Human presence in the Antarctic is increasing due to research activities and the rise in tourism. These activities contribute a number of potentially hazardous substances. The aim of this study is to ...conduct the first characterisation of the pharmaceuticals and recreational drugs present in the northern Antarctic Peninsula region, and to assess the potential environmental risk they pose to the environment. The study consisted of a single sampling of ten water samples from different sources, including streams, ponds, glacier drains, and a wastewater discharge into the sea. Twenty-five selected pharmaceuticals and 21 recreational drugs were analysed. The highest concentrations were found for the analgesics acetaminophen (48.74 μg L−1), diclofenac (15.09 μg L−1) and ibuprofen (10.05 μg L−1), and for the stimulant caffeine (71.33 μg L−1). All these substances were detected in waters that were discharged directly into the ocean without any prior purification processes. The hazard quotient (HQ) values for ibuprofen, diclofenac and acetaminophen were far in excess of 10 at several sampling points. The concentrations of each substance measured and used as measured environmental concentration values for the HQ calculations are based on a one-time sampling. The Toxic Unit values indicate that analgesics and anti-inflammatories are the therapeutic group responsible for the highest toxic burden.
This study is the first to analyse a wide range of substances and to determine the presence of pharmaceuticals and psychotropic drugs in the Antarctic Peninsula region. We believe it can serve as a starting point to focus attention on the need for continued environmental monitoring of these substances in the water cycle, especially in protected regions such as the Antarctic. This will determine whether pharmaceuticals and recreational drugs are hazardous to the environment and, if so, can be used as the basis for risk-assessment studies to prioritise the exposure to risk.
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•Sixteen pharmaceuticals and recreational drugs were found in concentrations of ngL−1 to μgL−1.•The highest concentrations were found for the analgesics acetaminophen, diclofenac and ibuprofen.•Caffeine was the most commonly found substance, followed by ephedrine.•Acetaminophen, diclofenac and ibuprofen presented the highest HQ values and therefore the highest environmental risk.•Analgesics and anti-inflammatories have been identified as the group posing the highest risk to the Antarctic ecosystem.
Sixteen emerging contaminants were found in the Antarctic Peninsula region. Analgesics and anti-inflammatories have been identified as the group posing the highest risk to the Antarctic ecosystem.
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.
•First fully automated on-line SPE–LC–MS/MS determination of UV filters.•Method suitable to determine UV F of a wide range of physicochemical properties.•Sensitivity achieved allowing trace UV F ...determination in several water matrices.•First determination of UV filters residues in groundwater.
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.
•A LC–MS/MS method was developed to determine 40 psychoactive drugs in milk.•The method allows the investigation of 10 drugs for the first time in milk.•Method was validated in breast milk and four ...different classes of bovine milk.•Caffeine was the only compound found to be present in the milk samples analysed.
This work presents a fast, sensitive and reliable multi-residue methodology based on fat and protein precipitation and liquid chromatography-tandem mass spectrometry for the determination of common legal and illegal psychoactive drugs, and major metabolites, in breast milk. One-fourth of the 40 target analytes is investigated for the first time in this biological matrix. The method was validated in breast milk and also in various types of bovine milk, as tranquilizers are occasionally administered to food-producing animals. Absolute recoveries were satisfactory for 75% of the target analytes. The use of isotopically labeled compounds assisted in correcting analyte losses due to ionization suppression matrix effects (higher in whole milk than in the other investigated milk matrices) and ensured the reliability of the results. Average method limits of quantification ranged between 0.4 and 6.8 ng/mL. Application of the developed method showed the presence of caffeine in breast milk samples (12–179 ng/mL).
Illicit and legal drugs of abuse, including alcohol, continue to be in the focus of many governmental national and international studies due to the important consequences of their consumption at both ...individual and social level. Estimation of drug use at the community level from the concentrations of the drugs themselves or their major metabolites measured in wastewater has become an increasingly accepted and extended tool, complementary to the methods traditionally used for this purpose. The present work describes the application of this approach, generally known as wastewater epidemiology, to investigate the latest drug consumption patterns and trends in the European city of Barcelona. To this end, a total of 19 selected drugs of abuse and metabolites were monitored at the inlet of one of the main wastewater treatment plants of Barcelona every day during one week in March between 2011 and 2015. Analysis of the selected drugs and metabolites in the wastewater samples was performed by means of two methodologies based on liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the concentrations obtained were translated into consumption data. In agreement with official records, alcohol, followed by cannabis, cocaine, amphetamine-like compounds, and methadone were the most consumed drugs. Alcohol, cannabis, and cocaine consumption were on average 18mL(14g)/day/inhabitant (>15), 38g/day/1000 inhabitants aging 15–64, and 2.4g/day/1000 inhabitants aging 15–64, respectively. As for drug use trends, consumption increased over the 5years monitored for all drugs, but for heroin and diazepam. Weekly profiles characterized by higher consumption over the weekend as compared to weekdays were observed only for alcohol, cocaine, and MDMA. Extrapolation of the data obtained for the area under study to the national Spanish territory yields consumption figures of 142t of illicit drugs per year and >2500 million euro turnover per year in the black market.
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•Drug use in Barcelona during 5years assessed using wastewater-based epidemiology.•Alcohol, cannabis and cocaine were the most consumed drugs.•Drug use increased from 2011 to 2015, contrary to national official data.•Temporal trends of drug use were in agreement with regional official data.•Consumption of alcohol, cocaine and MDMA increased during the weekend.
•High throughput automated determination of 37 psychoactive drugs in wastewater.•Reliability of results is improved through isotope dilution quantification.•Method quantification limits were below 23 ...ng/L for most analytes.•Twenty-five psychoactive substances were present in all the samples analyzed.•Average concentrations were between 7 ng/L (zolpidem) and 54 μg/L (caffeine).
