Publications by authors named "Erik Emke"

36 Publications

Changes in drug use in European cities during early COVID-19 lockdowns - A snapshot from wastewater analysis.

Environ Int 2021 Mar 26;153:106540. Epub 2021 Mar 26.

Environmental and Public Health Analytical Chemistry, Research Institute for Pesticides and Water, University Jaume I, Castellón, Spain; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, the Netherlands. Electronic address:

The COVID-19 outbreak has forced countries to introduce severe restrictive measures to contain its spread. In particular, physical distancing and restriction of movement have had important consequences on human behaviour and potentially also on illicit drug use and supply. These changes can be associated with additional risks for users, in particular due to reduced access to prevention and harm reduction activities. Furthermore, there have been limitations in the amount of data about drug use which can be collected due to restrictions. To goal of this study was to obtain information about potential changes in illicit drug use impacted by COVID-19 restrictions. Wastewater samples were collected in seven cities in the Netherlands, Belgium, Spain and Italy at the beginning of lockdowns (March-May 2020). Using previously established and validated methods, levels of amphetamine (AMP), methamphetamine (METH), MDMA, benzoylecgonine (BE, the main metabolite of cocaine) and 11-nor-9-carboxy-Δ-tetrahydrocannabinol (THC-COOH, main metabolite of tetrahydrocannabinol (THC)) were measured and compared with findings from previous years. Important differences in levels of consumed drugs were observed across the considered countries. Whilst for some substances and locations, marked decreases in consumption could be observed (e.g., 50% decrease in MDMA levels compared to previous years). In some cases, similar or even higher levels compared to previous years could be found. Changes in weekly patterns were also observed, however these were not clearly defined for all locations and/or substances. Findings confirm that the current situation is highly heterogeneous and that it remains very difficult to explain and/or predict the effect that the present pandemic has on illicit drug use and availability. However, given the current difficulty in obtaining data due to restrictions, wastewater analysis can provide relevant information about the situation at the local level, which would be hard to obtain otherwise.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.envint.2021.106540DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7997602PMC
March 2021

New psychoactive substances in several European populations assessed by wastewater-based epidemiology.

Water Res 2021 May 27;195:116983. Epub 2021 Feb 27.

Istituto di Ricerche Farmacologiche Mario Negri IRCCS, Department of Environmental Sciences, Via Mario Negri 2, 20156, Milan, Italy.

Wastewater-based epidemiology (WBE) can be a useful tool to face some of the existing challenges in monitoring the use of new psychoactive substances (NPS), as it can provide objective and updated information. This Europe-wide study aimed to verify the suitability of WBE for investigating the use of NPS. Selected NPS were monitored in urban wastewater by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The main classical illicit drugs were monitored in the same samples to compare their levels with those of NPS. Raw composite wastewater samples were collected in 2016 and 2017 in 14 European countries (22 cities) following best practice sampling protocols. Methcathinone was most frequent (>65% of the cities), followed by mephedrone (>25% of the cities), and only mephedrone, methcathinone and methylone were found in both years. This study depicts the use of NPS in Europe, confirming that it is much lower than the use of classical drugs. WBE proved able to assess the qualitative and quantitative spatial and temporal profiles of NPS use. The results show the changeable nature of the NPS market and the importance of large WBE monitoring campaigns for selected priority NPS. WBE is valuable for complementing epidemiological studies to follow rapidly changing profiles of use of drugs.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.watres.2021.116983DOI Listing
May 2021

Application of wastewater-based epidemiology to investigate stimulant drug, alcohol and tobacco use in Lithuanian communities.

Sci Total Environ 2021 Feb 19;777:145914. Epub 2021 Feb 19.

Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Antwerp, Belgium. Electronic address:

WBE was applied to evaluate illicit drug (i.e. amphetamine, cocaine, MDMA and methamphetamine), alcohol and tobacco use in three Lithuanian cities in 2018 and 2019. Considerable concentrations of methamphetamine and MDMA were found in the three locations, suggesting a specific Lithuanian consumption pattern. Yet, unexpected high concentrations of amphetamine (>4 μg/L) were detected in two samples of Kaunas in 2018. Through the use of chiral analysis and non-target and suspect drug precursor compound screening, these extreme values were confirmed to be the result of direct disposal of amphetamine in the sewers. Furthermore, substantial alcohol use was measured in the three investigated catchment populations of Lithuania with almost 4 standard drinks/day/inhabitant aged 15+ on average in 2019. For tobacco, an average of 5.6 cigarettes/day/inhabitant aged 15+ in 2019 was reported with large discrepancies between WBE figures and sales data, potentially highlighting illegal trade of tobacco products.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2021.145914DOI Listing
February 2021

International snapshot of new psychoactive substance use: Case study of eight countries over the 2019/2020 new year period.

Water Res 2021 Apr 3;193:116891. Epub 2021 Feb 3.

Health and Biomedical Innovation, UniSA: Clinical and Health Sciences, University of South Australia, Adelaide 5001, South Australia, Australia. Electronic address:

There is considerable concern around the use of new psychoactive substances (NPS), but still little is known about how much they are really consumed. Analysis by forensics laboratories of seized drugs and post-mortem samples as well as hospital emergency rooms are the first line of identifying both 'new' NPS and those that are most dangerous to the community. However, NPS are not necessarily all seized by law enforcement agencies and only substances that contribute to fatalities or serious afflictions are recorded in post-mortem and emergency room samples. To gain a better insight into which NPS are most prevalent within a community, complementary data sources are required. In this work, influent wastewater was analysed from 14 sites in eight countries for a variety of NPS. All samples were collected over the 2019/2020 New Year period, a time which is characterized by celebrations and parties and therefore a time when more NPS may be consumed. Samples were extracted in the country of origin following a validated protocol and shipped to Australia for final analysis using two different mass spectrometric strategies. In total, more than 200 were monitored of which 16 substances were found, with geographical differences seen. This case study is the most comprehensive wastewater analysis study ever carried out for the identification of NPS and provides a starting point for future, ongoing monitoring of these substances.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.watres.2021.116891DOI Listing
April 2021

Spatio-temporal assessment of illicit drug use at large scale: evidence from 7 years of international wastewater monitoring.

