on the impact of a large electronic music festival. The study involved the analysis of 57 urinary biomarkers of PS in raw municipal wastewater samples collected in three characteristic periods, including the festival week in the peak-tourist season (July) and reference weeks in the peak-tourist season (August) and the off-tourist season (November). Such a large number of biomarkers allowed the recognition of distinct patterns of PS use associated with the festival, but also revealed some subtle differences between summer and autumn seasons. The festival week was characterized by markedly increased use of illicit stimulants (MDMA: 30-fold increase; cocaine and amphetamine: 1.7-fold increase) and alcohol (1.7-fold increase), while consumption of other common illicit drugs (cannabis and heroin), major therapeutic opioids (morphine, codeine and tramadol) and nicotine remained rather constant. Interestingly, NPS and methamphetamine clearly contributed to the festival PS signature in wastewater, but their prevalence was rather low compared to that of common illicit drugs. Estimates of cocaine and cannabis use were largely consistent with prevalence data from national surveys, whereas differences were found for typical amphetamine-type recreational drugs, particularly MDMA, and for heroin. The WBE data suggest that the largest proportion of morphine came from heroin consumption and that the percentage of heroin users seeking treatment in Split is probably rather low. The prevalence of smoking calculated in this study (30.6 %) was consistent with national survey data for 2015 (27.5-31.5 %), while the average alcohol consumption per capita >15 years (5.2 L) was lower than sales statistics suggest (8.9 L).


Subject(s)
Cocaine , Illicit Drugs , Music , N-Methyl-3,4-methylenedioxyamphetamine , Substance-Related Disorders , Water Pollutants, Chemical , Humans , Wastewater , Nicotine/analysis , Analgesics, Opioid/analysis , Heroin/analysis , Holidays , Illicit Drugs/analysis , Amphetamine , Cocaine/analysis , Ethanol/analysis , Substance Abuse Detection , Water Pollutants, Chemical/analysis , Substance-Related Disorders/epidemiology
5.
J Chromatogr A ; 1690: 463788, 2023 Feb 08.
Article in English | MEDLINE | ID: mdl-36649666

ABSTRACT

For the first time, a very simple and fast method combining the use of a guard column coupled to tandem mass spectrometry (guard column-MS/MS) has been proposed for the determination of plasticizer metabolites in urine. Briefly, samples (1.0 mL) were submitted to enzymatic hydrolysis for 10 min, filtered, diluted 1/10 v/v with ultrapure water and directly injected into the system. A fast run of only 2 min (3 min including the injection cycle) allowed the determination of 19 analytes. Enzymatic hydrolysis, filtering material, and guard column-MS/MS conditions were optimized. Intra-day precision at the low-level concentration (expressed as relative standard deviation, %RSD) obtained from the analysis of synthetic urine samples varied between 11 and 20%. Limits of quantification ranged from 2.8 to 60 ng/mL. Trueness values, calculated as apparent recoveries, ranged from 70 to 135%. To correct for matrix effects, analyte concentrations in real urine were quantified by the standard addition method. To confirm the results obtained by guard column-MS/MS, an ultra(high)-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was also applied (total chromatographic run time 17 min, including column re-equilibration). Concentrations measured with both methods were in good agreement. Hence, we propose the use of guard column-MS/MS to analyse a large number samples in a very short time (semi-quantification), and apply the chromatographic analysis only to those samples with levels close to/higher than the concentrations equivalent to the safe maximum daily intakes of the parent compounds (confirmation). This double strategy (semi-quantification by guard column-MS/MS and confirmation-when needed-by UHPLC-MS/MS) implies important savings in time and money.


