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This study aimed to determine the effect of land-use changes on the non-carcinogenic health risk of nitrate ion exposure of underground drinking water resources in Shiraz (Iran). To this end, 175 chemical samples for the nitrate analysis were regularly taken from 35 drinking water wells of Shiraz from 2013 to 2017, and their results were zoned using GIS. Hazard quotient (HQ) induced by nitrate ion exposure was determined in four age groups: infants, children, adolescents, and adults. Area changes of four types of land-use, including residential, agricultural and green space, industrial, and bare land within a radius of 400 m of drinking water wells, were determined using the GIS and Google Earth software. Then, all data was imported to Matlab 2018 for statistical analysis. The results showed that mean nitrate concentration increased by 2.5 mg L-1 from 2013 to 2017. According to the zoning map, 5 and 11.4% of the area in 2013 and 2017, respectively, exceeded the drinking water standard set by nitrate (i.e., 50 mg/L). Air temperature and precipitation variations also influenced nitrate concentrations and HQ changes (Rtemperature = 0.67). Children's age group was the most vulnerable, and during the study period, this vulnerability was an increasing trend, so that the HQ from 0.93 in 2013 to 0.97 in 2017 has increased. The rate of land-use changes in agricultural, industrial, bare, and urban was -1.8%, 1.3%, -4.6%, and 2.1%, respectively, and the highest correlation was observed between HQ and Diff.l residential land use (Rinfant = 0.55). According to the results, the most influential factor in HQ was air temperature (R = 0.66), and urban land-use change (R > 0.44). To sum up, this study's results showed that land-use changes, especially urban and residential development, significantly affect groundwater nitrate concentration and its degree of HQ. Moreover, increasing temperature and decreasing annual precipitation can also increase the severity of this risk., The results presented in this study are from the performed research projects at Behbahan Faculty of Medical Sciences (Research Intercept Code: 98067). Availability of data and materials All data generated or analyzed during this study are included in this published article.

The expected growth of urban areas requires the construction of underground infrastructures, especially for improving transportation and mobility. These new infrastructures are commonly constructed below the water table because they must be deeper than previous underground structures. In addition, many urban areas are located near surface water bodies (i.e., seas, rivers and/or lakes) that induce a shallow water table. The “cut and cover” method combined with dewatering wells is a frequently used procedure under these conditions for the construction of underground infrastructures. The main concerns of this procedure are related to the stability of the excavation bottom, the behavior of the retaining walls and/or the impacts induced by the dewatering actions. These issues must be evaluated, and new solutions must be proposed to improve its weak points. This paper compiles the main publications focused on the construction of underground infrastructures below the water table and in urban areas by using the cut and cover method combined with pumping. This review reveals that, despite many published studies, more research is needed to address some relevant issues such as: (1) the mitigation of dewatering impacts by using artificial recharge, (2) the adaptation of methods for characterizing retaining walls to be used under heterogeneous conditions, (3) the improvement of the prediction of surface settlements produced by pumping, and (4) the consideration of non-Darcy flows in the design of dewatering systems.

Aquifers under agricultural areas are considered to be an indirect source of nitrous oxide emission (N2O) to the atmosphere, which is the greenhouse gas (GHGs) characterized with the highest global warning potential and acts as a stratospheric ozone depletion agent. Previous investigations performed in the Cretaceous Hesbaye chalk aquifer in Eastern Belgium suggested that the dynamics of N2O in the aquifer is controlled by overlapping biochemical processes such as nitrification and denitrification. The current study aims to obtain better insight concerning the factors controlling the distribution of N2O concentration along a vertical dimension in the aquifer, and to capture and quantify the occurrence of nitrification and denitrification processes in the groundwater system. Low-flow groundwater sampling technique was undertaken at different depths in the aquifer to collect groundwater samples aiming at obtaining information about ambient aquifer hydrogeochemical conditions and their effect on the accumulation of GHGs. Afterwards, laboratory stable isotope experiments, using NO3- and NH4+ compounds labeled with heavy 15N isotope, were applied to quantify the rates of nitrification and denitrification processes. Ambient studies suggest that the occurrence of N transformation was related to denitrification while laboratory incubation experiments did not detect it. Such controversial results might be explained by the discrepancy between real aquifer conditions and lab design studies. Thus, additional in situ tracer experiments should be carried out in areas where natural groundwater fluxes do not flush the injected tracer too rapidly. In addition, it would be useful to conduct microbiological studies to obtain better insight into the nature of subsurface biofilm biotope., This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 675120. Los Gatos Research OA-ICOS was funded by the Fonds National de la Rechecherche Scientifique (FNRS) (22547486). AVB is a Research Director at the FNRS.

