Assessing aquifer vulnerability to pollutants by electrical resistivity tomography (ERT) at a nitrate vulnerable zone in NE Spain

There is an increasing demand for groundwater vulnerability maps which illustrate the exposure of aquifers against pollution. These maps show areas of greatest potential for groundwater contamination on the basis of local subsurface conditions. Parameters affecting vulnerability are mainly permeability and thickness of each protective layer. For unconsolidated sediments, the permeability is strongly related to the clay content, which can be deduced from indirect resistivity methods, like electrical-imaging. Such geophysical methods can be of great help in groundwater vulnerability studies because they disturb neither the structure nor the dynamics of the soil. Sensibility analysis was performed of the electrical resistivity tomography method for accurately mapping soil media. Managers and public administrators may effectively use this method for assessing the potential risk of groundwater contamination. In the studied zone, electrical resistivity exhibits a wide range of variability that can be easily correlated to soil parameters, such as clay content and hydraulic conductivity. A numerical index of protection has been assessed from the geophysical information derived from 2D electrical resistivity tomography. This work represents a preliminary approach on the natural vulnerability evaluation of shallow aquifers at the Empordà basin (NE Spain) that is highly affected by diffuse pollution by nitrates.     

A riparian plant community from the upper Maastrichtian of the Pyrenees (Catalonia,NE Spain)

Angiosperms began to colonise riparian habitats very soon in their evolutionary history, probably already in the Aptian, but it is still poorly known when flowering plants finally dominated entirely these kind of communities as they do in the present. A new fossil plant locality (Molí del Baró-1) from the upper Maastrichtian of the Southern Pyrenees is described in which meandering river facies represent one of the first riparian communities formed only by angiosperms. The fossil assemblage consists of abundant leaves, seeds, logs and sporomorphs. Angiosperms remains dominate in all these cases and the leaf sample is mostly composed of a new eudicot willow-like species, Saliciphyllum gaetei sp. nov., the palm Sabalites longirhachis and an helophytic monocot. Pollen remains suggest that the later belonged to Typhaceae. Most of these plant remains were parautochthonous and deposited in a pond formed in the accretional part of a meander loop. The locality of Molí del Baró-1 represents an unique plant fossil assemblage in the uppermost Cretaceous of southern Europe. It clearly differs from those reported in other Maastrichtian localities of the Pyrenees (Fumanya and South Isona) and from the Campanian-Maastrichtian of Austria and Romania. In addition, it reflects a surprisingly modern physiognomy for a Late Cretaceous riverine plant assemblage that was built up with willow-like plants, palms and reeds.     

Comparative application of two methods (COP and PaPRIKa) for groundwater vulnerability mapping in Mediterranean karst aquifers (France and Spain)

A comparative test of two vulnerability mapping methods (COP and PaPRIKa) specifically dedicated to for karst aquifers was carried out on two Mediterranean carbonate aquifers. The vulnerability maps obtained for each aquifer present important differences. To identify and determine the origin of these differences, the results were statistically analyzed using sensitivity analysis, coefficients of determination and scatter graphs. In addition, the global vulnerability (Gv) parameter was used to measure the general vulnerability of the aquifer and to compare the results obtained. This statistical analysis led us to conclude that the main cause of differences between these two methods used to assess aquifer vulnerability lie in the relative importance of the parameters employed in calculating the vulnerability index. For the PaPRIKa method, the variable related to infiltration (slope and karst features) has the most influence, with less weight being assigned to the protective capacity of layers overlying the aquifer. For the COP method, the most influent variable is defined by the layers overlying the aquifer, together with infiltration characteristics, determined by the relative importance of different forms of infiltration in each aquifer. The vulnerability mappings performed using the COP method present greater coherence with the known hydrogeological behavior of the study areas, especially the Spanish aquifers. Nevertheless, further hydrogeological investigations are needed, such as ones to validate the obtained vulnerability maps.     