Addiction 2020 01 23;115(1):109-120. Epub 2019 Oct 23.

Faculty of Fisheries and Protection of Waters, University of South Bohemia in Ceske Budejovice, Zatisi, Czech Republic.

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 Δ -tetrahydrocannabinol (11-nor-9-carboxy-Δ -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.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1111/add.14767DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6973045PMC
January 2020

A comparison of trends in wastewater-based data and traditional epidemiological indicators of stimulant consumption in three locations.

Addiction 2020 03 29;115(3):462-472. Epub 2019 Nov 29.

Population Health Sciences, University of Bristol, Canynge Hall, Bristol, UK.

Aims: To compare long-term trends in wastewater data with other indicators of stimulant use in three locations and to test the reliability of estimates based on 1 week of sampling.

Design: Comparison of trends in quantities ('loads') of stimulants or their metabolites in wastewater with trends in other indicators of stimulant use (e.g. treatment, police, population survey data).

Setting And Participants: Populations in Oslo (Norway), South-East Queensland (Australia) and Eindhoven (the Netherlands).

Measurements: Wastewater data were modelled for MDMA (3,4-methyl​enedioxy​methamphetamine), benzoylecgonine (a metabolite of cocaine), amphetamine and methamphetamine in Oslo; benzoylecgonine in Eindhoven; and methamphetamine in South-East Queensland. Choice of stimulants modelled in each region was primarily determined by availability of useable data.

Findings: In Oslo, wastewater data, driving under the influence of drugs statistics and seizure data all suggested increasing MDMA use between 2009 and 2017. In South-East Queensland, there was an estimated 31.1% [95% confidence interval (CI) = 29.4-32.9%] annual increase in daily loads of methamphetamine in wastewater between 2009 and 2016, compared with a 14.1% (95% CI = 10.9-17.3%) annual increase in seizures. Some of the increase in wastewater can be explained by increased purity. In Eindhoven, there was no evidence of a change in cocaine consumption from wastewater, but a reduction was observed in numbers in treatment for cocaine use from 2012 to 2017. In approximately half the cases examined in Oslo, credible intervals around estimates of annual average loads from a regression model versus estimates based on a single week of sampling did not overlap.

Conclusions: Long-term trends in loads of stimulants in wastewater appear to be broadly consistent with trends in other indicators of stimulant use in three locations. Wastewater data should be interpreted alongside epidemiological indicators and purity data. One week of wastewater sampling may not be sufficient for valid inference about drug consumption.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1111/add.14852DOI Listing
March 2020

Chemical and bioassay assessment of waters related to hydraulic fracturing at a tight gas production site.

Sci Total Environ 2019 Nov 24;690:636-646. Epub 2019 Jun 24.

Copernicus Institute of Sustainable Development, Faculty of Geosciences, Utrecht University, Utrecht, the Netherlands; KWR Watercycle Research Institute, Nieuwegein, the Netherlands.

Publicly available chemical assessments of hydraulic fracturing related waters are generally based on shale gas practices in the U.S. There is a lack of information on hydraulic fracturing related gas development from EU countries and more generally on other types of extractions. This research fills this knowledge gap by presenting chemical and bioassay assessments of hydraulic fracturing related waters from a tight gas development in the Netherlands. Fracturing fluid, flowback water and groundwater from surrounding aquifers before and after the actual fracturing were analysed by means of high resolution liquid chromatography tandem mass spectrometry, the Ames test and three chemical activated luciferase gene expression bioassays aimed at determining genotoxicity, oxidative stress response and polyaromatic hydrocarbon contamination. After sample enrichment a higher number of peaks can be found in both fracturing fluid and flowback samples. No clear differences in chemical composition were shown in the groundwater samples before and after hydraulic fracturing. Preliminary environmental fate data of the tentatively identified chemicals points towards persistence in water. Clear genotoxic and oxidative stress responses were found in the fracturing fluid and flowback samples. A preliminary suspect screening resulted in 25 and 36 matches in positive and negative ionisation respectively with the 338 possible suspect candidates on the list. Extensive measures relating to the handling, transport and treatment of hydraulic fracturing related waters are currently in place within the Dutch context. The results of the present study provide a scientific justification for such measures taken to avoid adverse environmental and human health impacts.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2019.06.354DOI Listing
November 2019

Wastewater Analysis for Community-Wide Drugs Use Assessment.

Handb Exp Pharmacol 2018;252:543-566

Department of Chemistry, University of Bath, Bath, UK.

Wastewater-based epidemiology (WBE) complements existing epidemiology-based estimation techniques and provides objective, evidence-based estimates of illicit drug use. After consumption, biomarkers - drugs and their metabolites - excreted to toilets and flushed into urban sewer networks can be measured in raw wastewater samples. The quantified loads can serve as an estimate for the collective consumption of all people contributing to the wastewater sample. This transdisciplinary approach, further explained in this chapter, has developed, matured and is now established for monitoring substances such as cocaine and amphetamine-type stimulants. Research currently underway is refining WBE to new applications including new psychoactive substances (NPS).
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1007/164_2018_111DOI Listing
June 2019

Comparison of phosphodiesterase type V inhibitors use in eight European cities through analysis of urban wastewater.

Environ Int 2018 06 3;115:279-284. Epub 2018 Apr 3.