Underground pumped hydropower storage (UPHS) using abandoned mines is an alternative to store and produce electricity in flat regions. Excess of electricity is stored in form of potential energy by pumping mine water to a surface reservoir. When the demand of electricity increases, water is discharged into the mine (i.e., underground reservoir) through turbines producing electricity. During the complete operational process of UPHS plants, hydrochemical characteristics of water evolve continuously to be in equilibrium successively with the atmosphere (in the surface reservoir) and the surrounding porous medium (in the underground reservoir). It may lead to precipitation and/or dissolution of minerals and their associated consequences, such as pH variations. Induced hydrochemical changes may have an impact on the environment and/or the efficiency (e.g., corrosions and incrustations affect facilities) of UPHS plants. The nature of the hydrochemical changes is controlled by the specific chemical characteristics of the surrounding porous medium. However, the magnitude of the changes also depends on other variables, such as hydraulic parameters. The role of these parameters is established to define screening criteria and improve the selection procedure of abandoned mines for constructing UPHS plants. This work evaluates the role of the main hydrogeological factors for three different chemical composition of the porous medium. Results are obtained by means of numerical reactive transport modeling. Potential impacts on the environment (mainly on groundwater and surface water bodies) and on the efficiency of the UPHS plants vary considerably from a hydraulic parameter to another showing the need for a detailed characterization before choosing locations of future UPHS plants.

Groundwater is the main source of water supply in the European Union and therefore, the conservation and protection of this freshwater resource against pollution are key issues. Organic micropollutants have raised concern as wastewater treatment plants partly remove them and thus, they continuously enter the aquifers, threatening groundwater quality.

Pharmaceuticals, such as non-steroidal anti-inflammatory drugs (NSAIDs) and their metabolites, have become a major concern due to their increasing consumption and their widespread occurrence in the environment. In this paper, we investigate the occurrence of NSAIDs and their metabolites in an urban aquifer, which may serve as a potential resource for drinking water, and propose a methodology to assess the removal of these substances in the river–groundwater interface. Then, risk quotients (RQs) are computed, in order to determine the risk posed by the single NSAIDs and their mixture to human health. To this end, six NSAIDs and two metabolites were collected from an urban aquifer located in the metropolitan area of Barcelona (NE, Spain), in which the major pollution source is a contaminated river. All of the target NSAIDs were detected in groundwater samples, where the concentrations in the aquifer were higher than those found in the river water (except for ibuprofen). Diclofenac, ketoprofen, propyphenazone and salicylic acid were detected at high mean concentrations (ranging from 91.8 ng/L to 225.2 ng/L) in the aquifer. In contrast, phenazone and mefenamic acid were found at low mean concentrations (i.e., lower than 25 ng/L) in the aquifer. According to the proposed approach, the mixing of river water recharge into the aquifer seemed to some extent to promote the removal of the NSAIDs under the sub-oxic to denitrifying conditions found in the groundwater. The NSAIDs that presented higher mean removal values were 4OH diclofenac (0.8), ibuprofen (0.78), salicylic acid (0.35) and diclofenac (0.28), which are likely to be naturally attenuated under the aforementioned redox conditions. Concerning human health risk assessment, the NSAIDs detected in groundwater and their mixture do not pose any risk for all age intervals considered, as the associated RQs were all less than 0.05. Nevertheless, this value must be taken with caution, as many pharmaceuticals might occur simultaneously in the groundwater., IDAEA-CSIC is a Centre of Excellence Severo Ochoa (Spanish Ministry of Science and Innovation, Project CEX2018-000794-S). A. J gratefully acknowledges the support from the Secretary for Universities and Research of the Ministry of Economy and Knowledge of the Government of Catalonia and the Marie Sklodowska-Curie COFUND of the programme H2020 (BP3, contract number 801370). The authors would like to thank the European Commission, the Spanish Foundation for Science & Technology (FECYT) and State Research Agency (AEI)) for funding in the frame of the collaborative international consortium (URBANWAT) financed under the 2018 Joint call of the WaterWorks2017 ERA-NET Cofund. This ERA-NET is an integral part of the activities developed by the Water JPI. Additionally, authors would also thank the Ministry of Science, Innovation and Universities, for funding the projects UNBIASED (Ref: RTI2018-097346-B-I00) under the 2018 call of the “Proyectos de I+D Retos Investigación” and INTEGRATE (Ref: PID2019-107945RJ-I00) under the 2019 call of the “Proyectos de I+D Retos Investigación”.