This work presents a multi-residue method for the simultaneous determination of 37 legal and illicit psychoactive substances in wastewater, including the most common illicit drugs (cocaine-related compounds, amphetamine-type stimulants, hallucinogens, opiates/opioids, and cannabinoids), new psychoactive substances (two synthetic cathinones, the synthetic opioid AH-7921, and the arylcyclohexylamine methoxetamine), and legal but controlled psychoactive substances (stimulants, benzodiazepines, antidepressants, sedatives, antipsychotics, and hypnotics). To this end a fully automated analytical approach based on solid phase extraction coupled in series to liquid chromatography tandem mass spectrometry detection (on-line SPE- LC–MS/MS) was used. The methodology developed was validated in terms of linearity, recovery, repeatability, and sensitivity in wastewater. Method linearity was between 0.1 ng/L (or the analyte limit of quantification if higher) and 2,000 ng/L (10,250 ng/L in the case of caffeine). Absolute recoveries were variable (between 5% and 132%), depending on the analyte. However, the use of isotopically labeled compounds corrected for analyte losses during the extraction process and matrix effects (relative recoveries within the range of 80–120%). Repeatability of the method was satisfactory for all analytes, with RSD values lower than 13% for most compounds. Limits of detection and quantification in wastewater were below 7 and 23 ng/L, respectively, for all analytes except lormetazepam (10 and 32 ng/L), caffeine (13 and 44 ng/L), and the cannabinoids 11-nor-9-carboxy- Δ9-tetrahydrocannabinol (18 and 61 ng/L) and 11-hydroxy-Δ9- tetrahydrocannabinol (69 and 228 ng/L). The method was applied to the analysis of wastewater samples collected daily in Barcelona for one week. Twenty-five of the 37 analytes were detected in the samples analyzed. Average concentrations ranged from 7 ng/L in the case of zolpidem to 54 μg/L in the case of caffeine.
The knowledge on the presence of pharmaceutical compounds, and possible risks, in coastal and marine systems is still limited. This study represents the first attempt at monitoring psychoactive ...pharmaceuticals (PaPs) (benzodiazepines and anxiolytics) and illicit drugs (IDs) in the Rías Baixas coastal area of Northwestern Spain, an area of economic and ecological relevance, leader in shellfish production. Fourteen PaPs and 9 IDs were detected in the water samples with venlafaxine (59%), benzoylecgonine (40%), EDDP (40%), and citalopram (36%) showing the highest detection frequencies. The highest concentrations were measured for venlafaxine (291 ng L−1), benzoylecgonine (142 ng L−1), lorazepam (95.9 ng L−1), and citalopram (92.5 ng L−1). Risk assessment, based on hazard quotients suggested that venlafaxine, citalopram, sertraline, and EDDP were present in concentrations potentially able to cause chronic effects in exposed organisms. Based on the results obtained further monitoring of venlafaxine, citalopram, and EDDP in coastal waters is recommended.
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•Psychoactive and illicit drugs were present in 13 of the 22 sampled sites above LOD.•Ten drugs detected for the first time in coastal waters.•Venlafaxine, benzoylecgonine, EDDP, and citalopram were the most ubiquitous drugs.•Concentrations of venlafaxine, citalopram, sertraline and EDDP resulted in HQ > 1.•Venlafaxine led to HQ up to 128 and above 1 in 36% of the studied sites.
•A method for analysis of ethyl sulfate (EtS) in wastewater was developed.•Levels of the alcohol biomarker EtS in wastewaters ranged from 5.5 to 32.5μg/L.•A sewage epidemiology approach was applied ...for alcohol consumption estimation.•The estimated per capita alcohol consumption in the Barcelona area was 18mL/day.•Levels of EtS and some illicit drugs were correlated.
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 (r2=0.9391, n=5), benzoylecgonine (r2=0.9252, n=7), ecstasy (r2=0.8950, n=7), amphetamine (r2=0.8707, n=7) and cocaine (r2=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.
Caffeine is an emerging contaminant considered to be an indicator of human contamination that has been widely detected in various aquatic systems, especially in continental waters. Nevertheless, the ...extent of its possible environmental impact is yet to be determined. This study determined the presence of caffeine, and evaluated the environmental hazard posed by this substance, in the “Rías Gallegas”, a series of costal inlets in north-west Spain which are of great ecological value and in which fishing and bivalve farming, are a significant source of income. Caffeine was found to be present at concentrations higher than the limit of quantification (LOQ=3.07ngL−1) in 15 of the 23 samples analysed, with the highest seawater concentration being 857ngL−1 (the highest measured in seawater in Spain). Six out of 22 seawater samples resulted in a hazard quotient (HQ) from chronic exposure higher than 1 with the highest being 17.14, indicating a high probability of adverse effects in the aquatic environment. Environmental Exposure Distributions (EEDs) generated from a literature review of caffeine levels reported previously in four out of the five continents, showed that 28% of all seawater samples, and 69% of all estuary water samples where caffeine has ever been measured resulted in HQ>1 for chronic exposure. Further studies into the potential adverse effects that may arise from exposure to caffeine in aquatic systems are still required. Indeed, the need to gain a more in-depth understanding of the long-term ecotoxicological effects of caffeine is essential to ensure the quality of our health and environment.
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•Caffeine was present, in 15 of the 23 samples analysed.•The highest marine concentration of caffeine in Spain, and one of the highest in Europe, was detected in this study (857ng L−1).•Six out of 22 seawater samples resulted in a Hazard Quotient (HQ) from chronic exposure higher than 1.•Twenty-eight percent of all seawater and 69% of all estuary water samples where caffeine has ever been measured (Globally) exceeded an HQ of 1.
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.
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