Subject(s)
Plasticizers , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Chromatography, High Pressure Liquid/methods
6.
Water Res ; 206: 117719, 2021 Nov 01.
Article in English | MEDLINE | ID: mdl-34624656

ABSTRACT

Amphetamine (AMP), methamphetamine (MAMP) and 3,4-methylenedioxymethamphetamine (MDMA) occur in wastewater not only as a result of illicit consumption, but also, in some cases, from prescription drug use or by direct drug disposal into the sewage system. Enantiomeric profiling of these chiral drugs could give more insight into the origin of their occurrence. In this manuscript, a new analytical methodology for the enantiomeric analysis of amphetamine-like substances in wastewater has been developed. The method consists of a solid-phase extraction (SPE) followed by liquid chromatography-triple quadrupole-tandem mass spectrometry (LC-MS/MS), which showed low quantification limits in the 2.4-5.5 ng L-1 range. The LC-MS/MS method was first applied to characterize a total of 38 solid street drug samples anonymously provided by consumers. The results of these analysis showed that AMP and MDMA trafficked into Spain are synthesized as racemate, while MAMP is exclusively produced as the S(+)-enantiomer. Then, the analytical method was employed to analyse urban wastewater samples collected from the wastewater treatment plants (WWTPs) of five different cities in 2018 and 2019. Consumption estimated through normalized population loads in wastewater showed an increased pattern of AMP use in the Basque Country. Furthermore, the enantiomeric profiling of wastewater samples was contrasted to lisdexamfetamine (LIS) and selegiline (SEL) prescription figures, two pharmaceuticals which metabolize to S(+)-AMP, and to R(-)-AMP and R(-)-MAMP, respectively. From this analysis, and considering uncertainties derived from metabolism and adherence to treatment, it was concluded that LIS is a relevant source of AMP in those cases with low wastewater loads, i.e. up to a maximum of 60% of AMP detected in wastewater in some samples could originate from LIS prescription, while SEL does not represent a significant source of AMP nor MAMP. Finally, removal efficiencies could be evaluated for the WWTP (serving ca. 860,000 inhabitants) with higher AMP influent concentrations. The removal of AMP was satisfactory with rates higher than 99%, whereas MDMA showed an average removal of approximately 60%, accompanied by an enrichment of R(-)-MDMA.


Subject(s)
Wastewater , Water Pollutants, Chemical , Amphetamine , Chromatography, Liquid , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysis
7.
Sci Total Environ ; 772: 144794, 2021 Jun 10.
Article in English | MEDLINE | ID: mdl-33770873

ABSTRACT

Data obtained from wastewater analysis can provide rapid and complementary insights in illicit drug consumption at community level. Within Europe, Spain is an important country of transit of both cocaine and cannabis. The quantity of seized drugs and prevalence of their use rank Spain at the top of Europe. Hence, the implementation of a wastewater monitoring program at national level would help to get better understanding of spatial differences and trends in use of illicit drugs. In this study, a national wastewater campaign was performed for the first time to get more insight on the consumption of illicit drugs within Spain. The 13 Spanish cities monitored cover approximately 6 million inhabitants (12.8% of the Spanish population). Untreated wastewater samples were analyzed for urinary biomarkers of amphetamine, methamphetamine, MDMA, cocaine, and cannabis. In addition, weekend samples were monitored for 17 new psychoactive substances. Cannabis and cocaine are the most consumed drugs in Spain, but geographical variations showed, for instance, comparatively higher levels of methamphetamine in Barcelona and amphetamine in Bilbao, with about 1-fold higher consumption of these two substances in such metropolitan areas. For amphetamine, an enantiomeric profiling was performed in order to assure the results were due to consumption and not to illegal dumping of production residues. Furthermore, different correction factors for the excretion of cannabis were used to compare consumption estimations. All wastewater results were compared with previously reported data, national seizure data and general population survey data, were a reasonable agreement was found. Daily and yearly drug consumption were extrapolated to the entire Spanish population with due precautions because of the uncertainty associated. These data was further used to estimate the retail drug market, where for instance cocaine illicit consumption alone was calculated to contribute to 0.2-0.5% of the Spanish gross domestic product (ca. 3000-6000 million Euro/year).


