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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.Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017.Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries.Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of ΔBenzoylecgonine 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.The analysis of wastewater to quantify drug loads provides near real-time drug use estimates that globally correspond to prevalence and seizure data.

Wastewater-based epidemiology (WBE) was applied for the first time in seven cities across Europe with the aim of estimating quinolones consumption via the analysis of human urinary metabolites in wastewater. This report is also the first pan-European study focussed on the enantiomeric profiling of chiral quinolones in wastewater. By considering loads of (fluoro)quinolones in wastewater within the context of human stereoselective metabolism, we identified cities in Southern Europe characterised by both high usage and direct disposal of unused ofloxacin. In Northern European cities, S-(-)-ofloxacin loads were predominant with respect to R-(+)-ofloxacin. Much more potent, enantiomerically pure S-(-)-ofloxacin was detected in wastewaters from Southern European cities, reflecting consumption of the enantiomerically pure antibiotic. Nalidixic acid, norfloxacin and lomefloxacin were detected in wastewater even though they were not prescribed according to official prescription data. S,S-(-)-moxifloxacin and S,S-(-)-moxifloxacin-N-sulphate were detected in wastewater due to metabolism of moxifloxacin. For the first time, average population-normalised ulifloxacin loads of 22.3 and 1.5 mg day−1 1000 people−1 were reported for Milan and Castellón as a result of prulifloxacin metabolism. Enrichment of flumequine with first-eluting enantiomer in all the samples indicated animal metabolism rather than its direct disposal. Fluoroquinolone loads were compared with qnrS gene encoding quinolone resistance to correlate usage of fluoroquinolone and prevalence of resistance. The highest daily loads of the qnrS gene in Milan corresponded with the highest total quinolone load in Milan proving the hypothesis that higher usage of quinolones is linked with higher prevalence of quinolone resistance genes. Utrecht, with the lowest quinolones usage (low daily loads) had also one of the lowest daily loads of the qnrS gene. However, a similar trend was not observed in Oslo nor Bristol where higher qnrS gene loads were observed despite low quinolone usage.

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., This study was supported by the following countries, institutions and projects Australia: Thyne Reid foundation; Canada: Natural Sciences and Engineering Research Council of Canada (NSERC); Iceland: The Icelandic Research Fund (Grant number 163049–051); Slovenia: Slovene Research Agency (funding Project L1–9191); Spain: MINECO/AEI projects (CTM2014–56628‐C3–2‐R, CTQ2015–65603‐P, CTM2016–81935‐REDT, CTM2017–84763‐C3–2‐R), Galician Council of Culture, Education and Universities (ED481D 2017/003); UK: Environmental Sustainability Knowledge Transfer Network, Engineering and Physical Sciences Research Council and Thermo Fisher Scientific (CASE industrial scholarship for K. Munro, Ref.: EP/J502029/1). European Monitoring Centre for Drugs and Drug Addiction (EMCDDA); EU International Training Network SEWPROF (Marie Curie‐FP7‐PEOPLE, grant number 317205); COST Action ES1307 supported by COST (European Cooperation in Science and Technology); WATCH (Wastewater Analysis of Traces of illicit drug‐related Chemicals for law enforcement and public Health DG migration and Home affairs ‐ HOME/2015/ISFP/PR/DRUG/0062). Sampling support and provision of catchment information Austria: Klemens Geiger and Michael Schlapp; Belgium: Jonathan Phariseau, Bart Coene, Luc Van Os, Peter Nys, Dieter Lemaire, Jean‐François Mougel, Patrick Vantroyen and Karel Claes; Croatia: Marin Ganjto; Czech Republic: Jiri Stara and Robert Hrich Brněnské; France: Véronique Bremont; Italy: Roberto Mazzini and Francesca Pizza (Milan), Francesco Avolio (Bologna), Fabrizio Moratto and Sergio Ghezzi (Gorizia), Rosanna Brienza and Simona Panariello (Potenza), Pier Paolo Abis and Antonia Attanasio (Bari), Antonella Cicala (Palermo); Norway: Pia Ryrfors; Portugal: João Goulão, José Martins, Pedro Alvaro and Fátima Paixão; Slovakia: Silvia Antalová and Jozef Tichy; Spain: Begoña Martínez López, Cristian Mesa, Santiago Querol Rodriguez, Fernando Llavador, Enrique Albors and Gloria Fayos; the Netherlands: Alex Veltman, Peter Theijssen, Peter van Dijk, Stefan Wijers, Mark Stevens, Ferry de Wilde. Analytical support Australia: Maulik Ghetia; Cyprus: Popi Karaolia; Greece: Nikoilaos Raikos; Spain: Ana Maria Botero‐Coy, Clara Boix, Alberto Celma, Jorge Pitarch, Inés Racamonde and Eddie Fonseca; Italy: Emma Gracia‐Lor, Nikolaos I. Rousis and Noelia Salgueiro‐Gonzalez. Data repository and data screening Eawag: Harald von Waldow; EMCDDA: Renate Hochwieser, Liesbeth Vandam, João Matias and Federica Mathis.

