Monitoring groundwater nitrate attenuation in a regional system coupling hydrogeology with multi-isotopic methods: the case of Plana de Vic (Osona, Spain)

This paper describes an integrated application of classical hydrogeological methods and multi-isotopic methods (d15N, d18ONO3, d34S, d18OSO4, d13C) to assess the fate of groundwater nitrate in the Osona area, declared vulnerable to nitrate pollution by the Catalan Government in 1998, where nitrate is derived from intensive pig farming activities. Previous studies, involving a small area, indicated the occurrence of denitrification processes and their relationship with pyrite oxidation [Vitòria, L., Soler, A., Canals, A., Otero, N., 2008. Environmental isotopes (N, S, C, O, D) to determine natural attenuation processes in nitrate contaminated waters: example of Osona (NE Spain). Appl. Geochem. 23, 3597-3611]. For the present study, groundwater samples were collected at 60 production wells at three different periods between April 2005 and May 2006 to confirm that denitrification takes place in a larger area than that studied by Vitòria et al. [Vitòria, L., Soler, A., Canals, A., Otero, N., 2008. Environmental isotopes (N, S, C, O, D) to determine natural attenuation processes in nitrate contaminated waters: example of Osona (NE Spain). Appl. Geochem. 23, 3597-3611]. The aim of the study was to characterize the denitrification processes that control natural attenuation and to study their spatial and temporal variations. Nitrate concentration ranged from 10 to 529 mg/l, with 82% of the wells above the drinking water threshold of 50 mg NO3/l. Nitrate isotopic composition ranged from +5.3% to +35.3% for d15N and from +0.4% to +17.6% for d18ONO3 , and the samples showed a positive correlation between d15N and d18ONO3 , with a eN/eO ratio of 1.8, consistent with denitrification processes. The link between denitrification and pyrite oxidation is demonstrated by coupling chemical data with nitrate and sulfate isotopes. Furthermore, a spatial distribution of samples with significant denitrification was observed, allowing us to determine two main hydrogeological zones where natural attenuation was most effective. In several of the studied points, denitrification processes related to pyrite oxidation predominated and an estimation of the isotopic enrichment factors was performed using the temporal variations of nitrate concentration and the isotopic composition of dissolved nitrate (d15NNO3 and d18ONO3). Finally, using estimated isotopic enrichment factors, an approximation of the degree of natural attenuation of nitrate was performed on those samples showing clear denitrification, and a median value of 30% of contaminant diminution was obtained

Nitrate pollution of groundwater, all right... but nothing else?

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 different lithological units, to investigate the influence of manure fertilization on the overall hydrochemical composition of groundwater. Results indicate that high nitrate concentrations, resulting from intense manure application, homogenize the contents of the major dissolved ions (i.e.; Cl-, SO42-, Ca2+, Na+, K+, and Mg2+). Moreover, positive linear relationships between nitrate and some ions are found indicating the magnitude of the fertilization impact on groundwater hydrochemistry. Nevertheless, the increasing concentration of specific ions is not only attributed to the manure input, but to the enhancing effect of manure and slurry upon the biogeochemical processes that control water-rock interactions. Such results raise awareness that such processes should be evaluated in advance in order to assess adequate groundwater resources assessmen

Estudio multi-isotópico de la atenuación natural de la contaminación por nitratos en un sistema acuífero regional: Plana de Vic (Osona, NE España)

The presence of nitrate in groundwater of the Osona area is derived from the intensive cattle raising. Even though local administration regulates and controls the present use and distribution of manure as fertilizer, according to legal application rates, nitrate pollution in Osona shows the effect of decades of uncontrolled manure application. Vitòria (2004) using stable isotopes determined the presence of denitrification processe (natural attenuation of nitrate pollution) in a small area located in the Osona province. The main goal of this still on-going research (2005-2006) is to determine the extent of denitrification at a regional scale, and the processes that control natural attenuation, using multi-isotopic methods (dD, d18O, T, d34S, d15N,d13C). Results show that denitrification is active in two areas, and that this process is linked to pyrite oxidation. In the studied area, data do not allow to identify the role of organic matter oxidation in denitrification. The observed denitrification processes reveal optional strategies for nitrogen attenuation