Subject(s)
Illicit Drugs , Substance-Related Disorders , Water Pollutants, Chemical , Cities , Europe , Humans , Spain/epidemiology , Substance Abuse Detection , Substance-Related Disorders/epidemiology , Wastewater/analysis , Water Pollutants, Chemical/analysis
8.
Talanta ; 224: 121912, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33379114

ABSTRACT

Plasticizers are chemical compounds used in the production of flexible plastics for a large variety of applications. They are present in most of the environments and, hence, we are highly exposed to them via several routes (ingestion, inhalation, etc). Due to the endocrine disruption potential of some of these chemicals and the unknown toxicological effects of their alternatives, assessing human exposure to these contaminants is an issue of emerging concern. Herein we propose an analytical methodology for the determination of several plasticizer metabolites in wastewater as a non-invasive, cheap, and fast exposure monitoring tool complementary to the analysis of urine. A solid-phase extraction procedure followed by an ultra(high)-performance liquid chromatography-tandem mass spectrometry method was optimized and validated for 21 analytes among phthalate, terephthalate, and di-iso-nonyl cyclohexane-1,2-dicarboxylate metabolites. Method quantification limits ranged from 0.079 to 4.4 ng L-1. The method was applied to the analysis of seven daily composite wastewater samples collected in the NW of Spain. Metabolites of low molecular weight phthalates and of di-2-ethylhexyl phthalate were quantified in all samples, despite the existing regulations limiting the use of phthalates. Metabolites of terephthalates, introduced at the end of the 20th century as phthalate substituents, were also quantified in all samples, being the first time that they were detected in this matrix. Exposure back-calculation highlighted di-2-ethylhexyl terephthalate as the second most common plastic additive after diethyl phthalate in the population considered, reflecting the increasing substitution of di-2-ethylhexyl phthalate by its analogous terephthalate.

9.
J Hazard Mater ; 401: 123272, 2021 01 05.
Article in English | MEDLINE | ID: mdl-32645544

ABSTRACT

Phthalates are widely used plasticizers that produce endocrine-disrupting disorders. Quantifying exposure is crucial to perform risk assessments and to develop proper health measures. Herein, a wastewater-based epidemiology approach has been applied to estimate human exposure to six of the mostly used phthalates within the Spanish population. Wastewater samples were collected over four weekdays from seventeen wastewater treatment plants serving thirteen cities and ca. 6 million people (12.8 % of the Spanish population). Phthalate metabolite loads in wastewater were transformed into metabolite concentrations in urine and into daily exposure levels to the parent phthalates. Considering all the sampled sites, population-weighted overall means of the estimated concentrations in urine varied between 0.7 ng/mL and 520 ng/mL. Very high levels, compared to human biomonitoring data, were estimated for monomethyl phthalate, metabolite of dimethyl phthalate. This, together with literature data pointing to other sources of this metabolite in sewage led to its exclusion for exposure assessments. For the remaining metabolites, estimated concentrations were closer to those found in urine. Their 4-days average exposure levels ranged from 2 to 1347 µg/(day∙inh), exceeding in some sites the daily exposure thresholds set for di-i-butyl phthalate and di-n-buthyl phthalate by the European Food Safety Authority.


Subject(s)
Environmental Pollutants , Phthalic Acids , Cities , Environmental Exposure/analysis , Humans , Plasticizers , Wastewater
10.
Drug Alcohol Depend ; 215: 108241, 2020 10 01.
Article in English | MEDLINE | ID: mdl-32892109

