Nikolaos I. Rousis

Screening of pharmaceuticals and illicit drugs in wastewater and surface waters of Spain and Italy by high resolution mass spectrometry using UHPLC-QTOF MS and LC-LTQ-Orbitrap MS

AbstractThe existence of pharmaceuticals and illicit drugs (PIDs) in environmental waters has led many analytical chemists to develop screening methods for monitoring purposes. Water samples can contain a huge number of possible contaminants, commonly at low concentrations, which makes their detection and identification problematic. Liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) has proven itself effective in the screening of environmental contaminants. The present work investigates the use of the most popular HRMS instruments, quadrupole time-of-flight and linear trap quadrupole-Orbitrap, from two different laboratories. A suspect screening for PIDs was carried out on wastewater (influent and effluent) and surface water samples from Castellón, Eastern Spain, and Cremona, Northern Italy, incorporating a database of 107 PIDs (including 220 fragment ions). A comparison between the findings of both instruments and of the samples was made which highlights the advantages and drawbacks of the strategies applied in each case. In total, 28 compounds were detected and/or identified by either/both instruments with irbesartan, valsartan, benzoylecgonine and caffeine being the most commonly found compounds across all samples. Graphical AbstractA suspect screening of pharmaceuticals and illicit drugs in envrionmental waters of both Castellón, Spain and Cremona, Italy was carried out using liquid chromatography coupled with high resolution mass spectrometry

Comparison of pharmaceutical, illicit drug, alcohol, nicotine and caffeine levels in wastewater with sale, seizure and consumption data for 8 European cities

BackgroundMonitoring the scale of pharmaceuticals, illicit and licit drugs consumption is important to assess the needs of law enforcement and public health, and provides more information about the different trends within different countries. Community drug use patterns are usually described by national surveys, sales and seizure data. Wastewater-based epidemiology (WBE) has been shown to be a reliable approach complementing such surveys.MethodThis study aims to compare and correlate the consumption estimates of pharmaceuticals, illicit drugs, alcohol, nicotine and caffeine from wastewater analysis and other sources of information. Wastewater samples were collected in 2015 from 8 different European cities over a one week period, representing a population of approximately 5 million people. Published pharmaceutical sale, illicit drug seizure and alcohol, tobacco and caffeine use data were used for the comparison.ResultsHigh agreement was found between wastewater and other data sources for pharmaceuticals and cocaine, whereas amphetamines, alcohol and caffeine showed a moderate correlation. methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) and nicotine did not correlate with other sources of data. Most of the poor correlations were explained as part of the uncertainties related with the use estimates and were improved with other complementary sources of data.ConclusionsThis work confirms the promising future of WBE as a complementary approach to obtain a more accurate picture of substance use situation within different communities. Our findings suggest further improvements to reduce the uncertainties associated with both sources of information in order to make the data more comparable.

Measuring biomarkers in wastewater as a new source of epidemiological information: Current state and future perspectives

The information obtained from the chemical analysis of specific human excretion products (biomarkers) in urban wastewater can be used to estimate the exposure or consumption of the population under investigation to a defined substance. A proper biomarker can provide relevant information about lifestyle habits, health and wellbeing, but its selection is not an easy task as it should fulfil several specific requirements in order to be successfully employed. This paper aims to summarize the current knowledge related to the most relevant biomarkers used so far. In addition, some potential wastewater biomarkers that could be used for future applications were evaluated. For this purpose, representative chemical classes have been chosen and grouped in four main categories: (i) those that provide estimates of lifestyle factors and substance use, (ii) those used to estimate the exposure to toxicants present in the environment and food, (iii) those that have the potential to provide information about public health and illness and (iv) those used to estimate the population size. To facilitate the evaluation of the eligibility of a compound as a biomarker, information, when available, on stability in urine and wastewater and pharmacokinetic data (i.e. metabolism and urinary excretion profile) has been reviewed. Finally, several needs and recommendations for future research are proposed.