Nanofiltration can be used to separate succinic acid (SA) from other organic acids in a fermentation broth. However, commercial nanofiltration membranes can be insufficiently selective since some produced organic acids have similar molecular weights. SA production from biomass fermentation entails separation of succinic acid from the other concomitantly produced organic acids such as acetic acid, formic acid, pyruvic acid etc. In this study, five commercial nanofiltration membranes were tested for SA rejection and selectivity under dead-end and crossflow modes of SA recovery from selected synthetic solutions and a real fermentation broth. SA rejections up to 94.1 ± 1.5% and 95.5 ± 3.5% were observed for the synthetic broth and the fermentation broth, respectively. The SA fractions obtained in the retentate were nearly 70% and 60% for synthetic and fermentation broth, respectively. The highest rejections and SA fraction values were achieved with DK and NF270 membranes, which also showed the highest permeate flux. Model evaluation using the Donnan-steric pore model with dielectric exclusion (DSPM-DE) showed that 99% of the SA rejection occurs at the membrane interface and not inside the membrane. Based on the modelling, the most important mechanism affecting separation was dielectric exclusion at both sides of the membrane surfaces. Moreover, identified sensitive model parameters, i.e. pore dielectric constant ( e pore ) , charge density ( X d ) and pore radius ( r p ) , were estimated through model fitting and were found to be highly correlated with significant variations. Finally, for the first time, a calibrated model with synthetic broth was successfully used to predict organic acids rejection for a real fermentation broth (with 12% and 3% prediction error for succinate rejection by NF270 and DK, respectively). Such prediction was achieved only by measuring organic acid concentrations in the fermentation broth and using the three sensitive parameters. Furthermore, the potential contribution of different transport mechanisms of SA was quantified for the first time.

Pelagic Sargassum inundation of coastlines across the North Atlantic is an ongoing challenge but presents new opportunities for value-added resource recovery. This study assessed the techno-economic feasibility and environmental impact of utilising these invasive brown seaweed, and food waste as feedstock for energy production and fertiliser recovery in Barbados. The biorefinery concept evaluated was designed with hydrothermal pretreatment (HTP) and anaerobic digestion (AD) technologies. Financial analyses of four varied feedstock and process scenarios (S1-S4) established a linear relationship between profitability and the sale of products (electricity and fertiliser). In all cases, simple sale of power generated to the national grid resulted in a negative cash flow and required the introduction of fertiliser sales to achieve positive cash flows. Moreover, the net loss in the electricity only scenarios exceeded that of the landfill disposal, the present operation employed on the island for Sargassum management. The addition of the solid digestate to the revenue stream increased the profit margin and financial attractiveness of the process. Maximum income generation could be attained through 100% supply of the digestate to international markets. However, this approach provides zero support to local food security. The preferred option involves the 50/50 split utilisation of the solid digestate in local and international agricultural practice. While HTP is energy-intensive technology, the recirculation of waste heat generated by a combined heat and power unit for HTP reduced the input energy demand. It also lowered the potential environmental impact by more than 10-fold, relative to landfill disposal. Recycling of the liquid digestate also reduced the fresh water demand and its associated costs. Despite the promising results, process scale-up and commercialisation remain a main challenge, primarily due to the seasonality and variability of Sargassum seaweed for continuous bioprocessing.

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.

Human biomonitoring, i.e. the determination of chemicals and/or their metabolites in human specimens, is the most common and potent tool for assessing human exposure to pesticides, but it suffers from limitations such as high costs and biases in sampling. Wastewater-based epidemiology (WBE) is an innovative approach based on the chemical analysis of specific human metabolic excretion products (biomarkers) in wastewater, and provides objective and real-time information on xenobiotics directly or indirectly ingested by a population. This study applied the WBE approach for the first time to evaluate human exposure to pesticides in eight cities across Europe. 24 h-composite wastewater samples were collected from the main wastewater treatment plants and analyzed for urinary metabolites of three classes of pesticides, namely triazines, organophosphates and pyrethroids, by liquid chromatography-tandem mass spectrometry. The mass loads (mg/day/1000 inhabitants) were highest for organophosphates and lowest for triazines. Different patterns were observed among the cities and for the various classes of pesticides. Population weighted loads of specific biomarkers indicated higher exposure in Castellon, Milan, Copenhagen and Bristol for pyrethroids, and in Castellon, Bristol and Zurich for organophosphates. The lowest mass loads (mg/day/1000 inhabitants) were found in Utrecht and Oslo. These results were in agreement with several national statistics related to pesticides exposure such as pesticides sales. The daily intake of pyrethroids was estimated in each city and it was found to exceed the acceptable daily intake (ADI) only in one city (Castellon, Spain). This was the first large-scale application of WBE to monitor population exposure to pesticides. The results indicated that WBE can give new information about the "average exposure" of the population to pesticides, and is a useful complementary biomonitoring tool to study population-wide exposure to pesticides. (C) 2017 Elsevier Ltd. All rights reserved.