Identificación de flujos entre acuíferos a nivel regional en base a datos hidroquímicos (Alt Empordà, NE España)

A escala regional, los flujos de agua subterránea entre formaciones hidrogeológicas condicionan su ba lance hídrico y, con él, su régimen de explotación. En este estudio se caracteriza la dinámica hidrogeológica a nivel regional de la depresión del Alt Empordà (Girona, NE España) en base a datos hidroquímicos, con el objetivo de identificar flujos de agua subterránea entre las formaciones que constituyen la zona de recarga (relieves circundantes) y la depresión. En este sistema, el ión sulfato resulta un trazador adecuado para identificar los procesos hidroquímicos y de mezcla que acontecen en este zona. Los datos presentados sugieren que la presencia de sulfato, y por consiguiente la recarga, se debe a aportaciones de flujos profundos, en algunos casos desde las unidades geológicas inferiores, ajenos a la recarga local por precipitación desde la superficie.At a regional scale, groundwater flow between aquifer systems controls their water budget and, therefore, its exploitation regime. This study characterizes the hydrogeology at a regional level of the Alt Empordà Basin (Girona, NE Spain). Our goal consists in recognizing recharge flowpaths, based on hydrochemical data, between the aquifer systems located in the ranges (recharge) areas and these within the basin. Sulfate stands as an appropriate tracer to identify hydrochemical as well as mixing processes and, therefore, recharge relationships. Field data suggest that sulfate occurrence is related to deep groundwater fluxes unrelated to the local rainfall recharge.Universidad Nacional de La Plat

River Restoration in Spain: Theoretical and Practical Approach in the Context of the European Water Framework Directive.

River restoration is becoming a priority in many countries because of increasing the awareness of environmental degradation. In Europe, the EU Water Framework Directive (WFD) has significantly reinforced river restoration, encouraging the improvement of ecological status for water bodies. To fulfill the WFD requirements, the Spanish Ministry of the Environment developed in 2006 a National Strategy for River Restoration whose design and implementation are described in this paper. At the same time many restoration projects have been conducted, and sixty of them have been evaluated in terms of stated objectives and pressures and implemented restoration measures. Riparian vegetation enhancement, weir removal and fish passes were the most frequently implemented restoration measures, although the greatest pressures came from hydrologic alteration caused by flow regulation for irrigation purposes. Water deficits in quantity and quality associated with uncontrolled water demands seriously affect Mediterranean rivers and represent the main constraint to achieving good ecological status of Spanish rivers, most of them intensively regulated. Proper environmental allocation of in-stream flows would need deep restrictions in agricultural water use which seem to be of very difficult social acceptance. This situation highlights the need to integrate land-use and rural development policies with water resources and river management, and identifies additional difficulties in achieving the WFD objectives and good ecological status of rivers in Mediterranean countries

water chemistry are new challenges possible from coda compositional data analysis point of view

John Aitchison died in December 2016 leaving behind an important inheritance: to continue to explore the fascinating world of compositional data. However, notwithstanding the progress that we have made in this field of investigation and the diffusion of the CoDA theory in different researches, a lot of work has still to be done, particularly in geochemistry. In fact most of the papers published in international journals that manage compositional data ignore their nature and their consequent peculiar statistical properties. On the other hand, when CoDA principles are applied, several efforts are often made to continue to consider the log-ratio transformed variables, for example the centered log-ratio ones, as the original ones, demonstrating a sort of resistance to thinking in relative terms. This appears to be a very strange behavior since geochemists are used to ratios and their analysis is the base of the experimental calibration when standards are evolved to set the instruments. In this chapter some challenges are presented by exploring water chemistry data with the aim to invite people to capture the essence of thinking in a relative and multivariate way since this is the path to obtain a description of natural processes as complete as possible