Wastewater-based epidemiology to assess human exposure to pyrethroid pesticides

Pesticides are active substances with potentially adverse effects on human health, and therefore great effort is addressed to study the relation between their widespread use and the effects on humans. To track human exposure to pesticides, novel approaches are needed to give additional information on exposure at population level. In this study, a novel application of Wastewater-Based Epidemiology (WBE) was developed to measure the intake of pyrethroid pesticides in a population. Three human urinary metabolites of pyrethroids were selected and validated as biomarkers of exposure by evaluating their sources and stability in wastewater. They were measured by liquid chromatography-tandem mass spectrometry in raw urban wastewater collected from the wastewater treatment plants of six Italian cities. Their concentrations were used as biomarkers to back-calculate the intake of pyrethroid pesticides in the population. WBE results were in line with the urinary biomarker levels of biomonitoring studies considering dilution in wastewater. Significant differences in the metabolites levels were observed among different cities. Seasonal variations in human intake of pyrethroids were also seen, as expected, with higher intakes during spring/summer. Intakes in the six cities were compared with the acceptable daily intake (ADI) and it was concluded that some of the populations examined might face significant health risks. Results confirm that this method can provide supplementary information to biomonitoring studies and can be a valuable tool for obtaining objective, direct information on the real levels of exposure to pyrethroids of different populations.

Wastewater-Based Epidemiology To Monitor Synthetic Cathinones Use in Different European Countries

Synthetic cathinones are among the most consumed new psychoactive substances (NPS), but their increasing number and interchangeable market make it difficult to estimate the real size of their consumption. Wastewater-based epidemiology (WBE) through the analysis of metabolic residues of these substances in urban wastewater can provide this information. This study applied WBE for the first time to investigate the presence of 17 synthetic cathinones in four European countries. A method based on solid-phase extraction and liquid chromatography coupled to tandem mass spectrometry was developed, validated, and used to quantify the target analytes. Seven substances were found, with mephedrone and methcathinone being the most frequently detected and none of the analytes being found in Norway. Population-normalized loads were used to evaluate the pattern of use, which indicated a higher consumption in the U.K., followed by Spain and Italy, in line with the European prevalence data from population surveys. In the U.K., where an entire week was investigated, an increase of the loads was found during the weekend, indicating a preferential use in recreational contexts. This study demonstrated that WBE can be a useful additional tool to monitor the use of NPS in a population.

Monitoring a large number of pesticides and transformation products in water samples from Spain and Italy

ABSTRACT Assessing the presence of pesticides in environmental waters is particularly challenging because of the huge number of substances used which may end up in the environment. Furthermore, the occurrence of pesticide transformation products (TPs) and/or metabolites makes this task even harder. Most studies dealing with the determination of pesticides in water include only a small number of analytes and in many cases no TPs. The present study applied a screening method for the determination of a large number of pesticides and TPs in wastewater (WW) and surface water (SW) from Spain and Italy. Liquid chromatography coupled to high‐resolution mass spectrometry (HRMS) was used to screen a database of 450 pesticides and TPs. Detection and identification were based on specific criteria, i.e. mass accuracy, fragmentation, and comparison of retention times when reference standards were available, or a retention time prediction model when standards were not available. Seventeen pesticides and TPs from different classes (fungicides, herbicides and insecticides) were found in WW in Italy and Spain, and twelve in SW. Generally, in both countries more compounds were detected in effluent WW than in influent WW, and in SW than WW. This might be due to the analytical sensitivity in the different matrices, but also to the presence of multiple sources of pollution. HRMS proved a good screening tool to determine a large number of substances in water and identify some priority compounds for further quantitative analysis. HighlightsA large number of pesticides and transformation products was screened in waters.Spain and Italy were selected as study areas for their high use of pesticides.A retention time prediction model was applied to facilitate identification.More pesticides were detected in surface and treated water than in raw wastewater.HRMS was suitable for detecting a large number of substances.