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. This work was supported by the COST Action ES1307 “SCORE – Sewage biomarker analysis for community health assessment”. Emma Gracia-Lor is very grateful to Generalitat Valenciana, Conselleria d'Educació, Investigació, Cultura i Esport (APOSTD/2015, Programa VALi + d) for her post-doctoral contract. Lubertus Bijlsma acknowledges NPS-Euronet (HOME/2014/JDRUG/AG/DRUG/7086), co-funded by the European Union, for his post-doctoral fellowship. Erika Castrignanò, Richard Bade, Juliet Kinyua, Pedram Ramin, Nikolaos I. Rousis, Yeonsuk Ryu would like to thank the SEWPROF MC ITN project, ‘A new paradigm in drug use and human health risk assessment: Sewage profiling at the community level’ [grant agreement 317205] supported by the European Union's Seventh Framework Programme for research, technological development and demonstration for the financial support. Iria González-Mariño extends her gratitude to the Galician Council of Culture, Education and Universities for her postdoctoral contract (Plan Galego de Investigación, Innovación e Crecemento 2011–2015). Foon Yin Lai acknowledges her postdoctoral fellowship from the University of Antwerp. Luigi Lopardo, Axel Rydevik and Barbara Kasprzyk-Hordern would like to acknowledge Leverhulme Trust for funding ‘TOX-EDC, Wastewater profiling for community-wide human exposure assessment from environmental endocrine disrupting chemicals in personal care and consumer products’ (Project No: RPG-2013-297). Frederic Been would like to thank the Swiss National Science Foundation (SNF, P2LAP2_164892) for his post-doctoral grant. This publication reflects the views only of the authors, and the European Commission cannot be held responsible for any use which may be made of the information contained therein.

In this paper, a multi-scale model is used to assess the multiple mineral precipitation potential in a full-scale anaerobic granular sludge system. Reactor behaviour is analysed under different operational conditions (addition/no addition of reject water from dewatering of lime-stabilized biomass) and periods of time (short/long term). Model predictions suggest that a higher contribution of reject water promotes the risk of intra-granule CaCO3 formation as a result of the increased quantity of calcium arriving with that stream combined with strong pH gradients within the biofilm. The distribution of these precipitates depends on: (i) reactor height; and (ii) granule size. The study also exposes the potential undesirable effects of the long-term addition of reject water (a decrease in energy recovery of 20% over a 100-day period), caused by loss in biomass activity (due to microbial displacement), and the reduced buffer capacity. This demonstrates how both short-term and long-term operational conditions may affect the formation of precipitates within anaerobic granules, and how it may influence methane production and consequently energy recovery.

Sustainable growth of industries in fast developing but water-scarce countries like Kenya can only be achieved by optimizing water usage and reducing wastewater discharge. Besides internal recycling, industries can greatly reduce their freshwater intake by exchanging wastewater streams with neighboring industries and creating symbiosis relations. Previous studies have attempted to design an optimal network of water exchange streams in industrial parks by applying a global multi-objective optimization approach (e.g., [1]). However, only a few have considered the complexity of used water streams in terms of flow rate variation [2] and number of significant pollutants [3].In this study, we present the outcome of the optimization analysis, covering the above-mentioned knowledge gaps, for water exchange between 10 companies in an industrial park in Ruaraka, Nairobi. A combination of clarification, physico-chemical, membrane-based (Inside® by Aquaporin A/S, Denmark) and disinfection treatments was considered in the optimization exercise as decentralized fit-for-purpose treatment units. Information on volumes and quality of water usage and wastewater discharge was gathered through on-site visits and interviews. The analysis forms part of a research project, Gecko (Green and Circular Innovation for Kenyan Companies), investigating circular solutions within water, materials and energy by specifically focusing on wastewater reuse and targeting industrial symbiosis potentials.The formulation of the water reuse network is shown in the superstructure (an example for three processes) in Figure 1 using a series of multiple treatment units prior to reuse. The multi-objective evolutionary algorithm NSGA II [4] was applied, considering (i) an economic objective (i.e. capital and operational cost of treatment, piping cost and freshwater consumption volume); (ii) an environmental objective (i.e. CO2 emission, wastewater discharge pollution load); (iii) social constraints, considered as a matrix of collaboration interests among industries (as gathered during on-site surveys). LifeCycle Assessment (LCA) was performed on the applied water treatment processes, as well as post-optimization evaluation of multiple optimum solutions.Preliminary optimization results show the potential of 10% economic and 20% environmental improvements in the industrial park through a water exchange network among the considered companies. More detailed analysis on the optimization objectives including fresh water saving and wastewater discharge, as well as LCA of optimum solutions will be presented later. The water network will be expanded to up to 32 companies in the same industrial park. The presented methodology can also be used to perform uncertainty and flexibility assessments of water reuse networks