ABSTRACT

BACKGROUND: In this study, an alternative and complementary method to those approaches currently used to estimate alcohol consumption by the population is described. This method, known as wastewater-based epidemiology (WBE), allows back-calculating the alcohol consumption rate in a given population from the concentrations of a selected biomarker measured in wastewater. METHODS: Composite (24-h) wastewater samples were collected at the inlet of 17 wastewater treatment plants located in 13 Spanish cities for seven consecutive days in 2018. The sampled area covered 12.8% of the Spanish population. Wastewater samples were analyzed to determine the concentration of ethyl sulfate, the biomarker used to back-calculate alcohol consumption. RESULTS: Alcohol consumption ranged from 4.5 to 46 mL/day/inhabitant. Differences in consumption were statistically significant among the investigated cities and between weekdays and weekends. WBE-derived estimates of alcohol consumption were comparable to those reported by its corresponding region in the Spanish National Health Survey in most cases. At the national level, comparable results were obtained between the WBE-derived annual consumption rate (5.7 ± 1.2 L ethanol per capita (aged 15+)) and that reported by the National Health Survey (4.7 L ethanol per capita (aged 15+)). CONCLUSIONS: This is the largest WBE study carried out to date in Spain to estimate alcohol consumption rates. It confirms that this approach is useful for establishing spatial and temporal patterns of alcohol consumption, which could contribute to the development of health care management plans and policies. Contrary to established methods, it allows obtaining information in a fast and relatively economical way.


Subject(s)
Alcohol Drinking/epidemiology , Ethanol/analysis , Wastewater-Based Epidemiological Monitoring , Wastewater/analysis , Adolescent , Cities , Health Surveys , Humans , Policy , Spain , Sulfuric Acid Esters , Water Pollutants, Chemical/analysis
11.
Sci Total Environ ; 741: 140384, 2020 Nov 01.
Article in English | MEDLINE | ID: mdl-32603944

ABSTRACT

Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3'-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine consumption in the seven analyzed regions was 2.2 g/(day∙1000 inh.), without any daily pattern. This average estimated nicotine consumption value agreed with the value derived from official tobacco sales data. Differences in consumption among the seven studied regions were found, being Galicia, the region with the lowest rate, and the Basque Country and Catalonia those with the highest rates. However, no conclusive correlation was found between those values and the prevalence data taken from two different national surveys, nor sociodemographic and health data. This study demonstrates that this tool can complement other indicators in order to accurately assess tobacco consumption rates at regional and national levels and provides the most extensive application of the approach in the Spanish territory.


Subject(s)
Tobacco Use , Wastewater-Based Epidemiological Monitoring , Humans , Nicotine/analysis , Spain , Wastewater/analysis
12.
Sci Total Environ ; 698: 134207, 2020 Jan 01.
Article in English | MEDLINE | ID: mdl-31499350

ABSTRACT

This study used wastewater-based epidemiology (WBE) to investigate the lifestyle of the inhabitants of Malé, the capital of the Republic of Maldives. Raw wastewater 12-h composite samples were collected from nine pumping stations serving the city area - thus representative of the whole Malé population. Samples were analysed by liquid chromatography coupled to mass spectrometry for estimating the profile of use of a large number of substances including illicit drugs, alcohol, caffeine, tobacco and pharmaceuticals. The illicit drugs most used were cannabis (THC) and heroin (700 and 18 g/day), with lower consumption of cocaine and amphetamines (0.1-1.2 g/day). It is important to note that the consumption of cannabis in Malé was comparable to that measured in other countries, while the consumption of heroin was higher. Among cathinones, mephedrone was detected at the highest levels similar to other countries. Consumption of alcohol, which is not allowed in Maldives, was found (1.3 L/day/1000 inhabitants), but at a low level compared with other countries (6-44 L/day/1000 inhabitants), while the consumption of caffeine and tobacco was generally in line with reports from other countries. Unique information on pharmaceuticals use was also provided, since no official data were available. Human lifestyle was evaluated by applying for the first time the full set of WBE methodologies available in our laboratory. Results provided valuable epidemiological information, which may be useful for national and international agencies to understand population lifestyles better, including illicit drug issues, and for planning and evaluation of drug prevention programs in Malé.


