Contamination from agricultural sources and, in particular, nitrate pollution, is one of the main concerns in groundwater management. However, this type of pollution entails the entrance of other substances into the aquifer, as well as it may promote other processes. In this study, we deal with hydrochemical and isotopic analysis of groundwater samples from four distinct zones in Catalonia (NE Spain), which include 5 different aquifer types, to investigate the influence of fertilization on the overall hydrochemical composition of groundwater. Results indicate that intense fertilizer application, causing high nitrate pollution in aquifers, also homogenize the contents of the major dissolved ions (i.e.; Cl(-), SO4(2-), Ca(2+), Na(+), K(+), and Mg(2+)). Thus, when groundwater in igneous and sedimentary aquifers is compared, significant differences are observed under natural conditions for Cl(-), Na(+) and Ca(2+) (with p-values ranging from <0.001 to 0.038), and when high nitrate concentrations occur, these differences are reduced (most p-values ranged between 0.054 and 0.978). Moreover, positive linear relationships between nitrate and some ions are found indicating the magnitude of the fertilization impact on groundwater hydrochemistry (with R(2) values of 0.490, 0.609 and 0.470, for SO4(2-), Ca(2+) and Cl(-), respectively). Nevertheless, the increasing concentration of specific ions is not only attributed to agricultural pollution, but to their enhancing effect upon the biogeochemical processes that control water-rock interactions. Such results raise awareness that these processes should be evaluated in advance in order to assess an adequate groundwater resources management.Peer ReviewedPostprint (author's final draft

Antibiotics are an increasing focus of interest due to their high detection frequency in the environment. However, their presence in water bodies is not regulated by environmental policies. This field study investigates, for the first time, the occurrence, behavior and fate of a selection of 53 antibiotics, including up to 10 chemical groups, in an alluvial aquifer originated from manure application in an agricultural region using hydrogeological, hydrochemical and isotopic approaches. Up to 11 antibiotics were found in groundwater corresponding to 4 different chemical groups: fluoroquinolones, macrolides, quinolones and sulfonamides. In surface water, only 5 different antibiotics from 2 chemical groups: fluoroquinolones and sulfonamides, were quantified. The most frequent antibiotics were sulfamethoxazole and ciprofloxacin. Concentrations of antibiotics were in the order of ng/L, with maximum concentrations of 300ng/L in groundwater. Hydrochemistry and isotopic data and geostatistics confirmed the spatial trend observed for nitrates, where nitrate concentrations tend to be higher in the margin areas of the study area, and lower concentrations are found nearby the river. On the other hand, no clear continuous spatial concentration trend of antibiotics was observed in the aquifer, supported by the short spatial correlation found in the variograms. This indicates that the physical-chemical properties and processes of each antibiotic (mainly, sorption and degradation), and other environmental issues, such as a patchy diffuse input and the manure antibiotic content itself, play an important role in their spatial distribution in groundwater. A discussion on the estimation of the antibiotic sorption parameter reveals the difficulties of describing such phenomena. Furthermore, retardation factors will extend over several orders of magnitude, which highly affects the movement of individual antibiotics within the aquifer. To summarize, this study points out the difficulties associated with antibiotic research in groundwater in order to define water resources quality management strategies and environmental regulations.

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Intensive pumping in urban coastal areas is a common threat to water resource quality due to seawater intrusion. In those areas where subsurface water resources are not usually used for human consumption or irrigation, intensive pumping is associated with other activities like the lowering of the water table necessary to support underground structures and building foundations. This activity also increases the likelihood of soil settlement that affects building stability and the corrosion of concrete structures due to groundwater salinity. Under these circumstances, the awareness of a certain municipality (Calonge, NE Spain) of the potential effects of groundwater withdrawal upon foundations has led to an integrated approach to anticipate seawater intrusion related to urban development. Geological mapping and correlation of borehole logs, electrical resistivity tomography, and hydrochemical data provide comprehensive knowledge of the geology and hydrogeology of the area and act as screening tools necessary to discern the influence of hydrological processes in coastal areas. Developing Strack's analytical solution, new comprehensive, dimensionless expressions are herein derived to determine the critical pumping rate necessary to prevent seawater intrusion, as well as to reproduce the evolution of the wedge toe and the water table stagnation point under different withdrawal rates. Furthermore, the Dupuit-Forchheimer well discharge formula allows the estimation of the effects of the water table lowering due to such critical pumping in the surrounding building foundations. Field data from the Calonge coastal plain illustrate this approach and provide assessment criteria for future urban development and planning. Temperature (T) is given in C; electrical conductivity (EC) is in mS/cm; and alkalinity (as HCO 3 ), dissolved oxygen (DO) and other major elements/ compounds are in mg/l. Errors based on % ionic balance. *Seawater composition according to a Mediterranean Sea sample from the Costa Brava region (Kruse and Mas-Pla, 2009).

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