The objective of this paper is to present the main results of an engineering-research project dealing with model-based evaluation of waste streams treatment from a biotech company. This has been extensively done in domestic treatment systems, but is equally important, and with different challenges in industrial wastewater treatment. A new set of biological (activated sludge, anaerobic digestion), physicochemical (aqueous phase, precipitation, mass transfer) process models and model interfaces are required to describe removal of organics in an upflow anaerobic sludge blanket (UASB) reactor plus either traditional nitrification/denitrification (A 1 ) or partial nitritation (PN)/anammox (ANX) (A 2 ) processes. Model-based analysis shows that option A 1 requires a decrease in digestion energy recovery (E recovery ) in order to have enough organic substrate for subsequent post NO 3 reduction treatment (95 kWh.kg N −1 ). In contrast, A 2 in an aerobic granular sludge reactor allows for higher UASB conversion since N removal is carried out autotrophically. The study also reveals that the addition of an aerated pre-treatment unit prior to the PN/ANX (A 2 ) reactor promotes COD and H 2 S oxidation, CO 2 and CH 4 stripping, a pH increase (up to 8.5) and a reduction of the risk of intra-granular precipitation as well as sulfide inhibition. Simulations indicate clear differences regarding the microbial distribution/abundance within the biofilm in A 2 when comparing the two operational modes. Final results show the effects of different loading and operational conditions; dissolved oxygen (DO), Total Suspended Solids (TSS op ), energy recovery (E recovery ); on the overall process performance; N removal, aeration energy (E aeration ), net energy production (E recovery ); using response surfaces, highlighting the need of integrated approaches to avoid sub-optimal outcomes. The study shows the benefits of virtual plant simulation and demonstrates the potential of model-based evaluation when process engineers in industry have to decide between competing options.

Industrial parks have a high potential for recycling and reusing resources such as water across companies by creating symbiosis networks. In this study, we introduce a mathematical optimization framework for the design of water network integration in industrial parks formulated as a large-scale standard mixed-integer non-linear programming (MINLP) problem. The novelty of our approach relies on i) developing a multi-level incremental optimization framework for water network synthesis, ii) including prior knowledge of water demand growth and projected water scarcity to evaluate the significance of water-saving solutions, iii) incorporating a comprehensive formulation of the water network synthesis problem including multiple pollutants and different treatment units and iv) performing a multi-objective optimization of the network including freshwater savings and relative cost of the network. The significance of the proposed optimization framework is illustrated by applying it to an existing industrial park in a water-scarce region in Kenya. Firstly, we illustrated the benefits of including prior knowledge to prevent an over-design of the network at the early stages. In the case study, we achieved a more flexible and expandable water network with 36% lower unit cost at the early stage and 15% lower unit cost at later stages for overall maximum freshwater savings of 25%. Secondly, multi-objective analysis suggests an optimum freshwater savings of 14% to reduce the unit cost of the network by half. Moreover, the significance of symbiosis networks is highlighted by showing that intra-company connections can only achieve a maximum freshwater savings of 17% with significantly higher unit cost (+45%). Finally, we showed that the values of symbiosis connectivity index in the Pareto front correspond to higher freshwater savings, indicating the significant role of the symbiosis network in the industrial park under study. This is the first study, where all the above elements have been taken into account simultaneously for the design of a water reuse network.