An extensive survey of groundwater quality was performed at the regional scale in peri-urban and industrial contexts of the Walloon Region (Belgium). To this end, 243 sampling locations from 8 areas located in different geological contexts and different peri-urban areas of the region were sampled outside pollution hotspots related to contaminated sites. Each groundwater sample was analyzed for 19 inorganic trace elements, 59 organic micro-pollutants and 8 major and minor elements. Five physico-chemical parameters were measured in the field, at the time of sampling to determine the environmental conditions prevailing in groundwater. Existing groundwater chemical data available outside such peri-urban and industrial areas were also compiled from existing groundwater quality databases for comparison. Most of the organic and inorganic pollutants are detected and their levels of occurrence are described statistically. Cumulative distribution function plots allow comparing the distributions of inorganic trace elements in and outside the urbanized and industrialized areas and among the different prevailing geological contexts. Two indicators are introduced, one quantifying the impact on inorganic trace elements of diffuse pollution in urban and industrial areas, the other reflecting the influence of lithology on concentrations in groundwater. Results show that the composition of groundwater is altered in peri-urban and industrial areas with increased concentrations for several organic pollutants and for most inorganic trace elements. However, the results clearly indicate that for the inorganic trace elements, anthropogenic influence is not limited to increased discharge of pollutants in the urban and industrial areas but also to significant changes in environmental conditions, with more reducing and acidic conditions observed in groundwater. The influence of lithology is also marked in the data set. From a more pragmatic point of view, the data set has been also used to derive upper limits of pollutant background concentrations to be used in decision-making related to the management of contaminated groundwater in urban and industrial environments in the Walloon Region., This study is a contribution to the project POLLUSOL2. This project was supported by SPAQuE (Belgium) including news piezometers and new samples and analyses. We also thank the Service Public de Wallonie - DGO3 Département de l'Eau et l'Environnement – Direction des Eaux Souterraines for the databases provided.

This study investigates the occurrence of greenhouse gases (GHGs) and the role of groundwater as an indirect pathway of GHG emissions into surface waters in a gaining stretch of the Triffoy River agricultural catchment (Belgium). To this end, nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations, the stable isotopes of nitrate, and major ions were monitored in river and groundwater over 8 months. Results indicated that groundwater was strongly oversaturated in N2O and CO2 with respect to atmospheric equilibrium (50.1 vs. 0.55 μg L−1 for N2O and 14,569 vs. 400 ppm for CO2), but only marginally for CH4 (0.45 vs. 0.056 μg L−1), suggesting that groundwater can be a source of these GHGs to the atmosphere. Nitrification seemed to be the main process for the accumulation of N2O in groundwater. Oxic conditions prevailing in the aquifer were not prone for the accumulation of CH4. In fact, the emissions of CH4 from the river were one to two orders of magnitude higher than the inputs from groundwater, meaning that CH4 emissions from the river were due to CH4 in-situ production in riverbed or riparian zone sediments. For CO2 and N2O, average emissions from groundwater were 1.5 × 105 kg CO2 ha−1 year−1 and 207 kg N2O ha−1 year−1, respectively. Groundwater is probably an important source of N2O and CO2 in gaining streams but when the measures are scaled at catchment scale, these fluxes are probably relatively modest. Nevertheless, their quantification would better constrain nitrogen and carbon budgets in natural systems.

Underground pumped storage hydropower (UPSH) using abandoned mines is an alternative system to manage electricity production in flat regions. Water from an underground reservoir is pumped to a surface reservoir to store electricity in the form of potential energy. Later, water is discharged through turbines into the underground reservoir to produce electricity when demand increases. During this operation, the water hydrochemistry continuously evolves. It varies in order to reach chemical equilibrium with the atmosphere (in the surface reservoir) and with the surrounding porous medium and groundwater (in the underground reservoir). The hydrochemical variations may lead to reactions in the reservoirs and in the surrounding porous medium, causing potentially negative consequences for the environment and the system efficiency, especially when pyrite is present in the surrounding porous medium. In this case, pyrite oxidation leads to a decrease in pH and the precipitation of goethite or schwertmannite in the surface reservoir. The decrease in pH is mitigated when calcite is present in the porous medium. However, other concerns may arise, such as slight increases in pH, the precipitation of ferrihydrite and calcite in the surface reservoir, and the oxidation of pyrite and dissolution of calcite in the surrounding porous medium. Understanding the pH variations and the precipitation/dissolution of minerals is of paramount importance in terms of the environmental impacts and system efficiency. For this reason, this work investigates the main hydrochemical changes and their associated consequences when abandoned deep mines are used for UPSH by means of numerical modelling. The main objective is to highlight the importance of considering hydrochemical aspects when designing future UPSH plants.