The impact of hydrological conditions on salinisation and nitrate concentration in the coastal Velez River aquifer (southern Spain)

This study reports the impact of hydrological conditions on salinisation and nitrate concentrations of a coastal aquifer located at the Mediterranean Sea, southern Spain. Eighty-two samples of ground- and surface water taken during two extreme hydrological events between 1994 and 1996 at 25 different wells were evaluated with regard to hydrochemistry, focusing on nitrate concentrations and salinisation, which constitute the main hazard of this aquifer. Furthermore, hydrochemical data were analysed by principal component analysis (PCA). Additionally, in 2007 13 ground- and surface water samples taken at 12 different locations were analysed for stable isotopes of D/¹⁸O, and one sample was analysed for ¹⁵N. Since 1993 until present saltwater intrusion was observed only during dry hydrological conditions in 1994; it showed an irregular salinisation pattern probably related to locally elevated hydraulic conductivities. Nitrate concentrations increase significantly during wet hydrologic conditions owing to uptake of nitrate by rising groundwater. Stable isotopes of groundwater reveal an Atlantic origin of the precipitation that recharges the aquifer and a minor amount of groundwater recharge by the water coming from the La Viñuela reservoir, which is used for irrigation over the aquifer. ¹⁵N isotopes point to a considerable input of nitrates derived from organic fertilisers.     

Vertical vulnerability evaluation of middle-low Esino River valley alluvial aquifer (Marche, Italy)

 The methodology applied in this research work allows the evaluation of the vertical vulnerability of the Esino River alluvial aquifer (Marche). Main factors determining the ease with which possible pollutant may come from the soil surface to reach the groundwater beneath, through a prevalently vertical path, have been evaluated. Following a "raster" logic, the study area has been discretized into a set of elemental areas. For each of these areas, dimensionless indices able to characterize the actual possibility for the groundwater to be reached by polluting substances have been estimated. Received: 25 February 1997 · Accepted: 13 November 1997     

Assessment of aquifer vulnerability based on GIS and DRASTIC methods: a case study of the Senirkent-Uluborlu Basin (Isparta, Turkey)

Aquifer vulnerability has been assessed in the Senirkent-Uluborlu Basin within the Egirdir Lake catchment (Turkey) using the DRASTIC method, based on a geographic information system (GIS). There is widespread agriculture in the basin, and fertilizer (nitrate) and pesticide applications have caused groundwater contamination as a result of leaching. According to hydrogeological data from the study area, surface water and groundwater flow are towards Egirdir Lake. Hence, aquifer vulnerability in the basin should be determined by water quality in Egirdir Lake. DRASTIC layers were prepared using data such as rainfall, groundwater level, aquifer type, and hydraulic conductivity. These data were obtained from hydrogeological investigations and literature. A regional-scale aquifer-vulnerability map of the basin was prepared using overlay analysis with the aid of GIS. A DRASTIC vulnerability map, verified by nitrate in groundwater data, shows that the defined areas are compatible with land-use data. It is concluded that 20.8% of the basin area is highly vulnerable and urgent pollution-preventions measures should be taken for every kind of relevant activity within the whole basin.     

Hydrogeological origin of the CO2-rich mineral water of Vilajuïga in the Eastern Pyrenees (NE Catalonia,Spain)

The mineral water of Vilajuïga village in Alt Empordà (NE Catalonia, Spain) owes its uniqueness to an emanation of geogenic CO₂ that modifies groundwater hydrochemistry to produce a differentiated HCO₃–Na- and CO₂-rich groundwater among the usual Ca–HCO₃ type found in this region. A hydrogeological conceptual model attributes its occurrence to the intersection of two faults: La Valleta and Garriguella-Roses. The former provides a thrust of metamorphic over igneous rocks, formed during the Paleozoic, over a layer of ampelitic shale that, from a hydrogeological perspective, acts as a confining layer. The Garriguella-Roses normal fault, which originated during the Neogene, permits the degassing of geogenic CO₂ that is attributed to volcanic activity occurring in the Neogene. Groundwater mixing from the metamorphic and igneous rock units plus the local occurrence of CO₂ creates a HCO₃–Na water that still holds free-CO₂ in solution. Interaction with the gas phase is restricted at the intersection of the two faults. Radiocarbon dating, after correcting for geogenic dead carbon, estimates an age of 8,000 years BP. The low tritium content (0.7 TU) indicates that Vilajuïga water is a mix of “older” groundwater recharged in the metamorphic rocks of the Albera range and “younger” groundwater from the igneous rocks of the Rodes range, over a recharge area of 45 km² and a maximum elevation of 600 m. Given its origin as rare groundwater in the southern slope of the Eastern Pyrenees, purposeful monitoring is necessary to evaluate the groundwater vulnerability and anticipate impacts from nearby wells and climate-change effects.