KWR Watercycle Research Institute, Chemical Water Quality and Health, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE Amsterdam, The Netherlands. Electronic address:

In this work a step forward in investigating the use of prescription drugs, namely erectile dysfunction products, at European level was taken by applying the wastewater-based epidemiology approach. 24-h composite samples of untreated wastewater were collected at the entrance of eight wastewater treatment plants serving the catchment within the cities of Bristol, Brussels, Castellón, Copenhagen, Milan, Oslo, Utrecht and Zurich. A validated analytical procedure with direct injection of filtered aliquots by liquid chromatography-tandem mass spectrometry was applied. The target list included the three active pharmaceutical ingredients (sildenafil, tadalafil and vardenafil) together with (bio)transformation products and other analogues. Only sildenafil and its two human urinary metabolites desmethyl- and desethylsildenafil were detected in the samples with concentrations reaching 60 ng L. The concentrations were transformed into normalized measured loads and the estimated actual consumption of sildenafil was back-calculated from these loads. In addition, national prescription data from five countries was gathered in the form of the number of prescribed daily doses and transformed into predicted loads for comparison. This comparison resulted in the evidence of a different spatial trend across Europe. In Utrecht and Brussels, prescription data could only partly explain the total amount found in wastewater; whereas in Bristol, the comparison was in agreement; and in Milan and Oslo a lower amount was found in wastewater than expected from the prescription data. This study illustrates the potential of wastewater-based epidemiology to investigate the use of counterfeit medication and rogue online pharmacy sales.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.envint.2018.03.039DOI Listing
June 2018

Wastewater-based epidemiology generated forensic information: Amphetamine synthesis waste and its impact on a small sewage treatment plant.

Forensic Sci Int 2018 May 19;286:e1-e7. Epub 2018 Mar 19.

KWR Watercycle Research Institute, Chemical Water Quality and Health, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE Amsterdam, The Netherlands.

Chemical analysis of domestic wastewater can reveal the presence of illicit drugs either consumed by a population or directly discharged into the sewer system. In the search for causes of a recent malfunctioning of a small domestic wastewater treatment plant aberrantly high loads of amphetamine were observed in the influent of the plant. Direct discharges of chemical waste from illegal production sites were suspected to be the cause. Illegal manufacturing of amphetamines creates substantial amounts of chemical waste. Here we show that fly-tipping of chemical waste originating from an amphetamine synthesis in the catchment of a small sewage treatment plant resulted in failure of the treatment process. Target analysis of drugs of abuse and non-target screening using high resolution mass spectrometry provided evidence for the presence of amphetamine produced from the precursor 1-phenylpropan-2-one by the Leuckart process through specific synthesis markers. Furthermore the identity and presence of the pre-precursor 3-oxo-2-phenylbutanamide was confirmed and a route specific marker was proposed. This is the first study that demonstrates that non-target screening of wastewater can identify intermediates, impurities and by products of the synthesis routes used in illegal manufacturing of amphetamine. The profiles of chemicals thus obtained can be used in tracking productions sites within the corresponding sewer catchment.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.forsciint.2018.03.019DOI Listing
May 2018

Wastewater-based tracing of doping use by the general population and amateur athletes.

Anal Bioanal Chem 2018 Feb 15;410(6):1793-1803. Epub 2018 Jan 15.

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB, Nieuwegein, The Netherlands.

The present study investigates the applicability of the chemical analysis of wastewater to assess the use of doping substances by the general population and amateur athletes. To this end, an analytical methodology that can identify and quantify a list of 15 substances from the groups of anabolic steroids, weight loss products, and masking agents in wastewater has been developed. The method uses solid phase extraction to increase the detection sensitivity of the target analytes, expected to be present at very low concentrations (ng L range), and decrease possible matrix interferences. Instrumental analysis is performed by liquid chromatography coupled to high-resolution mass spectrometry, allowing data acquisition in both full scan and tandem MS mode. The method has been successfully validated at two concentration levels (50 and 200 ng L) with limits of quantification ranging between 0.7 and 60 ng L, intra- and inter-day precision expressed as relative standard deviation below 15%, procedural recoveries between 60 and 160% and matrix effects ranging from 45 to 121%. The stability of the analytes in wastewater was evaluated at different storage temperatures illustrating the importance of freezing the samples immediately after collection. The application of the method to 24-h composite wastewater samples collected at the entrance of three wastewater treatment plants and one pumping station while different sport events were taking place revealed the presence in wastewater, and hence the use, of the weight loss substances ephedrine, norephedrine, methylhexanamine, and 2,4-dinitrophenol. The use of these stimulants was visible just prior and during the event days and in greater amounts than anabolic steroids or masking agents. Graphical abstract Chemical analysis of untreated wastewater reveals the use of prohibited doping substances during amateur sport event.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1007/s00216-017-0835-3DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5807464PMC
February 2018

Improving wastewater-based epidemiology to estimate cannabis use: focus on the initial aspects of the analytical procedure.

Anal Chim Acta 2017 Oct 18;988:27-33. Epub 2017 Aug 18.

Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat s/n, E-12071, Castellón, Spain. Electronic address:

Wastewater-based epidemiology is a promising and complementary tool for estimating drug use by the general population, based on the quantitative analysis of specific human metabolites of illicit drugs in urban wastewater. Cannabis is the most commonly used illicit drug and of high interest for epidemiologists. However, the inclusion of its main human urinary metabolite 11-nor-9-carboxy-Δ-tetrahydrocannabinol (THC-COOH) in wastewater-based epidemiology has presented several challenges and concentrations seem to depend heavily on environmental factors, sample preparation and analyses, commonly resulting in an underestimation. The aim of the present study is to investigate, identify and diminish the source of bias when analysing THC-COOH in wastewater. Several experiments were performed to individually assess different aspects of THC-COOH determination in wastewater, such as the number of freeze-thaw cycles, filtration, sorption to different container materials and in-sample stability, and the most suitable order of preparatory steps. Results highlighted the filtration step and adjustment of the sample pH as the most critical parameters to take into account when analysing THC-COOH in wastewater. Furthermore, the order of these initial steps of the analytical procedure is crucial. Findings were translated into a recommended best-practice protocol and an inter-laboratory study was organized with eight laboratories that tested the performance of the proposed procedure. Results were found satisfactory with z-scores ≤ 2.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.aca.2017.08.011DOI Listing
October 2017

Transformation and Sorption of Illicit Drug Biomarkers in Sewer Biofilms.

