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.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

Preparation and Characterization of a Cerium(IV)-incorporated Manganese Oxide OMS-2. Effect of Cerium(IV) Template on Octahedral Molecular Sieves of Manganese Oxide and Characterization of Manganese Oxide Molecular Sieves with Cerium(IV) as Dopant

The manganese oxide material K-OMS-2 was synthesized both via a redox reaction between potassium permanganate and manganese nitrate in an acidic medium (nitric acid) under reflux conditions and by the sol–gel reaction between KMnO 4 and maleic acid employed in a 3:1 molar ratio. Cerium(IV) was then added by an ion-exchange method. The structures, morphologies, chemical compositions and thermal stabilities of the resulting materials were studied by X-ray diffraction (XRD), N 2 adsorption/desorption, scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC) and TGA techniques. Both the morphologies and the surface properties of the materials synthesized by these two methods were different. Thus, the material prepared via the sol–gel process possessed a higher surface area and exhibited both a different type of adsorption isotherm and smaller crystallite sizes than the material synthesized by redox reaction under reflux conditions. The physical and chemical properties of the Ce–K-OMS-2 materials were similar to those of pure cryptomelane. TGA and XRD studies showed that the K-OMS-2 and Ce–K-OMS-2 materials exhibited a greater thermal stability in O 2 rather than N 2 atmospheres. In fact, the Ce(IV) derivatives were more stable thermally than the pure material. For Ce–K-OMS-2 R , the data obtained showed that part of the manganese in the framework was substituted by Ce(IV) ions. In contrast, the data for Ce–K-OMS-2 S indicated that not only did Ce(IV) ions substitute part of the manganese in the framework but that Ce(IV) ions also replaced the K + ions in the tunnel structure of the material

Diclofenac biodegradation by newly isolated Klebsiella sp. KSC: Microbial intermediates and ecotoxicological assessment

The presence of diclofenac, a frequently used analgesic drug in the environment, can be harmful to a variety of organisms like algae, crustaceans and fish. In this study, a bacterial strain of Klebsiella sp. KSC (Gen Bank, accession number KX500307) able to biodegrade high concentration of diclofenac was isolated from livestock soil and identified. The exposure of Klebsiella sp. KSC to 70 mg/L of diclofenac resulted in diclofenac mineralization after 72 h. This is the first study that points out substantial biodegradation of high concentration of diclofenac (70 mg/L) in less than 72 h; and this shows the potential of this strain to be bioaugmented in contaminated sites or to bioreactors. The chemical structure of twelve biotransformation products of diclofenac are proposed. Its transformation pathway may involve hydroxylation, dehydroxylation, decarboxylation and dechlorination of the central ring of diclofenac. Acute ecotoxicity assay with Vibrio fischeri test showed that the main biotransformation product (TP298) of diclofenac by Klebsiella sp. KSC was less toxic than the parent compound

DEGRADATION OF 4-TERT-BUTYLPHENOL IN WATER USING MONO-DOPED (M1: MO, W) AND CO-DOPED (M2-M1: CU, CO, ZN) TITANIA CATALYSTS

Mono-doped (Mo-TiO2 and W-TiO2) and co-doped TiO2 (Co-Mo-TiO2, Co-W-TiO2, Cu-Mo- TiO2, Cu-W-TiO2, Zn-Mo-TiO2, and Zn-W-TiO2) catalysts were synthesized by simple impregnation methods and tested for the photocatalytic degradation of 4-tert-butylphenol in water under UV (365 nm) light irradiation. The catalysts were characterized with various analytical methods. X-ray diffraction (XRD), Raman, Diffuse reflectance (DR) spectroscopies, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and Energy dispersive spectroscopy (EDS) were applied to investigate the structure, optical properties, morphology, and elemental composition of the prepared catalysts. The XRD patterns revealed the presence of peaks corresponding to the WO3 in W-TiO2, Co-W-TiO2, Cu-W-TiO2, and Zn-W-TiO2. The co-doping of Cu and Mo to the TiO2 lattice was evidenced by the shift of XRD planes towards higher 2 values, confirming the lattice distortion. Elemental mapping images confirmed the successful impregnation and uniform distribution of metal particles on the TiO2 surface. Compared to undoped TiO2, Mo-TiO2 andW-TiO2 exhibited a lower energy gap. Further incorporation of Mo–TiO2 with Co or Cu introduced slight changes in energy gap and light absorption characteristics, particularly visible light absorption. In addition, photoluminescence (PL) showed that Cu-Mo–TiO2 has a weaker PL intensity than undoped TiO2. Thus, Cu-Mo-TiO2 showed better catalytic activity than pure TiO2, achieving complete degradation of 4-tert-butylphenol under UV light irradiation after 60 min. The application of Cu-Mo-TiO2 under solar light conditions was also tested, and 70% of 4-tert-butylphenol degradation was achieved within 150 min

Uptake and bioaccumulation of three widely prescribed pharmaceutically active compounds in tomato fruits and mediated effects on fruit quality attributes