Monitoring population drug use through wastewater-based epidemiology (WBE) is a useful method to quantitatively follow trends and estimate total drug consumption in communities. Concentrations of drug biomarkers might be low in wastewater due to dilution; and therefore analysis of pooled urine (PU) is useful to detect consumed drugs and identify targets of illicit drugs use. The aims of the study were (1) to screen PU and urinated soil (US) samples collected at festivals for illicit drug excretion products using hyphenated techniques; (2) to develop and validate a hydrophilic interaction liquid chromatography - mass spectrometry / mass spectrometry (HILIC-MS/MS) method of quantifying urinary targets of identified drugs in wastewater; and (3) to conduct a 24 h stability study, using PU and US to better reflect the chemical environment for targets in wastewater. Cocaine (COC) and ecstasy-like compounds were the most frequently detected illicit drugs; an analytical method was developed to quantify their excretion products. Hydroxymethoxymethamphetamine (HMMA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), HMMA sulfate (HMMA-S), benzoylecgonine (BE), and cocaethylene (CE) had 85-102% of initial concentration after 8 h of incubation, whereas COC and ecgonine methyl ester (EME) had 74 and 67% after 8 h, respectively. HMMA showed a net increase during 24 h of incubation (107% ± 27, n = 8), possibly due to the cleavage of HMMA conjugates, and biotransformation of MDMA. The results suggest HMMA as analytical target for MDMA consumption in WBE, due to its stability in wastewater and its excretion as the main phase I metabolite of MDMA. Copyright © 2016 John Wiley & Sons, Ltd. Language: en

The authors regret for inconvenience caused but several affiliations should be corrected as follows: Erika Castrignanὁ , Zhugen Yang , Edward J. Feil , Richard Bade , Sara Castiglioni , Ana Causanilles , Emma Gracia-Lor , Felix Hernandez , Benedek G. Plosz , Pedram Ramin , Nikolaos I. Rousis , Yeonsuk Ryu , Kevin V. Thomas , Pim de Voogt , Ettore Zuccato , Barbara Kasprzyk-Hordern , ∗ Department of Chemistry, Faculty of Science, University of Bath, Bath, BA2 7AY, United Kingdom Department of Biology and Biochemistry, University of Bath, Bath, BA27AY, United Kingdom Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat s/n, E-12071, Castellὁn, Spain School of Pharmacy and Medical Sciences, University of South Australia, Adelaide, South Australia 5000, Australia Norwegian Institute for Water Research (NIVA), Gaustadalleen 21, 0349, Oslo, Norway Istituto di Ricerche Farmacologiche Mario Negri IRCCS, Department of Environmental Health Sciences, Via Mario Negri 2, 20156, Milan, Italy 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 Department of Environmental Engineering, Technical University of Denmark, Bygningstorvet, Building 115, 2800, Kgs. Lyngby, Denmark Process and Systems Engineering Center (PROSYS), Department of Chemical and Biochemical Engineering, Technical University of Denmark, Building 229,2800, Kgs. Lyngby, Denmark Department of Analytical, Environmental & Forensic Sciences, School of Population Health & Environmental Sciences, King's College London, London, SE19NH, United Kingdom School of Water, Energy and Environment, Cranfield University, Cranfield, MK43 0AL, United Kingdom Department of Chemical Engineering, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom Queensland Alliance for Environmental Health Science (QAEHS), University of Queensland, 20 Cornwall Street, Woolloongabba, QLD, 4102, Australia Department of Analytical Chemistry, Faculty of Chemistry, Complutense University of Madrid, Avenida Complutense s/n, Madrid, Spain The authors would like to apologise for any inconvenience caused.

In this chapter, the importance of risk assessment in biodiesel-based economy is first discussed. The importance of risk analysis to identify the most promising production schemes is also discussed from an economic point of view. Next, a systematic framework for economic risk assessment of biodiesel production processes and its associated by-products is presented. The application of the framework is highlighted through the production of 1,2-propanediol and 1,3-propanediol as value-added products from glycerol, which are critically assessed in terms of its techno-economic performance through the estimation of economic indicators, net present value (NPV), and minimum selling price (MSP). The Monte Carlo method with Latin Hypercube Sampling (LHS) is used to propagate the market price and technical uncertainties to the economic indicator calculations and to quantify the respective economic risk. In order to decrease the economic risk, the integrated production of the product as a module added to the biodiesel plant was tested as an alternative scenario. Using the integrated concept of utilizing the waste glycerol stream in biodiesel plants contributes to the diversification of the product portfolio for vegetable oil-based biorefineries, and in turn improves cost-competitiveness and robustness against market price fluctuations. The developed generic framework can be applied to other biodiesel by-products to assess the potentials of obtaining value-added products from them. Finally, future perspectives and other approaches toward economic production of biodiesel with lower risks are highlighted. The framework proposed in this work is to provide some detailed perspectives to facilitate the economic risk analysis of biodiesel production for any given technology.