Environ Sci Technol 2017 Sep 28;51(18):10572-10584. Epub 2017 Aug 28.

Department of Environmental Engineering, Technical University of Denmark (DTU) , Bygningstorvet, Bygning 115, 2800 Kgs. Lyngby, Denmark.

In-sewer transformation of drug biomarkers (excreted parent drugs and metabolites) can be influenced by the presence of biomass in suspended form as well as attached to sewer walls (biofilms). Biofilms are likely the most abundant and biologically active biomass fraction in sewers. In this study, 16 drug biomarkers were selected, including the parent forms and the major human metabolites of mephedrone, methadone, cocaine, heroin, codeine, and tetrahydrocannabinol (THC). Transformation and sorption of these substances were assessed in targeted batch experiments using laboratory-scale biofilm reactors operated under aerobic and anaerobic conditions. A one-dimensional model was developed to simulate diffusive transport, abiotic and biotic transformation, and partitioning of drug biomarkers. Model calibration to experimental results allowed estimating biotransformation rate constants in sewer biofilms, which were compared to those obtained for suspended biomass. Our results suggest that sewer biofilms can enhance the biotransformation kinetics of most selected compounds. Through scenario simulations, we demonstrated that the estimation of biotransformation rate constants in biofilm can be significantly biased if the boundary layer thickness is not accurately estimated. This study complements our previous investigation on the transformation and sorption of drug biomarkers in the presence of only suspended biomass in untreated sewage. A better understanding of the role of sewer biofilms-also relative to the in-sewer suspended solids-and improved prediction of associated fate processes can result in more accurate estimation of daily drug consumption in urban areas in wastewater-based epidemiological assessments.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.est.6b06277DOI Listing
September 2017

Qualitative screening for new psychoactive substances in wastewater collected during a city festival using liquid chromatography coupled to high-resolution mass spectrometry.

Chemosphere 2017 Oct 26;184:1186-1193. Epub 2017 Jun 26.

KWR Watercycle Research Institute, Chemical Water Quality and Health, P.O. Box 1072, 3430 BB, Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE, Amsterdam, The Netherlands. Electronic address:

The inclusion of new psychoactive substances (NPS) in the wastewater-based epidemiology approach presents challenges, such as the reduced number of users that translates into low concentrations of residues and the limited pharmacokinetics information available, which renders the choice of target biomarker difficult. The sampling during special social settings, the analysis with improved analytical techniques, and data processing with specific workflow to narrow the search, are required approaches for a successful monitoring. This work presents the application of a qualitative screening technique to wastewater samples collected during a city festival, where likely users of recreational substances gather and consequently higher residual concentrations of used NPS are expected. The analysis was performed using liquid chromatography coupled to high-resolution mass spectrometry. Data were processed using an algorithm that involves the extraction of accurate masses (calculated based on molecular formula) of expected m/z from an in-house database containing about 2,000 entries, including NPS and transformation products. We positively identified eight NPS belonging to the classes of synthetic cathinones, phenethylamines and opioids. In addition, the presence of benzodiazepine analogues, classical drugs and other licit substances with potential for abuse was confirmed. The screening workflow based on a database search was useful in the identification of NPS biomarkers in wastewater. The findings highlight the specific classical drugs and low NPS use in the Netherlands. Additionally, meta-chlorophenylpiperazine (mCPP), 2,5-dimethoxy-4-bromophenethylamine (2C-B), and 4-fluoroamphetamine (FA) were identified in wastewater for the first time.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.chemosphere.2017.06.101DOI Listing
October 2017

Occurrence and fate of illicit drugs and pharmaceuticals in wastewater from two wastewater treatment plants in Costa Rica.

Sci Total Environ 2017 Dec 3;599-600:98-107. Epub 2017 May 3.

KWR Watercycle Research Institute, Chemical Water Quality and Health, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE Amsterdam, The Netherlands. Electronic address:

Chemical analysis of raw wastewater in order to assess the presence of biological markers entering a wastewater treatment plant can provide objective information about the health and lifestyle of the population connected to the sewer system. This work was performed in a tropical country of Central America, Costa Rica, with the aim of extending this knowledge to new world regions. This work is the first to report wastewater-based epidemiological data on the use of illicit drugs in this region of the world. Composite wastewater samples from the influents of two different wastewater treatment facilities and surface water samples from surrounding areas were collected applying the best practice protocol and analysed to investigate the occurrence and fate of selected illicit drugs of abuse and pharmaceuticals. Results showed the presence of chemical indicators of the classic drugs cocaine and cannabis at high concentration levels, besides the moderate presence of the opiates codeine and morphine. Neither the worldwide commonly used psychoactive substances of abuse such as synthetic phenethylamines, nor pharmaceuticals from the family of benzodiazepines were detected, demonstrating the spatial differences in drug use among different world regions. In addition, effluent wastewater samples were analysed and compared to influent concentrations in order to evaluate the decrease in concentration of the targeted analytes through two treatment technologies. As a final step, a wide-scope qualitative screening, including hundreds of suspect compounds, was applied in order to have a better knowledge on the presence of pharmaceuticals in waters and to assess the potential impact of the treated wastewater into the receiving aquatic ecosystems.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2017.04.202DOI Listing
December 2017

Is there evidence for man-made nanoparticles in the Dutch environment?