Pharmaceutically active compounds (PhACs) released in agroecosystems have been found to be taken up by and accumulated in the edible parts of crop plants. By employing simulated hydroponic cultivation under controlled conditions, the present study aimed at evaluating 1) the uptake and bioaccumulation of three common PhACs (diclofenac, DCF; sulfamethoxazole, SMX; trimethoprim, TMP), either applied individually (10 μg L-1) or as mixture (10 μg L-1 each), in tomato fruits harvested from the first three fruit sets, and 2) the PhACs-mediated effects on fruit quality attributes. DCF was not detected in tomato fruits, whereas both SMX and TMP were detected in varying concentrations in fruits, depending on the time of harvest, the mode of application and the allocation of plants in the greenhouse. The studied PhACs applied at environmentally relevant concentrations did not significantly affect plant productivity. Nevertheless, important fruit quality attributes, such as soluble solids and carbohydrate (fructose, glucose, sucrose, total sugars) content were significantly impacted by all studied PhACs applied individually, suggesting that for DCF, potentially its transformation products (TPs) (not examined in this study) may exert significant effects on fruits quality attributes. In addition, no additive or synergistic effects of the mixture of PhACs on studied fruits quality attributes were revealed. Gene expression analysis showed that the PhACs-mediated effects on the carbohydrate content of fruits can be attributed, at least to some extent, to the significant modulation of the abundance of transcripts related to the biosynthesis and catabolism of sucrose, such as SlSuSys, SlLin5 and SlLin7. To our knowledge, this is the first report highlighting the potential effects of PhACs released in agroecosystems on the quality of widely consumed agricultural products. In any case, further studies are warranted for the overall assessment of the potential impacts of PhACs on the quality of agricultural products under conventional agricultural conditions

Uptake and bioaccumulation of three widely prescribed pharmaceutically active compounds in tomato fruits and mediated effects on fruit quality attributes

Pharmaceutically active compounds (PhACs) released in agroecosystems have been found to be taken up by and accumulated in the edible parts of crop plants. By employing simulated hydroponic cultivation under controlled conditions, the present study aimed at evaluating 1) the uptake and bioaccumulation of three common PhACs (diclofenac, DCF; sulfamethoxazole, SMX; trimethoprim, TMP), either applied individually (10 μg L-1) or as mixture (10 μg L-1 each), in tomato fruits harvested from the first three fruit sets, and 2) the PhACs-mediated effects on fruit quality attributes. DCF was not detected in tomato fruits, whereas both SMX and TMP were detected in varying concentrations in fruits, depending on the time of harvest, the mode of application and the allocation of plants in the greenhouse. The studied PhACs applied at environmentally relevant concentrations did not significantly affect plant productivity. Nevertheless, important fruit quality attributes, such as soluble solids and carbohydrate (fructose, glucose, sucrose, total sugars) content were significantly impacted by all studied PhACs applied individually, suggesting that for DCF, potentially its transformation products (TPs) (not examined in this study) may exert significant effects on fruits quality attributes. In addition, no additive or synergistic effects of the mixture of PhACs on studied fruits quality attributes were revealed. Gene expression analysis showed that the PhACs-mediated effects on the carbohydrate content of fruits can be attributed, at least to some extent, to the significant modulation of the abundance of transcripts related to the biosynthesis and catabolism of sucrose, such as SlSuSys, SlLin5 and SlLin7. To our knowledge, this is the first report highlighting the potential effects of PhACs released in agroecosystems on the quality of widely consumed agricultural products. In any case, further studies are warranted for the overall assessment of the potential impacts of PhACs on the quality of agricultural products under conventional agricultural conditions

Stress-related phenomena and detoxification mechanisms induced by common pharmaceuticals in alfalfa (Medicago sativa L.) plants

Pharmaceutically active compounds (PhACs) have been recently shown to exert phytotoxic effects. The present study explores the uptake, systemic translocation, and abiotic stress responses and detoxification mechanisms induced by the exposure of alfalfa plants grown in sand under greenhouse conditions to four common, individually applied PhACs (10 μg L-1) (diclofenac, sulfamethoxazole, trimethoprim, 17a-ethinylestradiol) and their mixture. Stress physiology markers (lipid peroxidation, proline, H2O2 and NO content, antioxidant activity assays) and gene expression levels of key plant detoxification components (including glutathione S-transferases, GST7, GST17; superoxide dismutases, CuZnSOD, FeSOD; proton pump, H+-ATP, and cytochrome c oxidase, CytcOx), were evaluated. PhACs were detected in significantly higher concentrations in roots compared with leaves. Stress related effects, manifested via membrane lipid peroxidation and oxidative burst, were local (roots) rather than systemic (leaves), and exacerbated when the tested PhACs were applied in mixture. Systemic accumulation of H2O2 in leaves suggests its involvement in signal transduction and detoxification responses. Increased antioxidant enzymatic activities, as well as upregulated transcript levels of GST7, GST17, H+-ATPase and CytcOx, propose their role in the detoxification of the selected PhACs in plants. The current findings provide novel biochemical and molecular evidence highlighting the studied PhACs as an emerging abiotic stress factor, and point the need for further research on wastewater flows under natural agricultural environments