Subject(s)
Illicit Drugs/analysis , Wastewater/chemistry , Water Pollutants, Chemical/analysis , Amphetamines/analysis , Caffeine/analysis , Cocaine/analysis , Humans , Indian Ocean Islands , Substance Abuse Detection , Substance-Related Disorders/epidemiology
13.
Addiction ; 115(1): 109-120, 2020 01.
Article in English | MEDLINE | ID: mdl-31642141

ABSTRACT

BACKGROUND AND AIMS: Wastewater-based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population-normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011-17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data. DESIGN: Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017. SETTING AND PARTICIPANTS: Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries. MEASUREMENTS: Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of Δ9 -tetrahydrocannabinol (11-nor-9-carboxy-Δ9 -tetrahydrocannabinol) were measured in wastewater using liquid chromatography-tandem mass spectrometry. Daily mass loads (mg/day) were normalized to catchment population (mg/1000 people/day) and converted to the number of combined doses consumed per day. Spatial differences were assessed world-wide, and temporal trends were discerned at European level by comparing 2011-13 drug loads versus 2014-17 loads. FINDINGS: Benzoylecgonine was the stimulant metabolite detected at higher loads in southern and western Europe, and amphetamine, MDMA and methamphetamine in East and North-Central Europe. In other continents, methamphetamine showed the highest levels in the United States and Australia and benzoylecgonine in South America. During the reporting period, benzoylecgonine loads increased in general across Europe, amphetamine and methamphetamine levels fluctuated and MDMA underwent an intermittent upsurge. CONCLUSIONS: The analysis of wastewater to quantify drug loads provides near real-time drug use estimates that globally correspond to prevalence and seizure data.


Subject(s)
Environmental Monitoring/methods , Illicit Drugs , Spatio-Temporal Analysis , Substance Abuse Detection/methods , Wastewater/chemistry , Amphetamine/analysis , Chromatography, Liquid , Cocaine/analogs & derivatives , Cocaine/analysis , Humans , Internationality , Methamphetamine/analysis , N-Methyl-3,4-methylenedioxyamphetamine/analysis , Tandem Mass Spectrometry
14.
J Chromatogr A ; 1602: 450-457, 2019 Sep 27.
Article in English | MEDLINE | ID: mdl-31208794

ABSTRACT

The analysis of wastewater for the determination of human biomarkers of exposure (human metabolites) is a non-intrusive, economic and complementary alternative to the analysis of urine in the monitoring of human exposure to chemicals of concern. This study provides the first gas chromatography-based method for the determination of three metabolites of chlorinated organophosphorous flame retardants (OPFRs: bis(2-chloroethyl) phosphate, bis(chloropropyl) phosphate and bis(1,3-dichloro-2-propyl) phosphate) in wastewater. A solid-phase extraction procedure based on the use of mixed-mode reversed-phase weak anion exchange sorbents was optimized including a fractionated elution of OPFRs and their metabolites. Analytes derivatization was investigated by comparing two silylating reagents, N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide and N-methyl-N-(trimethylsilyl)trifluoroacetamide, the first one providing better results. Determination was performed by gas chromatography-high resolution mass spectrometry with a quadrupole-time-of-flight system (GC-QTOF) in order to improve selectivity. Furthermore, the use of GC-QTOF combined with the specific ion obtained from silylated metabolites (m/z 154.9924) can be exploited to screen for other phosphate ester metabolites. Under final conditions, the overall method performance was satisfactory, affording method detection limits ranging from 1.1 to 4.6 ng/L, percentages of recovery from 90% to 110%, and relative standard deviations below 13%. The analysis of composite raw wastewater samples collected over 24 h in the NW of Spain allowed to quantify, for the first time in this matrix, the metabolite bis(chloropropyl) phosphate at levels over 60 ng/L.