Sci Total Environ 2017 Jan 24;576:273-283. Epub 2016 Oct 24.

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Copernicus Institute, Utrecht University, The Netherlands.

Only very limited information is available on measured environmental concentrations of nanoparticles. In this study, several environmental compartments in The Netherlands were probed for the presence of nanoparticles. Different types of water were screened for the presence of inorganic (Ag, Au, TiO) and organic nanoparticles (C, C, [6,6]-phenyl-C-butyric acid octyl ester, [6,6]-phenyl-C-butyric acid butyl ester, [6,6]-phenyl-C-butyric acid methyl ester, [6,6]-bis-phenyl-C-butyric acid methyl ester, [6,6]-phenyl-C-butyric acid methyl ester, [6,6]-thienyl-C-butyric acid methyl ester). Air samples were analysed for the presence of nanoparticulate Mo, Ag, Ce, W, Pd, Pt, Rh, Zn, Ti, Si, B as well as Fe and Cu. ICP-MS, Orbitrap-HRMS, SEM and EDX were used for this survey. Water samples included dune and bank filtrates, surface waters and ground waters as well as influents, effluents and sludge of sewage treatment plants (STPs), and surface waters collected near airports and harbours. Air samples included both urban and rural samples. C was detected in air, sewage treatment plants, influents, effluents and sludge, but in no other aqueous samples despite the low detection limit of 0.1ng/L. C and functionalised fullerenes were not detected at all. In STP sludge and influent the occurrence of Ag and Au nanoparticles was verified by SEM/EDX and ICP-MS. In air up to about 25m% of certain metals was found in the nanosize fraction. Overall, between 1 and 6% of the total mass from metals in the air samples was found in the size fraction <100nm.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2016.09.206DOI Listing
January 2017

Mass spectrometric strategies for the investigation of biomarkers of illicit drug use in wastewater.

Mass Spectrom Rev 2018 05 17;37(3):258-280. Epub 2016 Oct 17.

Research Institute for Pesticides and Water, University Jaume I, Castellón, Spain.

The analysis of illicit drugs in urban wastewater is the basis of wastewater-based epidemiology (WBE), and has received much scientific attention because the concentrations measured can be used as a new non-intrusive tool to provide evidence-based and real-time estimates of community-wide drug consumption. Moreover, WBE allows monitoring patterns and spatial and temporal trends of drug use. Although information and expertise from other disciplines is required to refine and effectively apply WBE, analytical chemistry is the fundamental driver in this field. The use of advanced analytical techniques, commonly based on combined chromatography-mass spectrometry, is mandatory because the very low analyte concentration and the complexity of samples (raw wastewater) make quantification and identification/confirmation of illicit drug biomarkers (IDBs) troublesome. We review the most-recent literature available (mostly from the last 5 years) on the determination of IDBs in wastewater with particular emphasis on the different analytical strategies applied. The predominance of liquid chromatography coupled to tandem mass spectrometry to quantify target IDBs and the essence to produce reliable and comparable results is illustrated. Accordingly, the importance to perform inter-laboratory exercises and the need to analyze appropriate quality controls in each sample sequence is highlighted. Other crucial steps in WBE, such as sample collection and sample pre-treatment, are briefly and carefully discussed. The article further focuses on the potential of high-resolution mass spectrometry. Different approaches for target and non-target analysis are discussed, and the interest to perform experiments under laboratory-controlled conditions, as a complementary tool to investigate related compounds (e.g., minor metabolites and/or transformation products in wastewater) is treated. The article ends up with the trends and future perspectives in this field from the authors' point of view. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:258-280, 2018.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1002/mas.21525DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6191649PMC
May 2018

Transformation and Sorption of Illicit Drug Biomarkers in Sewer Systems: Understanding the Role of Suspended Solids in Raw Wastewater.

Environ Sci Technol 2016 12 21;50(24):13397-13408. Epub 2016 Nov 21.

Technical University of Denmark (DTU) , Department of Environmental Engineering, Miljøvej 113, 2800 Kgs. Lyngby, Denmark.

Sewer pipelines, although primarily designed for sewage transport, can also be considered as bioreactors. In-sewer processes may lead to significant variations of chemical loadings from source release points to the treatment plant influent. In this study, we assessed in-sewer utilization of growth substrates (primary metabolic processes) and transformation of illicit drug biomarkers (secondary metabolic processes) by suspended biomass. Sixteen drug biomarkers were targeted, including mephedrone, methadone, cocaine, heroin, codeine, and tetrahydrocannabinol (THC) and their major human metabolites. Batch experiments were performed under aerobic and anaerobic conditions using raw wastewater. Abiotic biomarker transformation and partitioning to suspended solids and reactor wall were separately investigated under both redox conditions. A process model was identified by combining and extending the Wastewater Aerobic/anaerobic Transformations in Sewers (WATS) model and Activated Sludge Model for Xenobiotics (ASM-X). Kinetic and stoichiometric model parameters were estimated using experimental data via the Bayesian optimization method DREAM. Results suggest that biomarker transformation significantly differs from aerobic to anaerobic conditions, and abiotic conversion is the dominant mechanism for many of the selected substances. Notably, an explicit description of biomass growth during batch experiments was crucial to avoid significant overestimation (up to 385%) of aerobic biotransformation rate constants. Predictions of in-sewer transformation provided here can reduce the uncertainty in the estimation of drug consumption as part of wastewater-based epidemiological studies.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.est.6b03049DOI Listing
December 2016

Analysis of fullerenes in soils samples collected in The Netherlands.

Environ Pollut 2016 Dec 20;219:47-55. Epub 2016 Sep 20.