     

Delineating spring recharge areas in a fractured sandstone aquifer (Luxembourg) based on pesticide mass balance

A simple method to delineate the recharge areas of a series of springs draining a fractured aquifer is presented. Instead of solving the flow and transport equations, the delineation is reformulated as a mass balance problem assigning arable land in proportion to the pesticide mass discharged annually in a spring at minimum total transport cost. The approach was applied to the Luxembourg Sandstone, a fractured-rock aquifer supplying half of the drinking water for Luxembourg, using the herbicide atrazine. Predictions of the recharge areas were most robust in situations of strong competition by neighbouring springs while the catchment boundaries for isolated springs were extremely sensitive to the parameter controlling flow direction. Validation using a different pesticide showed the best agreement with the simplest model used, whereas using historical crop-rotation data and spatially distributed soil-leaching data did not improve predictions. The whole approach presents the advantage of integrating objectively information on land use and pesticide concentration in spring water into the delineation of groundwater recharge zones in a fractured-rock aquifer.     

Groundwater nitrate vulnerability assessment in alluvial aquifer using process-based models and weights-of-evidence method: Lower Savinja Valley case study (Slovenia)

This paper describes the implementation of process-based models reflecting relative groundwater nitrate vulnerability of the shallow alluvial Lower Savinja Valley (LSV) aquifer in Slovenia. A spatially explicit identification of the potentially vulnerable priority areas within groundwater bodies at risk from a chemical point of view is being required for cost-effective measures and monitoring planning. The shallow LSV unconfined aquifer system consists of high-permeable Holocene and middle- to low-permeable Pleistocene gravel and sand, with a maximum thickness of about 30 m, mainly covered by shallow eutric fluvisoils or variously deep eutric cambisoil. The hydrogeological parameters, e.g. the depth to the groundwater, hydrological role of the topographic slope, etc. usually used in different point count schemes are, in the case of the lowland aquifer and shallow groundwater, spatially very uniform with low variability. Furthermore, the parametric point count methods are generally not able to illustrate and analyze important physical processes, and validation of the results is difficult and expensive. Instead of a parametric point count scheme, we experimentally used the Arc-WofE extension for weights-of-evidence (WofE) modelling. All measurement locations with a concentration higher than the value of 20 mg NO₃ ⁻ per litre of groundwater have been considered as training points (173), and the three process-based models generalized output layers of groundwater recharge (GROWA), nitrate leached from the soil profile (SWAT) and groundwater flow velocity (FEFLOW), served as evidential themes. The technique is based on the Bayesian idea of phenomena occurrences probability before (prior probability) and after consideration of any evidential themes (posterior probability), which were measured by positive and negative weights as an indication of the association between a phenomena and a prediction pattern. The response theme values describe the relative probability that a 100 × 100 m spatial unit will have a groundwater nitrate concentration higher than the training points’ limit values with regard to prior probability value. The lowest probability of groundwater nitrate occurrence is in the parts of the LSV aquifer, which are known as anoxic condition areas with very likely denitrification processes. The cross-validation of the dissolved oxygen and dissolved nitrate response theme confirmed the accuracy of the groundwater nitrate prediction. The WofE model results very clearly indicate regional groundwater nitrate distribution and enable spatial prediction of the probability for increased groundwater nitrate concentration in order to plan the groundwater nitrate reduction measures and optimize the programme for monitoring the effects of these measures.     