Subject(s)
Acetamides/chemistry , Flame Retardants/analysis , Fluoroacetates/chemistry , Gas Chromatography-Mass Spectrometry/methods , Halogenation , Metabolome , Organosilicon Compounds/chemistry , Phosphorus/analysis , Wastewater/chemistry , Humans , Limit of Detection , Organophosphates/analysis , Reference Standards , Solid Phase Extraction
15.
Drug Test Anal ; 11(7): 1018-1027, 2019 Jul.
Article in English | MEDLINE | ID: mdl-30891957

ABSTRACT

This work provides a new analytical method for the determination of cocaine, its metabolites benzoylecgonine and cocaethylene, the pyrolytic products anhydroecgonine and anhydroecgonine methyl ester, and the pharmaceutical levamisole in wastewater. Samples were solid-phase extracted and extracts analyzed by liquid chromatography-tandem mass spectrometry using, for the first time in the illicit drug field, a stationary phase that combines reversed-phase and weak cation-exchange functionalities. The overall method performance was satisfactory, with limits of detection below 1 ng/L, relative standard deviations below 21%, and percentages of recovery between 93% and 121%. Analysis of 24-hour composite raw wastewater samples collected in Santiago de Compostela (Spain) and Brasilia (Brazil) highlighted benzoylecgonine as the compound showing the highest population-normalized mass loads (300-1000 mg/day/1000 inhabitants). In Brasilia, cocaine and levamisole loads underwent an upsurge on Sunday, indicating a high consumption, and likely a direct disposal, of cocaine powder on this day. Conversely, the pyrolytic product resulting from the smoke of crack, anhydroecgonine methyl ester, and its metabolite anhydroecgonine were relatively stable over the four days, agreeing with a non-recreational-associated use of crack.


Subject(s)
Cocaine/analysis , Drug Residues/analysis , Illicit Drugs/analysis , Wastewater/analysis , Brazil , Chromatography, High Pressure Liquid , Chromatography, Liquid , Chromatography, Reverse-Phase , Cocaine/analogs & derivatives , Levamisole/analysis , Pyrolysis , Solid Phase Extraction , Substance Abuse Detection , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysis
16.
J Chromatogr A ; 1569: 91-100, 2018 Sep 28.
Article in English | MEDLINE | ID: mdl-30072231

ABSTRACT

This study presents a new multi-residue analytical method for the simultaneous determination of 38 psychoactive drugs (including benzodiazepines, antidepressants and drugs of abuse) and related metabolites in raw wastewater. Potential analyte losses during sample filtration and stability in wastewater were evaluated. Analyte losses, especially for 12 compounds, were observed during filtration, indicating a strong sorption onto the filter material. In order to overcome this effect, filtered water samples were combined with methanolic washes of the corresponding filters and the resulting solutions were solid-phase extracted on mixed-mode (reverse-phase plus cation-exchange) sorbents. Extracts were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry. Quantification was performed by the internal standard method with isotopic labeled analogs. Recovery percentages varied between 65% and 137%; method quantification limits ranged between 0.2 and 22 ng/L in ultrapure water and between 0.3 and 30 ng/L in wastewater for all the analytes but three (for which they were ∼60-80 ng/L). The analysis of 24 h-composite samples collected during one week in the city of Santiago de Compostela demonstrated the ubiquity of 31 analytes, which were positively quantified in all samples. The highest concentrations were found for some of the antidepressants, with mean and maximum levels exceeding, in some cases, the levels previously reported in literature. This fact could be related to the additional washing step of the filters using methanol, which allowed to desorb retained analytes highlighting the importance of this step during the sample preparation protocol.