University of Amsterdam - IBED, Science Park 904, 1098 XH Amsterdam, The Netherlands; KWR, Watercycle Research Institute, P.O. Box 1072, 3433 PE Nieuwegein, The Netherlands.

Fullerenes are carbon based nanoparticles that may enter the environment as a consequence of both natural processes and human activities. Although little is known about the presence of these chemicals in the environment, recent studies suggested that soil may act as a sink. The aim of the present work was to investigate the presence of fullerenes in soils collected in The Netherlands. Samples (n = 91) were taken from 6 locations and analyzed using a new developed LC-QTOF-MS method. The locations included highly trafficked and industrialized as well as urban and natural areas. In general, C was the most abundant fullerene found in the environment, detected in almost a half of the samples and at concentrations in the range of ng/kg. Other fullerenes such as C and an unknown structure containing a C cage were detected to a lower extent. The highest concentrations were found in the proximity of combustion sites such as a coal power plant and an incinerator, suggesting that the nanoparticles were unintentionally produced during combustions processes and reached the soil through atmospheric deposition. Consistent with other recent studies, these results show that fullerenes are widely present in the environment and that the main route for their entrance may be due to human activities. These data will be helpful in the understanding of the distribution of fullerenes in the environment and for the study of their behavior and fate in soil.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.envpol.2016.09.034DOI Listing
December 2016

Qualitative screening of new psychoactive substances in pooled urine samples from Belgium and United Kingdom.

Sci Total Environ 2016 Dec 26;573:1527-1535. Epub 2016 Aug 26.

Toxicological Center, Department of Pharmaceutical Sciences, Campus Drie Eiken, University of Antwerp, Universiteitsplein 1, 2610 Antwerp, Belgium. Electronic address:

Concerns about new psychoactive substances (NPS) are increasing due to the rising frequency of serious intoxications. Analysis of biological fluids (urine) is necessary to get reliable information about the use of these substances. However, it is a challenging task due to the lack of analytical standards and the dynamic character of the NPS market. In the present work, a qualitative screening of NPS was carried out in 23 pooled urine samples collected from a city center in the UK and festivals in the UK and Belgium. The analytical method was based on data-independent acquisition mode using liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. An in-house library was used with >1500 entries corresponding to NPS, classical drugs and metabolites. All samples contained 53 and 28 compounds of interest from the UK and Belgium respectively. Of the different compounds detected, about 70% were confirmed using retention time and product ions while the remaining compounds were identified using elucidated fragmentation pathways. The highest numbers of NPS identified in both countries were from the cathinone and phenylethylamine families, with a higher number being detected in samples from the festival in the UK. Moreover, several cathinone metabolites in human urine were detected and identified. The screening method proved useful to detect a large number of compounds and determine the use of NPS.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2016.08.124DOI Listing
December 2016

Facilitating high resolution mass spectrometry data processing for screening of environmental water samples: An evaluation of two deconvolution tools.

Sci Total Environ 2016 Nov 25;569-570:434-441. Epub 2016 Jun 25.

KWR Watercycle Research Institute, Chemical Water Quality and Health, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE Amsterdam, The Netherlands. Electronic address:

A screening approach was applied to influent and effluent wastewater samples. After injection in a LC-LTQ-Orbitrap, data analysis was performed using two deconvolution tools, MsXelerator (modules MPeaks and MS Compare) and Sieve 2.1. The outputs were searched incorporating an in-house database of >200 pharmaceuticals and illicit drugs or ChemSpider. This hidden target screening approach led to the detection of numerous compounds including the illicit drug cocaine and its metabolite benzoylecgonine and the pharmaceuticals carbamazepine, gemfibrozil and losartan. The compounds found using both approaches were combined, and isotopic pattern and retention time prediction were used to filter out false positives. The remaining potential positives were reanalysed in MS/MS mode and their product ions were compared with literature and/or mass spectral libraries. The inclusion of the chemical database ChemSpider led to the tentative identification of several metabolites, including paraxanthine, theobromine, theophylline and carboxylosartan, as well as the pharmaceutical phenazone. The first three of these compounds are isomers and they were subsequently distinguished based on their product ions and predicted retention times. This work has shown that the use deconvolution tools facilitates non-target screening and enables the identification of a higher number of compounds.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2016.06.162DOI Listing
November 2016

Comparative measurement and quantitative risk assessment of alcohol consumption through wastewater-based epidemiology: An international study in 20 cities.

Sci Total Environ 2016 Sep 14;565:977-983. Epub 2016 May 14.

Norwegian Institute for Water Research (NIVA), Gaustadalleen 21, 0349 Oslo, Norway.

Quantitative measurement of drug consumption biomarkers in wastewater can provide objective information on community drug use patterns and trends. This study presents the measurement of alcohol consumption in 20 cities across 11 countries through the use of wastewater-based epidemiology (WBE), and reports the application of these data for the risk assessment of alcohol on a population scale using the margin of exposure (MOE) approach. Raw 24-h composite wastewater samples were collected over a one-week period from 20 cities following a common protocol. For each sample a specific and stable alcohol consumption biomarker, ethyl sulfate (EtS) was determined by liquid chromatography coupled to tandem mass spectrometry. The EtS concentrations were used for estimation of per capita alcohol consumption in each city, which was further compared with international reports and applied for risk assessment by MOE. The average per capita consumption in 20 cities ranged between 6.4 and 44.3L/day/1000 inhabitants. An increase in alcohol consumption during the weekend occurred in all cities, however the level of this increase was found to differ. In contrast to conventional data (sales statistics and interviews), WBE revealed geographical differences in the level and pattern of actual alcohol consumption at an inter-city level. All the sampled cities were in the "high risk" category (MOE<10) and the average MOE for the whole population studied was 2.5. These results allowed direct comparisons of alcohol consumption levels, patterns and risks among the cities. This study shows that WBE can provide timely and complementary information on alcohol use and alcohol associated risks in terms of exposure at the community level.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2016.04.138DOI Listing
September 2016

Determination of phosphodiesterase type V inhibitors in wastewater by direct injection followed by liquid chromatography coupled to tandem mass spectrometry.