We report a data-set of CO2, CH4, and N2O concentrations in the surface waters of the Meuse river network in Belgium, obtained during four surveys covering 50 stations (summer 2013 and late winter 2013, 2014 and 2015), from yearly cycles in four rivers of variable size and catchment land cover, and from 111 groundwater samples. Surface waters of the Meuse river network were over-saturated in CO2, CH4, N2O with respect to atmospheric equilibrium, acting as sources of these greenhouse gases to the atmosphere, although the dissolved gases also showed marked seasonal and spatial variations. Seasonal variations were related to changes in freshwater discharge following the hydrological cycle, with highest concentrations of CO2, CH4, N2O during low water owing to a longer water residence time and lower currents (i.e. lower gas transfer velocities), both contributing to the accumulation of gases in the water column, combined with higher temperatures favourable to microbial processes. Inter-annual differences of discharge also led to differences in CH4 and N2O that were higher in years with prolonged low water periods. Spatial variations were mostly due to differences in land cover over the catchments, with systems dominated by agriculture (croplands and pastures) having higher CO2, CH4, N2O levels than forested systems. This seemed to be related to higher levels of dissolved and particulate organic matter, as well as dissolved inorganic nitrogen in agriculture dominated systems compared to forested ones. Groundwater had very low CH4 concentrations in the shallow and unconfined aquifers (mostly fractured limestones) of the Meuse basin, hence, should not contribute significantly to the high CH4 levels in surface riverine waters. Owing to high dissolved concentrations, groundwater could potentially transfer important quantities of CO2 and N2O to surface waters of the Meuse basin, although this hypothesis remains to be tested.

Urban groundwater has often been over-exploited for industrial uses. Now, this usage tends to be reduced or the resource abandoned due to pollution and/or changes in land use. The use and the subsequent disuse of groundwater has resulted in rising water tables that damage underground structures (e.g., building basements and underground car parks and tunnels), leading to the need for additional pumping in urban areas. In the case of the underground parking lot of Sant Adria del Besos (Barcelona, NE Spain), large amounts of urban groundwater are pumped to avoid seepage problems. Can this pumped groundwater be used for other purposes (e.g., drinking water and urban irrigation) instead of wasting this valuable resource? To answer this question, it was necessary to quantify the groundwater recharge and to assess the evolution of groundwater quality. The limiting factor at this study site is the groundwater quality because ammonium and some metals (iron and manganese) are present at high concentrations. Hence, further treatment would be needed to meet drinking water requirements. The pumped groundwater could also be used for supplementing river flow for ecological benefit and/or for mitigating seawater intrusion problems. Currently, only a small amount of this urban groundwater is used for cleaning public areas and watering public gardens. This situation highlighted the urgent need to manage this resource in a responsible and more efficient manner, especially in moments of high water demand such as drought periods.

This work presents the occurrence and fate of selected personal care products (PCPs) in the urban river-groundwater interface. To this end, urban river and groundwater samples were collected in Sant Adrià del Besòs (NE of Spain) and a total of 16 PCPs were analyzed including benzophenone derivatives, camphor derivatives, p-aminobenzoic acid derivatives, triazoles and parabens in three different campaigns (from May 2010 to July 2014). These compounds reach the aquifer through the recharge of Besòs River that receives large amounts of effluents from waste water treatment plants. Results have shown that most of the compounds were not or barely detected (maximum concentrations around 200ng/L) in groundwater samples during the different sampling campaigns. Only two triazoles, namely benzotriazole (BZT) and methyl benzotriazol (MeBZT) were found at high concentrations in groundwater samples (maximum concentration around 2000ng/L). The fate of PCPs in the aquifer was assessed using mixing analysis considering the seasonal variability of the Besòs River. Overall, measured groundwater concentrations were significantly much lower than those estimated by the mixing of the river water. This observation suggested that most of the PCPs are naturally removed when river water infiltrates the aquifer. However, some compounds were more persistent in the aquifer. These compounds were in descending order: the triazoles BZT and MeBZT followed by the camphor derivative 4MBC and the paraben MePB. The measured concentrations allowed us to assess the environmental risk posed by the selected UV-filters and parabens in the river and groundwater samples. Hazard Quotients (HQs) for different aquatic species were calculated in order to characterize the ecotoxicity potential of the studied compounds in the river-groundwater interface. HQ values were always below 1 indicating that at the concentrations observed in the surface or aquifer water of Besòs River these compounds pose no risk to the selected aquatic organisms.