Subject(s)
Chromatography, High Pressure Liquid/methods , Illicit Drugs/analysis , Metabolome , Psychotropic Drugs/analysis , Tandem Mass Spectrometry/methods , Wastewater/chemistry , Water Pollutants, Chemical/analysis , Antidepressive Agents/analysis , Filtration , Methanol , Water/analysis
17.
Rev Esp Salud Publica ; 922018 Aug 20.
Article in Spanish | MEDLINE | ID: mdl-30124223

ABSTRACT

This manuscript introduces Wastewater-Based Epidemiology (WBE) and its potential in the assessment of diverse aspects related to public health. This methodology can provide data in a relatively short temporal and local scale (typically dialy-weekly at the municipal level) on consumption patterns of illicit drugs (e.g. cocaine or cannabis), licit substances of abuse (e.g. alcohol) by measuring their consumption biomarkers (i.e. the original unmetabolized substance or some of its metabolite) in wastewater. Besides discussing the fundaments, advantages and shortcomings of WBE, it reviews some of the main precedents at international level and most remarkable activities that have been taken place in this field in Spain. Finally, the Spanish Network of Wastewater-Based Epidemiology (ESAR-Net) as is presented. ESAR-Net is an Excellence Network that sums up the efforts of the most relevant Spanish researchers in the field of WBE, aiming to investigate future perspectives of this methodology and its impact on Public Health competences in Spain.


En este artículo se presenta la metodología de análisis de aguas residuales con fines epidemiológicos (wastewater-based epidemiology, WBE) y su potencial para abordar diversos aspectos relacionados con la salud pública. Esta metodología permite obtener datos a una escala temporal y espacial relativamente pequeña (típicamente datos diarios-semanales sobre un municipio) de hábitos de consumo de sustancias de abuso, ilegales (como la cocaína o el cannabis) o legales (como el alcohol) a través de la determinación de biomarcadores de consumo (el compuesto original no metabolizado o alguno de sus metabolitos) en el agua residual. Aparte de discutir los fundamentos, ventajas y limitaciones de WBE, se comentan los precedentes más relevantes a nivel internacional, y las actividades más destacables en España en este ámbito. Finalmente, se exponen, los objetivos de la Red Española de Análisis de Aguas Residuales con Fines Epidemiológicos (ESAR-Net), una "Red de Excelencia" que agrupa a investigadores españoles con amplia experiencia en el área de WBE, así como las perspectivas de futuro de esta metodología puede tener para mejorar las competencias de la Salud Pública en España.


Subject(s)
Illicit Drugs/analysis , Substance Abuse Detection/methods , Substance-Related Disorders/epidemiology , Wastewater/chemistry , Health Promotion , Humans , Public Health , Spain/epidemiology , Substance-Related Disorders/diagnosis , Substance-Related Disorders/prevention & control , Wastewater/analysis
18.
Drug Test Anal ; 10(1): 222-228, 2018 Jan.
Article in English | MEDLINE | ID: mdl-28371432

ABSTRACT

For the first time, ultra-high performance supercritical fluid chromatography (UHPSFC) coupled to tandem mass spectrometry has been used to determine cannabinoid and synthetic cannabinoid residues in wastewater. Combined with a downscaled version of the classic liquid-liquid extraction, the proposed method allows for the quantification of Δ9-tetrahydrocannabinol, three of its major metabolites (the monohydroxylated, the dehydroxylated, and the carboxylated species) and four synthetic cannabinoid metabolites (from the JWH-series) at low ng L-1 levels. Limits of quantification are in the 1-59 ng L-1 range, with recovery between 62 and 122% in ultrapure water and between 59 and 138% in wastewater. The applicability of the developed methodology was confirmed by the analysis of real wastewater, where cannabis metabolites could be positively quantified in all the samples analyzed. It is, therefore, a fast and simple alternative to common solid-phase extraction-liquid chromatography-mass spectrometry procedures for the determination of these low polar substances in water. Copyright © 2017 John Wiley & Sons, Ltd.