Sci Total Environ 2016 Sep 7;565:140-147. Epub 2016 May 7.

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE Amsterdam, The Netherlands. Electronic address:

A simple, fast and reliable analytical method for the determination of phosphodiesterase type V inhibitors in wastewater was developed and validated. The method was based on direct injection followed by liquid chromatography coupled to tandem mass spectrometry with triple quadrupole as mass analyzer. Transformation products and analogues were included in the target list besides the three active pharmaceutical ingredients (sildenafil, vardenafil and tadalafil). The method performance was thoroughly investigated, including the analyte stability in wastewater and matrix effect. All target compounds presented linear fits between their LOD and 500ng/L. The quantification limits ranged from 1.6 to 30ng/L for all compounds except for n-octylnortadalafil (LOQ: 100ng/L); precision calculated as intraday repeatability was lower than 30%; accuracy calculated as procedural recovery ranged successfully between 85 and 105% in all cases. The method was applied to samples collected during three week-long monitoring campaigns performed in 2013, 2014 and 2015 in three Dutch cities. Only sildenafil and its two metabolites, desmethyl- and desethylsildenafil, were present with normalized loads ranging from LOQ to 8.3, 11.8 and 21.6mg/day/1000 inh, respectively. Two additional week-long sets of samples were collected in Amsterdam at the time that a festival event took place, bringing around 350,000 visitors to the city. The difference in drug usage patterns was statistically studied: "weekday" versus "weekend", "normal" versus "atypical" week; and results discussed. The metabolite to parent drug concentration ratio evolution during consecutive years was discussed, leading to several possible explanations that should be further investigated. Finally, wastewater-based epidemiology approach was applied to back-calculate sildenafil consumption.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2016.04.158DOI Listing
September 2016

Size and concentration determination of (functionalised) fullerenes in surface and sewage water matrices using field flow fractionation coupled to an online accurate mass spectrometer: method development and validation.

Anal Chim Acta 2015 Apr 18;871:77-84. Epub 2015 Feb 18.

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, Sciencepark 904, 1098 XH Amsterdam, The Netherlands.

In order to assess the environmental risks of a compound it is imperative to have suitable and reliable techniques for its determination in environmental matrices. In this paper, we focused on a method development for the recently introduced online coupling of a field flow fractionation (FFF) system to an Orbitrap-HRMS, that allows the simultaneous size and concentration determination of different aqueous fullerene aggregates and their concentrations in different size fractions. A 0.05% NH4OH solution in water was identified as the best carrier liquid for the analysis of the three different aqueous fullerene suspensions (C60 [60], [6,6]-phenyl-C61 butyric acid methyl ester ([60]PCBM) and [6,6]-(bis)phenyl-C61 butyric acid methyl ester ([60]bisPCBM)). The multi-angle light scattering (MALS) data received after employing the ammonia solution was consistent with both the theory and calibration using well defined Au and latex particles. The LODs obtained using Orbitrap HRMS detection were 0.1 μg L(-1) for an injection volume of 100 μL which are significantly better than the LODs obtained by using UV (20 μg L(-1)) and MALS detectors (5 μg L(-1)). However, these LODs can be further improved as in theory there is no limit to the amount of sample that can be injected into the FFF. Environmental samples (river and sewage water) were spiked with fullerenes and the fractograms obtained for these samples revealed that the matrix does affect the size of fullerene aggregates. Information on the size distribution can be useful for the risk assessment of these particles.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.aca.2015.02.042DOI Listing
April 2015

Success of rogue online pharmacies: sewage study of sildenafil in the Netherlands.

BMJ 2014 Jul 2;349:g4317. Epub 2014 Jul 2.

National Institute for Public Health and the Environment RIVM, PO Box 1, 3720 BA Bilthoven, Netherlands.

View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1136/bmj.g4317DOI Listing
July 2014

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

Addiction 2014 Aug 27;109(8):1338-52. Epub 2014 May 27.

Swiss Federal Institute of Aquatic Science and Technology (Eawag), Dübendorf, Switzerland.

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.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1111/add.12570DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4204159PMC
August 2014

An analytical method for determination of fullerenes and functionalized fullerenes in soils with high performance liquid chromatography and UV detection.

Anal Chim Acta 2014 Jan 16;807:159-65. Epub 2013 Nov 16.

University of Amsterdam - IBED, Sciencepark 904, 1098 XH Amsterdam, The Netherlands; KWR, Watercycle Research Institute, P.O. Box 1072, 3433 PE Nieuwegein, The Netherlands.

Fullerenes are carbon-based nanomaterials expected to play a major role in emerging nanotechnology and produced at an increasing rate for industrial and household applications. In the last decade a number of novel compounds (i.e. fullerene derivatives) is being introduced into the market and specific analytical methods are needed for analytical purposes as well as environmental and safety issues. In the present work eight fullerenes (C60 and C70) and functionalized fullerenes (C60 and C70 exohedral-derivatives) were selected and a novel liquid chromatographic method was developed for their analysis with UV absorption as a method of detection. The resulting HPLC-UV method is the first one suitable for the analysis of all eight compounds. This method was applied for the analysis of fullerenes added to clayish, sandy and loess top-soils at concentrations of 20, 10 and 5 μg kg(-1) and extracted with a combination of sonication and shaking extraction. The analytical method limits of detection (LoD) and limits of quantification (LoQ) were in the range of 6-10 μg L(-1) and 15-24 μg L(-1) respectively for the analytical solutions. The extraction from soil was highly reproducible with recoveries ranging from 47±5 to 71±4% whereas LoD and LoQ for all soils tested were of 3 μg kg(-1) and 10 μg kg(-1) respectively. No significant difference in the extraction performance was observed depending of the different soil matrices and between the different concentrations. The developed method can be applied for the study of the fate and toxicity of fullerenes in complex matrices at relatively low concentrations and in principle it will be suitable for the analysis of other types of functionalized fullerenes that were not included in this work.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.aca.2013.11.015DOI Listing
January 2014

Enantiomer profiling of high loads of amphetamine and MDMA in communal sewage: a Dutch perspective.