Antibiotics, such as sulfonamides (SAs), have recently raised concern as wastewater treatment plants (WWTPs) partly remove them, and thus, SAs continuously enter the aquifers. In this context, the aims of this work are to (1) investigate the temporal evolution of SAs and metabolites in an urban aquifer recharged by a polluted river; (2) identify the potential geochemical processes that might affect SAs in the river-groundwater interface and (3) evaluate the ecological and human health risk assessment of SAs. To this end, 14 SAs and 4 metabolites were analyzed in river and urban groundwater from the metropolitan area of Barcelona (NE, Spain) in three different sampling campaigns. These substances had a distinct behavior when river water, which is the main recharge source, infiltrates the aquifer. Mixing of the river water recharge into the aquifer drives several redox reactions such as aerobic respiration and denitrification. This reducing character of the aquifer seemed to favor the natural attenuation of some SAs as sulfamethoxazole, sulfapyridine, and sulfamethizole. However, most of the SAs detected were not likely to undergo degradation and adsorption because their concentrations were constant along groundwater flow path. In fact, the intensity of SAs adsorption is low as the retardation factors are close to 1 at average groundwater pH of 7.2 for most SAs. Finally, risk quotients (RQs) are used to evaluate the ecological and human health risks posed by single and mixture of SAs in river water and groundwater, respectively. Life-stage RQs of the SAs detected in groundwater for the 8 age intervals were low, indicating that SAs and their mixture do not pose any risk to human beings. Concerning the environmental risk assessment, SAs do not pose any risk for algae, fish and crustaceans as the RQs evaluated are further lower than 0.1., A.J acknowledges the support from the Secretary for Universities and Research of the Ministry of Economy and Knowledge of the Government of Catalonia and the Marie Sklodowska-Curie COFUND of the programme H2020 (BP3, contract number 801370). M.S.D.C acknowledges the Generalitat de Catalunya (Water and Soil Quality Unit, 2017-SGR-1404) and the Spanish Ministry of Science and Innovation (Project CEX 2018-000794-S). E.V.S would like to thank the European Commission, the Spanish Foundation for Science & Technology (FECYT) and State Research Agency (AEI)) for funding in the frame of the collaborative international consortium (URBANWAT) financed under the 2018 Joint call of the WaterWorks2017 ERA-NET Cofund. This ERA-NET is an integral part of the activities developed by the Water JPI. Additionally E.V.S also thank the Ministry of Science, Innovation and Universities, for funding the project UNBIASED (Ref: RTI 2018-097346-B-I00) under the 2018 call of the “Proyectos de I + D Retos Investigación.

AkvaGIS is a novel, free and open source module included in the FREEWAT plugin for QGIS that supplies a standardized and easy-to-use workflow for the storage, management, visualization and analysis of hydrochemical and hydrogeological data. The main application is devised to simplify the characterization of groundwater bodies for the purpose of building rigorous and data-based environmental conceptual models (as required in Europe by the Water Framework Directive). For data-based groundwater management, AkvaGIS can be used to prepare input files for most groundwater flow numerical models in all of the available formats in QGIS. AkvaGIS is applied in the Walloon Region (Belgium) to demonstrate its functionalities. The results support a better understanding of the hydrochemical relationship among aquifers in the region and can be used as a baseline for the development of new analyses, e.g., further delineation of nitrate vulnerable zones and management of the monitoring network to control chemical spatial and temporal evolution. AkvaGIS can be expanded and adapted for further environmental applications as the FREEWAT community grows. © 2018 The Authors, Funding text This paper is presented within the framework of the project FREEWAT , which received funding from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement n. 642224 . R. Criollo thanks the financial support from the Catalan Industrial Doctorates Plan of the Secretariat for Universities and Research , Ministry of Economy and Knowledge of the Generalitat de Catalunya . A. Jurado and E. Pujades gratefully acknowledge the financial support from the University of Liège and the EU through the Marie Curie BeIPD-COFUND postdoctoral fellowship programme (2015–2017 and 2014–2016 fellows from FP7-MSCA-COFUND , 600405 ).

Water scarcity periods will increase in frequency and magnitude in the near future, especially in Mediterranean regions, and proper groundwater management has been recognized as a key issue to mitigate possible impacts. In this context, numerical models acquire a special relevance to quantify the availability of water resources and predict their behavior under changing climate conditions. This work shows the procedure followed to model a mountainous fractured aquifer located in the northern Apennines (Italy) using an open source code. This aquifer feeds springs with an average discharge of about 96.8 L/s. Even though they are not exploited at the moment, these springs might represent a relevant resource of freshwater for public water supply and are essential for ecosystem sustainment. The main limitation faced to model the aquifer in a realistic way is the lack of data, which hinders the calibration of the model. A nonconventional procedure was followed to obtain information on the hydraulic parameters. The hydraulic conductivity is computed from a steady-state calibration for which a limited number of groundwater head observations are available, whilst information concerning the storage coefficient is obtained analytically from the spring discharge recession curve. Finally, the model is used for predicting the system behavior under different groundwater recharge scenarios. Numerical simulations and analytical approximations reveal that the studied aquifer can provide fresh water under different groundwater recharge conditions and has the capacity to smooth the effects of short drought periods, representing an option for water management strategies in the region.