Dinámica de la contaminación por nitrato en el sistema acuífero de la Plana de Vic (Osona, Barcelona). Nitrate pollution processes in the Plana de Vic aquifers (Osona, Barcelona)

ABSTRACT. Nitrate pollution in the Plan

River-aquifer interactions and their relationship to stygofauna assemblages : a case study of the Gwydir River alluvial aquifer (New South Wales, Australia)

In contrast to surface water ecosystems, groundwater ecosystems are usually considered to have relatively stable conditions and physically inert environments. However, many groundwater ecosystems undergo substantial changes through space and time, related to fluxes in groundwater flow, exchange and nutrient imports. In this study we used hydrochemical data to: 1) determine the different hydrogeological conditions in an alluvial system, the shallow Gwydir River alluvial aquifer (located in Northern New South Wales, Australia); and 2) analyze the relationship between hydrochemical conditions and the composition of stygofauna assemblages in the aquifer. Using hydrochemical modeling and multivariate analyses, four main hydrogeological situations were defined as occurring in the aquifer. Bores were classified as having either a high, low or no influence from or exchange with the river. The latter group was further subdivided into those of low and high salinity. Further analysis combining the biological and hydrochemical data identified two main groups of samples. The first group was composed mainly of samples related to the aquifer groundwater which had higher richness and abundance of fauna compared to samples in the second group which was comprised of samples affected by stream water leakage and samples related to the highest salinities. These results suggest that more stable conditions (mainly related to steadier groundwater head levels) and lower nitrate concentrations promoted a more diverse and abundant stygofauna community.14 page(s

Dataset for analyzing and modelling the eutrophication processes in groundwater-coastal lagoon systems: The La Pletera lagoons case study (NE Spain)

A comprehensive hydrogeological report was conducted to determine the origin, occurrence and processes affecting nitrogen in a Mediterranean coastal aquifer-lagoon system. Water levels, hydrochemical and isotopic data was gathered during a 4-year period in the La Pletera salt marsh area (NE Spain). They were collected from the alluvial aquifer, two natural lagoons and four other permanent lagoons excavated during a restoration process (in 2002 and 2016), two watercourses (the Ter River and the Ter Vell artificial channel), 21 wells (considering six of them for groundwater sampling) and the Mediterranean Sea. Potentiometric surveys were carried out seasonally, however twelve-monthly campaigns (from November 2014 to October 2015), and nine seasonal campaigns (from January 2016 to January 2018) were conducted for hydrochemical and environmental isotopes analyses. The evolution of the water table was analysed for each well, and potentiometric maps were plotted to determine the relationship between the aquifer and the lagoons, sea, watercourses, and groundwater flow. Hydrochemical data included physicochemical data measured in situ (temperature, pH, Eh, dissolved oxygen, and electrical conductivity), major and minor ions (HCO3−, CO32−, Cl−, SO42−, F−, Br−, Ca2+, Mg2+, Na+, and K+), and nutrients (NO2−, NO3−, NH4+, Total Nitrogen (TN), PO43−, and Total Phosphorus (TP)). Environmental isotopes included stable water isotopes (δ18O and δD), nitrate (δ15NNO3 and δ18ONO3) and sulphate isotopes (δ34SSO4 and δ18OSO4). Water isotopes were analysed for all campaigns, however, nitrate and sulphate isotopes water samples were only analysed in some particular surveys (November and December 2014; January, April, June, July and August 2015). Additionally, two more surveys for sulphate isotopes were conducted in April and October of 2016. The data generated through this research may be used as a starting point to analyse the evolution of these recently restored lagoons, and their future responses to global change. In addition, this dataset may be used to model the hydrological and hydrochemical behaviour of the aquifer