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−1. 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. Keywords: Erectile dysfunction, Prescription drugs, LC-MS/MS, Consumption, Counterfeit, Wastewater-based epidemiology

Temperature is one of the key factors, influencing the transformation kinetics of organic chemicals. In the context of wastewater-based epidemiology, however, temperature differences among sewer catchments and within the same catchment (due to, e.g., seasonal variations) have been neglected to date as a factor influencing the estimation of illicit drug consumption. In this study, we assessed the influence of temperature on the transformation of biomarkers in wastewater and its ensuing implications on the back-calculation of chemical consumption rate in urban catchments using the example of selected illicit drugs. Literature data, obtained in laboratory-scale experiments, on the stability of drug biomarkers in untreated wastewater at trace levels was systematically reviewed, and transformation rates obtained at different temperatures were collected. Arrhenius-based equations were fitted to empirical data and identified to describe the transformation of selected cocaine and morphine biomarkers at applicability temperature range (from 2–9 °C to 30–31 °C), with estimated exponential Arrhenius coefficients between 1.04 and 1.18. These empirically-derived relationships were used to assess the influence of temperature on the transformation of drug biomarkers during in-sewer transport and its effect on the back-calculation of drug consumption rate in hypothetical urban catchment scenario simulations. Up to 4-fold increase in removal efficiency was estimated when wastewater temperature increased from 15 °C to 25 °C. Findings from this study can help reducing the uncertainty intrinsic to wastewater-based epidemiology studies, and will be beneficial in comparing chemical consumption estimates from different catchments worldwide.

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. (C) 2017 Elsevier B.V. All rights reserved.

The popularity of new psychoactive substances (NPS) has grown in recent years, with certain NPS commonly and preferentially consumed even following the introduction of preventative legislation. With the objective to improve the knowledge on the use of NPS, a rapid and very sensitive method was developed for the determination of ten priority NPS (N-ethylcathinone, methylenedioxypyrovalerone (MDPV), methylone, butylone, methedrone, mephedrone, naphyrone, 25-C-NBOMe, 25-I-NBOMe and 25-B-NBOMe) in influent wastewater. Sample clean-up and pre-concentration was made by off-line solid phase extraction (SPE) with Oasis MCX cartridges. Isotopically labelled internal standards were used to correct for matrix effects and potential SPE losses. Following chromatographic separation on a C18 column within 6 min, the compounds were measured by tandem mass spectrometry in positive ionization mode. The method was optimised and validated for all compounds. Limits of quantification were evaluated by spiking influent wastewater samples at 1 or 5 ng/L. An investigation into the stability of these compounds in influent wastewater was also performed, showing that, following acidification at pH 2, all compounds were relatively stable for up to 7 days. The method was then applied to influent wastewater samples from eight European countries, in which mephedrone, methylone and MDPV were detected. This work reveals that although NPS use is not as extensive as for classic illicit drugs, the application of a highly sensitive analytical procedure makes their detection in wastewater possible. The developed analytical methodology forms the basis of a subsequent model-based back-calculation of abuse rate in urban areas (i.e. wastewater-based epidemiology). The authors would like to thank all the personnel of the wastewater treatment plants for their collaboration in providing the samples: Sociedad de Fomento Agrícola Castellonense (FACSA, Castellon, Spain), VEAS (Oslo, Norway), Aquiris (Brussels, Belgium), Hoogheemraadschap de Stichtse Rijnlanden (Utrecht, the Netherlands), Wessex Water (Bristol, UK), Metropolitana Milanese (Milan, Italy), Werdhölzli (Zurich, Switzerland) and BIOFOS (Copenhagen, Denmark). RB, JBL, EC, AC, JK, AKM, PR and NIR acknowledge the European Union for their Early Stage Researcher (ESR) contracts and EGL for her Experienced Researcher (ER) contract as part of the EU-International Training Network SEWPROF (Marie Curie- PEOPLE Grant #317205). LB acknowledges NPS-Euronet (HOME/2014/JDRUG/AG/DRUG/7086), co-funded by the European Union, for his post-doctoral fellowship. This publication reflects the views only of the authors, and the European Commission cannot be held responsible for any use which may be made of the information contained therein. AvN acknowledges the support of the Flanders Foundation for Research (FWO). EGL is also thankful for the financial support from Generalitat Valenciana (APOSTD/2015, Programa VALi+d). The financial support of Generalitat Valenciana and of the Spanish Ministry of Economy and Competitiveness (Project ref CTQ2015-65603) is also acknowledged by the authors of University Jaume I.

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(ZS). 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.

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. This work is part of the EU Marie Curie Initial Training Network SEWPROF (Marie Curie-FP7-PEOPLE, grant No. 317205) and the financial support of the EU is greatly acknowledged. E.G.L. is also grateful to Generalitat Valenciana (APOSTD/2015, Programa VALi + d). The authors thank all personnel of the wastewater treatment plants for their collaboration in the collection of the wastewater samples.