The aim of this study is to investigate the occurrence of faecal indicator and microbial pathogens (bacteria and virus) in the shallow urban aquifer of the Besòs River Delta (NE Spain). To this end, human adenovirus (HAdV) and Norovirus of genogroups I and II (NoV GI and NoV GII) as well as the faecal indicator bacteria (FIB) Escherichia coli (EC) and faecal enterococci (FE) were monitored in groundwater and in the River Besòs in December 2013 and in July 2104. None of the targeted pathogens were detected in groundwater in December 2013 but contamination of human origin was observed in approximately 50% of the points sampled in July 2014 reaching concentrations up to 99 GC/100 mL for HAdV. Generally, microbial concentrations in river water were higher than those detected in groundwater. This observation indicates that pathogens are naturally attenuated when river water infiltrates and flows through the aquifer, however HAdV were detected at a sampling point located at 380 m from the river in the absence of FIB. The presence of human viral contamination may represent a risk for the use of groundwater as a drinking water source. Further research is needed to understand the dynamics of pathogens in river–groundwater interface over long time periods and a wide range of flow conditions (wet and dry periods) since the urban groundwater of this aquifer might be a valuable drinking water resource in Barcelona especially during drought periods. The methodology followed in this research can be applied to other urban aquifers with similar purposes since the scarcity and contamination of freshwater resources are worldwide issues. © 2019 Elsevier B.V., A. J gratefully acknowledges the financial support from the Excellence Initiative of the German Federal and State Governments through the “Open Topic Postdoc Position Fellow” at the Technische Universität Dresden. The authors would like to thank the European Commission, the Spanish Foundation for Science and Technology (FECYT) and Spanish State Research Agency (AEI) for funding in the frame of the collaborative international consortium (URBANWAT) financed under the 2018 Joint call of the WaterWorks2017 ERA-NET Cofund. This ERA-NET is an integral part of the activities developed by the Water JPI. Additionally authors would also thank the Ministry of Science, Innovation and Universities, for funding the project UNBIASED (Ref: RTI2018-097346-B-I00) under the 2018 call of the “Proyectos de I+D Retos Investigación.

This paper aims to review the existing occurrence data in Spanish groundwater (GW) for the emerging organic contaminants (EOCs) defined in the surface water Watch Lists of Decisions 2015/495/EU and 2018/840/EU since these contaminants are likely to reach GW bodies because surface waters show close interaction with GW. These two lists include 20 substances: 9 pesticides (5 neonicotinoids, 2 carbamates, 1 oxadiazole and 1 semicarbazone), 6 pharmaceuticals (diclofenac and 5 antibiotics), 3 estrogens, 1 UV filter (2-ethylhexyl-4-methoxycinnamate, EHMC) and 1 antioxidant (2,6-di-tert-butyl-4-methylphenol, BHT). Most of these substances are usually detected at low ng/L concentration range or not detected in the GW bodies of Spain. However, eventually they are reported at concentrations > 100 ng/L (e.g., imidacloprid, methiocarb, diclofenac, macrolide antibiotics, ciprofloxacin, EHMC and BHT). Consequently, it is required to set up drinking water standards, and/or GW threshold quality values because GW is a valuable water resource worldwide. Overall, GW is less contaminated than other water bodies, such as rivers, suggesting that aquifers possess a natural attenuation capacity and/or are less vulnerable than rivers to contamination. Nevertheless, the natural hydrogeochemical processes that control the fate and transformation of these substances during infiltration and in the aquifer have been barely investigated so far. The concentrations of the target EOCs are used to calculate hazard quotients (HQs) in the Spanish GW bodies as an estimation of their ecotoxicity and in order to compare somehow their chemical quality with respect to those of surface water. Due to the limited ecotoxicity data for most EOCs, HQs can only be calculated for few substances. The results pointed out the risk posed by the anti-inflammatory diclofenac towards Ceriodaphnia dubia (HQ = 21) and the medium risk associated to the antibiotic erythromycin for Brachionus calyciflorus (HQ = 0.46). © 2019 Elsevier B.V., AJ gratefully acknowledges the financial support from the Excellence Initiative of the German Federal and State Governments through the “Open Topic Postdoc Position” Fellow at the Technische Universität Dresden . MSDC acknowledges the Spanish Ministry of Science, Innovation and University and the European Commission (Project ACWAPUR PCIN 2015-245 ). Appendix A