Development, validation and accreditation of a method for the determination of Pb, Cd, Cu and As in seafood and fish feed samples

A rapid, sensitive, accurate and precise method for the determination of Pb, Cd, As and Cu in seafood and fish feed samples by Simultaneous Electrothermal Atomic Absorption Spectrometry was developed in regard to Council Directive 333/2007EC and ISO/IEC 17025 (2005). Different approaches were investigated in order to shorten the analysis time, always taking into account the sensitivity. For method validation, precision (repeatability and reproducibility) and accuracy by addition recovery tests have been assessed as performance criteria. The expanded uncertainties based on the Eurachem/Citac Guidelines were calculated. The method was accredited by the Hellenic Accreditation System and it was applied for an 8 years study in seafood (n=202) and fish feeds (n=275) from the Greek market. The annual and seasonal variation of the elemental content and correlation among the elemental content in fish feeds and the respective fish samples were also accomplished.

Increased levels of the oxidative stress biomarker 8-iso-prostaglandin F2α in wastewater associated with tobacco use

Wastewater analysis has been demonstrated to be a complementary approach for assessing the overall patterns of drug use by a population while the full potential of wastewater-based epidemiology has yet to be explored. F2-isoprostanes are a prototype wastewater biomarker to study the cumulative oxidative stress at a community level. In this work, 8-iso-prostaglandin F2α (8-iso-PGF2α) was analysed in raw 24 h-composite wastewater samples collected from 4 Norwegian and 7 other European cities in 2014 and 2015. Using the same samples, biomarkers of alcohol (ethyl sulfate) and tobacco (trans-3′-hydroxycotinine) use were also analysed to investigate any possible correlation between 8-iso-PGF2α and the consumption of the two drugs. The estimated per capita daily loads of 8-iso-PGF2α in the 11 cities ranged between 2.5 and 9.9 mg/day/1000 inhabitants with a population-weighted mean of 4.8 mg/day/1000 inhabitants. There were no temporal trends observed in the levels of 8-iso-PGF2α, however, spatial differences were found at the inter-city level correlating to the degree of urbanisation. The 8-iso-PGF2α mass load was found to be strongly associated with that of trans-3′-hydroxycotinine while it showed no correlation with ethyl sulfate. The present study shows the potential for 8-iso-PGF2α as a wastewater biomarker for the assessment of community public health.

Estimation of caffeine intake from analysis of caffeine metabolites in wastewater

Caffeine metabolites in wastewater were investigated as potential biomarkers for assessing caffeine intake in a population. The main human urinary metabolites of caffeine were measured in the urban wastewater of ten European cities and the metabolic profiles in wastewater were compared with the human urinary excretion profile. A good match was found for 1,7-dimethyluric acid, an exclusive caffeine metabolite, suggesting that might be a suitable biomarker in wastewater for assessing population-level caffeine consumption. A correction factor was developed considering the percentage of excretion of this metabolite in humans, according to published pharmacokinetic studies. Daily caffeine intake estimated from wastewater analysis was compared with the average daily intake calculated from the average amount of coffee consumed by country per capita. Good agreement was found in some cities but further information is needed to standardize this approach. Wastewater analysis proved useful to providing additional local information on caffeine use.

Attenuation of interference in collision/reaction cell inductively coupled plasma mass spectrometry, using helium and hydrogen as cell gases – application to multi-element analysis of mastic gum

A collision/reaction cell ICP-MS was used to develop a method for the multi-element determination of Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Nb, Mo, Ag, Cd, Sb, Cs, Ba, Hg and Pb in mastic gum. Evaluation of helium and hydrogen as cell gases took place and their ability to reduce several types of interference arising from a Si, S, P, C, Cl and F based matrix was investigated. Likewise, much polyatomic interference was attenuated efficiently by the effect of kinetic energy discrimination. Moreover, a study of stopping curve measurements was performed. Thus, measurements of the ion loss caused by collisions, reaction cross-sections given by the Langevin–Gioumousis–Stevenson model and collision cross-sections were carried out. The method was validated and the calculated recoveries for all elements (at three concentration levels) were ranged between 92.6% (Ti) and 105% (Ag) and the relative standard deviation (%RSD) of reproducibility was ranged between 1.6% (Co) and 9.9% (Ca). The limits of detection ranged between 0.11 ng g−1 (Cs) and 1.12 μg g−1 (Ca). The trueness of the method was also checked by the analysis of a standard reference material (SRM, 1573a tomato leaves).