Background: Monitoring 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. Method: This 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. Results: High 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. Conclusions: This 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. Jose Antonio Baz Lomba, Stefania Salvatore, Richard Bade, Erika Castrignanò, Ana Causanilles, Juliet Kinyua, Ann-Kathrin McCall, Pedram Ramin, Nikolaos I. Rousis, and Yeonsuk Ryu acknowledge the EU Marie-Skłodowska Curie Initial Training Network SEWPROF (Marie Curie-FP7-PEOPLE, grant number 317205) for their Early Stage Researcher grant and Emma Gracia-Lor for her Experienced Researcher grant. We thank the people and agencies who assisted in the collection of the wastewater samples, in particular Pia Ryrfors and colleagues at Vestfjorden Avløpselskap (VEAS, Oslo, Norway).

Monitoring population drug use through wastewater-based epidemiology (WBE) is a useful method to quantitatively follow trends and estimate total drug consumption in communities. Concentrations of drug biomarkers might be low in wastewater due to dilution; and therefore analysis of pooled urine (PU) is useful to detect consumed drugs and identify targets of illicit drugs use. The aims of the study were (1) to screen PU and urinated soil (US) samples collected at festivals for illicit drug excretion products using hyphenated techniques; (2) to develop and validate a hydrophilic interaction liquid chromatography - mass spectrometry / mass spectrometry (HILIC-MS/MS) method of quantifying urinary targets of identified drugs in wastewater; and (3) to conduct a 24 h stability study, using PU and US to better reflect the chemical environment for targets in wastewater. Cocaine (COC) and ecstasy-like compounds were the most frequently detected illicit drugs; an analytical method was developed to quantify their excretion products. Hydroxymethoxymethamphetamine (HMMA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), HMMA sulfate (HMMA-S), benzoylecgonine (BE), and cocaethylene (CE) had 85-102% of initial concentration after 8 h of incubation, whereas COC and ecgonine methyl ester (EME) had 74 and 67% after 8 h, respectively. HMMA showed a net increase during 24 h of incubation (107% ± 27, n = 8), possibly due to the cleavage of HMMA conjugates, and biotransformation of MDMA. The results suggest HMMA as analytical target for MDMA consumption in WBE, due to its stability in wastewater and its excretion as the main phase I metabolite of MDMA. Copyright © 2016 John WileySons, Ltd.

The measurement of illicit drugs and their human urinary metabolites in influents of municipal wastewater treatment plants (WWTPs) has been recently used to estimate prohibited drug consumption in catchment communities. In this study, a preliminary estimation of the consumption of cocaine (COC) in Lynetten catchment (Copenhagen, Denmark) was performed. The estimation was done from measured levels of the biomarker benzoylecgonine (BE), its major metabolite and COC by coupling hydrodynamics and biokinetics models. To assess the impact of hydraulic residence time (HRT) prediction on COC consumption estimates, we tested two methods. The conceptual hydrodynamic catchment model was developed to estimate HRT distribution in the catchment. Additionally, a simplified scaling equation was used to estimate mean HRT. A combination of hydrodynamics model and activated sludge model for xenobiotics (ASM-X) simulation results allowed to predict the extent of in-pipe removal of COC and BE in the sewer system. The preliminary assessment results showed that COC consumption rate when mean HRT is considered was 17% lower than HRT from conceptual model. The prediction of COC consumption rates when no diurnal variation of consumption was considered showed that this assumption could impose an error up to 40% as compared to considering 6-hour resolution sampling.

Wastewater samples information for the 8 European cities studied in 2015. The estimated population using the sewer network is showed in brackets (thousands of inhabitants within the catchment area). (DOCX 18 kb)

Wastewater samples information for the 8 European cities studied in 2015. The estimated population using the sewer network is showed in brackets (thousands of inhabitants within the catchment area). (DOCX 18 kb)

The study presents a global optimization strategy in designing a water reuse network for industrial symbiosis. Two optimization approaches, stochastic and deterministic, are compared based on the level of complexity of the network such as the number of contaminants, treatment unit selection, flow variation. Preliminary results on a general superstructure formulated as a mixed integer nonlinear programing shows promising performance of a stochastic model using a non-dominated sorting genetic algorithm. The developed optimization methodology will be extended to perform uncertainty and flexibility assessments of water reuse networks.