This work is motivated by a sound understanding of the chemical processes that affect the organic pollutants in an urban aquifer. We propose an approach to quantify such processes using mixing calculations. The methodology consists of the following steps: (1) identification of the recharge sources (end-members) and selection of the species (conservative and non-conservative) to be used, (2) identification of the chemical processes and (3) evaluation of mixing ratios including the chemical processes. This methodology has been applied in the Besòs River Delta (NE Barcelona, Spain), where the River Besòs is the main aquifer recharge source. A total number of 51 groundwater samples were collected from July 2007 to May 2010 during four field campaigns. Three river end-members were necessary to explain the temporal variability of the River Besòs: one river end-member is from the wet periods (W1) and two are from dry periods (D1 and D2). This methodology has proved to be useful not only to compute the mixing ratios but also to quantify processes such as calcite and magnesite dissolution, aerobic respiration and denitrification undergone at each observation point.

This work aims to (1) identify the most conductive conditions for the generation of greenhouses gases (GHGs) in groundwater (e.g., hydrogeological contexts and geochemical processes) and (2) evaluate the indirect emissions of GHGs from groundwater at a regional scale in Wallonia (Belgium). To this end, nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations and the stable isotopes of nitrate (NO3-) and sulphate were monitored in 12 aquifers of the Walloon Region (Belgium). The concentrations of GHGs range from 0.05μg/L to 1631.2μg/L for N2O, 0μg/L to 17.1μg/L for CH4, and 1769 to 100,514ppm for the partial pressure of CO2 (pCO2). The highest average concentrations of N2O and pCO2 are found in a chalky aquifer. The coupled use of statistical techniques and stable isotopes is a useful approach to identify the geochemical conditions that control the occurrence of GHGs in the aquifers of the Walloon Region. The accumulation of N2O is most likely due to nitrification (high concentrations of dissolved oxygen and NO3- and null concentrations of ammonium) and, to a lesser extent, initial denitrification in a few sampling locations (medium concentrations of dissolved oxygen and NO3-). The oxic character found in groundwater is not prone to the accumulation of CH4 in Walloon aquifers. Nevertheless, groundwater is oversaturated with GHGs with respect to atmospheric equilibrium (especially for N2O and pCO2); the fluxes of N2O (0.32kgN2O-NHa-1y-1) and CO2 (27kgCO2Ha-1y-1) from groundwater are much lower than the direct emissions of N2O from agricultural soils and fossil-fuel-related CO2 emissions. Thus, indirect GHG emissions from the aquifers of the Walloon Region are likely to be a minor contributor to atmospheric GHG emissions, but their quantification would help to better constrain the nitrogen and carbon budgets.

This paper deals with urban groundwater contaminated with carbamazepine (CBZ) and five of its human metabolites in Barcelona. Groundwater samples were accordingly collected in the aquifers of Poble Sec and Besos River Delta. Higher concentrations and more compounds were found in the Besos River Delta aquifer, which is recharged by a river contaminated with treated effluent from numerous treatment plants. By contrast, the urban area of Poble Sec presented lower concentrations and fewer compounds. The results showed that CBZ could be attenuated in the Poble Sec aquifer since concentrations in groundwater were lower than those evaluated from mixing of the recharge sources. Conversely, CBZ and its human metabolites were not removed under the reducing conditions of the Besos River Delta aquifer probably because of the short residence time in this aquifer. (C) 2014 Elsevier Ltd. All rights reserved.

The present paper presents the occurrence of 72 pharmaceuticals and 23 transformation products (TPs) in groundwaters (GWs) underlying the city of Barcelona, Spain. Thirty-one samples were collected under different districts, and at different depths. Aquifers with different geologic features and source of recharge were included, i.e., natural bank filtration, infiltration from wastewater and water supply pipes, rainfall recharge, etc. Antibiotics were the most frequently found compounds detected at levels reaching 1000 ng L −1 . Natural bank filtration from the river that receives large amounts of effluents from waste water treatment plants (WWTPs), turned out being the most influencing source of contamination, thus GW showed high range of compounds and concentrations as high as or even higher than in the river itself. In general, TPs were found at lower concentrations than the corresponding parent compounds, with some exceptions, such as 4OH propranolol and enalaprilat.