Subject(s)
Cannabinoids/analysis , Cannabinoids/metabolism , Chromatography, Supercritical Fluid/methods , Liquid-Liquid Extraction/methods , Tandem Mass Spectrometry/methods , Wastewater/analysis , Chromatography, High Pressure Liquid/methods , Chromatography, High Pressure Liquid/standards , Chromatography, Supercritical Fluid/standards , Liquid-Liquid Extraction/standards , Tandem Mass Spectrometry/standards , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/metabolism
19.
Sci Total Environ ; 644: 995-1005, 2018 Dec 10.
Article in English | MEDLINE | ID: mdl-30743897

ABSTRACT

The photodegradation of the neonicotinoid insecticide nitenpyram (NPY) under UV and solar irradiation has been investigated in water solutions in order to assess its persistence in the environment and its transformation into other potentially more toxic species. Time-courses were followed by ultra-high performance liquid chromatography-tandem mass spectrometry. Transformation products (TPs) were identified by their accurate product ion spectra, obtained with a quadrupole time-of-flight mass spectrometer after their liquid chromatographic separation. NPY was rapidly photodegraded under all the investigated conditions, following a first-order model and with half-lives varying from seconds to <10 min. Quantum yields were between 0.0385 and 0.0534 mol einstein-1. The identified TPs, some of them reported for the first time in this study, were formed through different reactions involving the nitro-ethylene moiety of the parent insecticide. Conversely to the lability of NPY, its TPs were more photo-stable in both ultrapure and river water. Moreover, in-silico toxicity assessment showed that most of them display a higher acute toxicity than NPY.

20.
Rev. esp. salud pública ; 92: 0-0, 2018. ilus, tab, mapas, graf
Article in Spanish | IBECS | ID: ibc-177568

ABSTRACT

En este artículo se presenta la metodología de análisis de aguas residuales con fines epidemiológicos (wastewater-based epidemiology, WBE) y su potencial para abordar diversos aspectos relacionados con la salud pública. Esta metodología permite obtener datos a una escala temporal y espacial relativamente pequeña (típicamente datos diarios-semanales sobre un municipio) de hábitos de consumo de sustancias de abuso, ilegales (como la cocaína o el cannabis) o legales (como el alcohol) a través de la determinación de biomarcadores de consumo (el compuesto original no metabolizado o alguno de sus metabolitos) en el agua residual. Aparte de discutir los fundamentos, ventajas y limitaciones de WBE, se comentan los precedentes más relevantes a nivel internacional, y las actividades más destacables en España en este ámbito. Finalmente, se exponen, los objetivos de la Red Española de Análisis de Aguas Residuales con Fines Epidemiológicos (ESAR-Net), una "Red de Excelencia " que agrupa a investigadores españoles con amplia experiencia en el área de WBE, así como las perspectivas de futuro de esta metodología puede tener para mejorar las competencias de la Salud Pública en España


This manuscript introduces Wastewater-Based Epidemiology (WBE) and its potential in the assessment of diverse aspects related to public health. This methodology can provide data in a relatively short temporal and local scale (typically dialy-weekly at the municipal level) on consumption patterns of illicit drugs (e.g. cocaine or cannabis), licit substances of abuse (e.g. alcohol) by measuring their consumption biomarkers (i.e. the original unmetabolized substance or some of its metabolite) in wastewater. Besides discussing the fundaments, advantages and shortcomings of WBE, it reviews some of the main precedents at international level and most remarkable activities that have been taken place in this field in Spain. Finally, the Spanish Network of Wastewater-Based Epidemiology (ESAR-Net) as is presented. ESAR-Net is an Excellence Network that sums up the efforts of the most relevant Spanish researchers in the field of WBE, aiming to investigate future perspectives of this methodology and its impact on Public Health competences in Spain


Subject(s)
Humans , 24961 , Wastewater Biological Characteristics/statistics & numerical data , Substance Abuse Detection/methods , Illicit Drugs/isolation & purification , Ethanol/isolation & purification , Nicotine/isolation & purification , Biomarkers/analysis , Social Problems/statistics & numerical data , Drug-Seeking Behavior/trends , Tobacco Use/epidemiology
SELECTION OF CITATIONS
SEARCH DETAIL