Aim: Pooled human urine and soil from urinating spots were collected anonymously at a Scandinavian music festival. Samples should be screened for drugs of abuse, particularly novel psychoactive substances (NPS), but also therapeutic drugs and ethanol. Methods: Twenty-one urine samples were collected anonymously from urinal and HMMA-d3 and trimipramin-d3 were added as internal standards. Additionally, 12 soil samples were collected near fences where people urinated. Urine samples were processed by enzymatic conjugate cleavage, SPE (HCX and C18), and acetylation prior to GC-MS. Soil samples and urine samples were also prepared by adding acetonitrile, shaking, centrifugation, and evaporation. Extracts were then analyzed by UHPLC-MSn (TF LXQ), UHPLC-HRMS/MS (TF Q-Exactive), and GC-MS (TF ISQ). Urine samples were additionally tested for 9-carboxy-THC by immunoassay and ethanol by headspace GC-MS Results: In the urine samples, the following compounds (and their metabolites) could be detected: cocaine (in 13 samples), levamisole (11), MDMA (9), amphetamine (2), and methamphetamine (2). Furthermore, therapeutic drugs such as metoprolol, carbamazepine, citalopram, quetiapine, methylphenidate, sertraline, and loperamide could be detected. 9-carboxy-THC was detected in most samples by immunoassay and confirmed by GC-MS; six thereof with immunoassay concentrations >50 ng/mL. The average ethanol concentration was 0.60 g/L ± 0.12 (α=0.05, n=21). In the soil samples, the following drugs of abuse could be detected besides several therapeutic drugs: cocaine (9), MDMA (7), sildenafil (2), ketamine (1), amphetamine (1), and oxycodone (1). Conclusions: NPS were detected neither in urine nor in soil samples. This might be due to low concentrations based on their negligible consumption at the studied festival side or chemical instability. Soil samples could be proved to be useful for investigating consumption of drugs of abuse as a supplement to urine samples

It is a common approach to report daily community-wide drug consumption, based on single daily measurements of the influent from a treatment plant. This article suggests that neglecting diurnal variations of loads and flow can result in misestimating daily drug consumption.

Biochemical processes determining the fate of micropollutants in wastewater are not limited to treatment plants (WWTPs), occurring also in sewer systems after discharge by excretion. In-sewer processes are associated mainly to the presence of biofilm attached on pipelines and suspended solids in raw sewage. Among existing micropollutants, in-sewer fate assessment is specifically relevant to illicit drugs, impacting the calculation of consumption levels in catchments according to the wastewater-based epidemiology approach (Zuccato et al., 2005). However, there is still a knowledge gap on the fate of illicit drugs in sewer systems. This study aims at assessing the role of suspended solids on the biotransformation and sorption in raw sewage of eight illicit drug biomarkers (cocaine, heroin, methadone, mephedrone, ketamine, methamphetamine, MDMA and THC and their urinary metabolites). Separate sets of batch experiments were performed to assess biotransformation and sorption of illicit drugs under aerobic and anaerobic conditions, prevailing in sewer systems. Biotransformation experiments were started by spiking a mixture of standards in methanol to batch reactors (final concentration of 10 μg L-1). Nine samples (240 ml) were taken over 48 h. Immediately after collection, samples were spiked with deuterated standards (final concentration 360 ngL-1) and stored at -20°C. Control experiments were also performed using mineral water under same experimental conditions of biotransformation experiments. Sorption experiments were performed according to the same procedure and with inactivation of biomass using sodium azide (0.05% v/v). Sample preparation and analysis consisted of solid phase extraction (SPE) with Oasis HLB cartridges followed by liquid chromatography coupled to high resolution mass spectrometry. The Activated Sludge Model for Xenobiotics (ASM-X) (Plósz et al., 2013) was used to simulate biotransformation and sorption of spiked chemicals. Monte Carlo method employing Latin Hypercube Sampling (LHS) of parameter space was used to estimate first-order abiotic (kabiotic, d-1) and pseudo-first-order biotransformation rate constants (kbio, L g-1 d-1), with root mean square normalized error as objective function. Sorption coefficients (Kd) were calculated from the decrease of aqueous concentrations during experiments.Experimental and modelling results are illustrated in Figure 1 and Table 1, which summarize experimental results and estimated parameter values for cocaine (COC) and its major metabolites benzoylecgonine (BE), ecgonine-methyl-ester (EME) and cocaethylene (CE). Our results suggest the formation of BE from COC and CE. COC transformation to CE and EME was assumed negligible (Plósz et al., 2013; Bisceglia and Lippa, 2014). A comparison of results from different experiments showed that abiotic transformation was overall prevalent under both redox conditions. Under anaerobic condition, in particular, transformation was almost completely associated to abiotic processes. Biotransformation rate constants (kbio) could not be estimated and should be considered negligible. These evidences are in agreement with earlier studies illustrating that chemical hydrolysis plays a major role in the transformation of cocaine biomarkers (Bisceglia and Lippa 2014). In addition, limited sorption for EME (Kd=0.7 L g-1) and BE (Kd=0.1 L g-1) and no sorption for COC and CE were observed.