Sci Total Environ 2014 Jul 28;487:666-72. Epub 2013 Nov 28.

KWR Watercycle Research Institute, Chemical Water Quality and Health, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands; Institute for Biodiversity and Ecosystem Dynamics, University of Amsterdam, P.O. Box 94248, 1090 GE Amsterdam, The Netherlands.

Analysis of wastewater with an aim of community-wide estimation of drug use is a new and very promising approach. Until now it was very difficult to determine if mass loads of studied drugs were actually originating from consumption, or disposal of unused drugs or production waste. This uncertainty in the estimation of community wide drugs use should not be underestimated. This paper aims to apply for the first time enantiomeric profiling in verifying sources of the presence of MDMA and amphetamine in wastewater based on a case study in two Dutch cities: Utrecht and Eindhoven. The results showed that MDMA is usually present in wastewater due to its consumption (MDMA enriched with R(-)-enantiomer). Excessively high mass loads of MDMA during a sampling campaign in Utrecht in 2011 proved to be racemic indicating direct disposal of unused MDMA possibly as a result of a police raid at a nearby illegal production facility. Enantiomeric profiling was also undertaken in order to verify the origin of unexpectedly high mass loads of amphetamine in the city of Eindhoven in 2011. Unfortunately, a distinction between consumption and direct disposal of unused amphetamine in Dutch wastewater could not be achieved. Further work will have to be undertaken to fully understand sources of amphetamine in Dutch wastewaters.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.scitotenv.2013.11.043DOI Listing
July 2014

Sample preparation for combined chemical analysis and in vitro bioassay application in water quality assessment.

Environ Toxicol Pharmacol 2013 Nov 23;36(3):1291-303. Epub 2013 Oct 23.

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands. Electronic address:

The combination of in vitro bioassays and chemical screening can provide a powerful toolbox to determine biologically relevant compounds in water extracts. In this study, a sample preparation method is evaluated for the suitability for both chemical analysis and in vitro bioassays. A set of 39 chemicals were spiked to surface water, which were extracted using Oasis MCX cartridges. The extracts were chemically analyzed by liquid chromatography linear ion trap Orbitrap analysis and recoveries appeared to be on average 61% Compounds with logK(ow) values in the range between 0 and 4 are recovered well using this method. In a next step, the same extracts were tested for genotoxic activity using the Comet assay and Ames fluctuation test and for specific endocrine receptor activation using a panel of CALUX assays, for estrogenic (ER), androgenic (AR), glucocorticoid (GR), progestagenic (PR), and thyroidogenic (TR) agonistic activities. The results of the genotoxicity assays indicated that spiked genotoxic compounds were preserved during sample preparation. The measured responses of the GR CALUX and ER CALUX assays were similar to the predicted responses. The measured responses in the AR CALUX and PR CALUX assays were much lower than expected from the analytical concentration, probably due to antagonistic effects of some spiked compounds. Overall, the presented sample preparation method seems to be suitable for both chemical analysis and specific in vitro bioassay applications.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.etap.2013.10.009DOI Listing
November 2013

Analysis of (functionalized) fullerenes in water samples by liquid chromatography coupled to high-resolution mass spectrometry.

Anal Chem 2013 Jun 24;85(12):5867-74. Epub 2013 May 24.

KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands.

One of the main challenges in environmental risk assessment of fullerenes is to develop analytical methods that detect and quantify fullerenes at low concentrations. In this paper we report on the development and optimization of a highly specific, robust, and relatively simple method for the quantitative determination of C60, C70, and six functionalized fullerenes, namely, [6,6]-phenyl-C61-butyric acid methyl ester, [6,6]-phenyl-C61-butyric acid butyl ester, [6,6]-phenyl-C61-butyric acid octyl ester, [6,6]-bis(phenyl)-C61-butyric acid methyl ester, [6,6]-thienyl-C61-butyric acid methyl ester, and [6,6]-phenyl-C71-butyric acid methyl ester ([70PCBM], in different aqueous matrixes. For this method fullerenes were extracted from the aqueous phase using solid-phase extraction (SPE), with subsequent analysis on a liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS) system. SPE was optimized by varying different conditions to improve recovery of all fullerenes. Different SPE column materials (C18, C18e, C8, CN) were tested, and recoveries appeared to be the highest for the C18-material. Recoveries were improved by adding NaCl to the water during extraction. Very low limit of detection (LOD) values were obtained for all compounds with this method, ranging from 0.17 ng/L for [70]PCBM to 0.28 ng/L for C60, and subsequent limit of quantitation (LOQ) values of 0.57-0.91 ng/L. Recoveries for the fullerenes were on average 120% in ultrapure and drinking water. Recoveries appeared to be lower, but still acceptable (e.g., >78%), in surface water. The developed approach is promising and will be applied, for example, in (1) environmental monitoring, (2) a more in-depth study of environmental fate and transformation products, and (3) studying water treatment efficiency of C60, C70, and the various functionalized fullerenes.
View Article and Find Full Text PDF

Download full-text PDF

Source
http://dx.doi.org/10.1021/ac400619gDOI Listing
June 2013