Underground Pumped Storage Hydropower (UPSH) is an alternative to manage the electricity production in flat regions. UPSH plants consist of two reservoirs of which at least one is underground. For this last reservoir, abandoned mines could be considered. UPSH related activities may induce hydrochemical variations, such as the increase of the oxygen (O2) partial pressure (pO2), which may entail negative consequences in terms of environment and efficiency, especially in coal mined areas where the presence of sulfide minerals is common. This work assesses the main expected environmental impacts that UPSH using abandoned coal mines may induce. © 2017 The Authors. Published by Elsevier Ltd., E. Pujades and A. Jurado gratefully acknowledge the financial support from the University of Liège and the EU through the Marie Curie BeIPD-COFUND postdoctoral fellowship programme (2014/16 and 2015/17 fellows from “FP7-MSCA-COFUND, 600405”). This research has been supported by the Public Service of Wallonia – Department of Energy and Sustainable Building.

This study is concerned with drugs of abuse (DAs) and their metabolites in urban groundwater at field scale in relation to (1) the spatial distribution of DAs in Barcelona's groundwater, (2) the depth of the groundwater samples, (3) the presence of DAs in recharge sources, and (4) the assessment of the fate of DAs in Barcelona aquifers. To this end, 37 urban groundwater samples were collected in the city of Barcelona and a total of 21 drugs were analyzed including cocainics, amphetamine-like compounds, opioids, lysergics and cannabinoids and the prescribed drugs benzodiazepines. Overall, the highest groundwater concentrations (around 200 ng/L in SAP-4) and the largest number of detected DAs were found in zones basically recharged by a river that receives large amounts of effluents from waste water treatment plants (WWTPs). In contrast, the urbanized areas yielded not only lower concentrations but also a much smaller number of drugs, which suggests a local origin. In fact, cocaine and its metabolite were dominant in more prosperous neighborhoods, whereas the cheaper MDMA was the dominant DA in poorer districts. Measured concentrations were consistently smaller than those estimated from the waste water fraction in groundwater samples, suggesting that DAs undergo removal processes in both reducing and oxidizing conditions.

In this chapter we take a look at the presence of emerging organic compounds (EOCs) in groundwater, with emphasis in sources of pollution, processes affecting the spatial and temporal concentration of these compounds as they move through the aquifer and interact with the soil. Emphasis is placed on the combination of transport mechanisms and physical and biogeochemical processes that combine for natural attenuation and the potential eventual output to the biosphere. Some considerations about risks associated to the presence of such substances are also included.

The occurrence and fate of UV filters (UV F) in an urban aquifer in correlation with (1) the spatial distribution of UV Fin Barcelona's groundwater, (2) the depth of the groundwater sample, (3) the physicochemical properties of the target compounds, (4) the recharge sources, and (5) the redox conditions of the Barcelona aquifers, were studied for the first time. The highest groundwater concentrations and the largest number of detected UV F were observed in an aquifer recharged by a polluted river (around 55 ng/L in SAP-4). In contrast, the urbanized areas had lower concentrations (around 20 ng/L in MPSP-1). Two pathways can be identified for UV F to enter the aquifers: (1) leakage of row sewage from the sewage network in urbanized areas and (2) wastewater treatment plant (WWTP) effluents discharged into the river. Measured concentrations of UV F were significantly much lower than those estimated from the waste water proportion in groundwater samples suggesting that UV F might undergo transformation processes in both reducing and oxidizing conditions. (c) 2014 Elsevier B.V. All rights reserved.

In this study the variability of greenhouse gases (GHGs) concentrations along lateral and vertical dimensions of the chalk aquifer located in the eastern part of Belgium was examined in order to understand its dependence on hydrogeological and hydrogeochemical conditions. Groundwater samples from 29 wells/piezometers were analyzed for concentrations of nitrous oxide (N2O), carbon dioxide (CO2), methane (CH4), major and minor elements and stable isotopes of nitrate (NO3−), nitrous oxide (N2O), sulfate (SO42−) and boron (B). For lateral investigations, four zones with different environmental settings were identified (southern, central, north-eastern and northern). Groundwater was oversaturated with GHGs with respect to its equilibrium concentrations with the atmosphere in all zones, except the northern one, undersaturated in N2O (0.07 ± 0.08 μgN/L vs. 0.3 μgN/L). Vertical dimension studies showed the decrease in CO2 concentration and significant changes in both isotope signatures and concentration of N2O with depth. The production of N2O could be attributed to a combination of nitrification and denitrification processes occurring at different depths. CO2 concentration is controlled by the process of dissolution of carbonate minerals which constitute aquifer geology. CH4 is produced due to methanogenesis in deeper parts of the aquifer, though its thermogenic origin is also possible. Differences in hydrogeochemical settings and changing intensity of biogeochemical processes across the area and with depth have considerable effect on GHGs concentrations. Thus, before estimating GHGs fluxes at the groundwater–river interface insights obtained from larger-scale investigations are required in order to identify the representative spatial zones which govern GHGs emissions.