Subsidence hazard avoidance based on geomorphological mapping in the Ebro River valley mantled evaporite karst terrain (NE Spain)

In the valley of the Ebro River to the southeast of the city of Zaragoza (NE Spain), the dissolution of evaporite sediments (gypsum, halite and Na-sulphates) which underlie alluvial deposits gives rise to numerous sinkholes. These sinkholes are a potential hazard to human safety, particularly where they develop in a catastrophic way. Even slow-developing sinkholes are problematic, as they damage urban and agricultural infrastructure, necessitating costly repairs and vigilant maintenance. To assist in developing avoidance strategies for these hazards, the factors controlling sinkhole occurrence have been assessed using geomorphological maps produced from aerial photographs for 1956 and 1981. Important controls on sinkhole development are found to include underlying geological structure (manifest in preferred orientations of sinkholes on the azimuths N130-150E and N30-40E), and the presence of glauberite in the groundwater flow path, which apparently promotes accelerated gypsum dissolution. Perhaps surprisingly, alluvium thickness does not appear to significantly correlate with the density of sinkholes on the floodplain in this area. The maps for 1956 and 1981 reveal that both human activity and natural processes can serve to obscure the true density of sinkhole development. For instance, a large number of sinkholes which were conspicuous in 1956 have since been back-filled by farmers. In the most fluvially active zone of the Ebro valley (the meander belt), the relatively low density of sinkholes compared with adjoining zones suggests that subsidence is being masked by morpho-sedimentary dynamic processes (aggradation and erosion). Careful geomorphological mapping for different time periods yields a much more accurate impression of the frequency of sinkhole development than would be gained from surveying currently visible sinkholes in the area of interest.     

Identification of potential sites for aquifer storage and recovery (ASR) in coastal areas using ASR performance estimation methods

Performance of freshwater aquifer storage and recovery (ASR) systems in brackish or saline aquifers is negatively affected by lateral flow, density effects, and/or dispersive mixing, causing ambient groundwater to enter ASR wells during recovery. Two recently published ASR performance estimation methods are applied in a Dutch coastal area, characterized by brackish-to-saline groundwater and locally high lateral-flow velocities. ASR performance of existing systems in the study area show good agreement with the predicted performance using the two methods, provided that local vertical anisotropy ratios are limited (<3). Deviations between actual and predicted ASR performance may originate from simplifications in the conceptual model and uncertainties in the hydrogeological and hydrochemical input. As the estimation methods prove suitable to predict ASR performance, feasibility maps are generated for different scales of ASR to identify favorable ASR sites. Successful small-to-medium-scale ASR varies spatially in the study area, emphasizing the relevance of reliable a priori spatial mapping.     

基于级别特征值的岩溶含水层水质模糊综合评价修正

为改进传统水质模糊综合评价中存在评价指标不能全面反映水质状况、评价结果不清晰,评价等级区分度不明显等缺陷,文章以位于六枝特区威宁-郎岱褶皱群的第一层岩溶含水层水质为例,根据岩溶区水质评价特点和研究区含水层超标因子特征,建立涵盖物理、化学和微生物等因子的评价指标体系,利用级别特征值对传统模糊综合评价结果进行了适当修正,并与综合污染指数法、传统模糊评价综合法的评价精度进行定量化比较。研究结果表明:六枝特区的研究区探采点水质综合评价等级都达到Ⅲ类生活饮用水卫生标准,但仍有71%的探采点存在氨氮（NH4+）、氟化物(F-)、高锰酸盐指数(CODMn)、溶解性总固体（TDS）和大肠杆菌等指标超标,且超标因子浓度呈点状扩散分布于三叠系中下统地层;另外,传统模糊综合评价中有57.1%的水质达到Ⅰ类标准,与多个探采点存在因子超标的情况不符,而通过级别特征值修正的模糊综合评价结果中分别有57.1%和28.6%的探采点水质为Ⅱ类或Ⅲ类标准,与着重突出最大超标因子权重的综合指数法类别标准差低0.011。因此,基于级别特征值的模糊综合评价能有效的反映水质整体水平,探采点水样超标因子浓度和同类水质的区分度,评价结果合理、可信。      

Environmental isotopes (N, S, C, O, D) to determine natural attenuation processes in nitrate contaminated waters: Example of Osona (NE Spain)

Nitrate-contaminated groundwater from an aquifer in the Osona region (NE Spain) was chemically and isotopically (δ¹⁵N_NO3,δ¹⁸O_NO3,δ³⁴S_SO4,δ¹⁸O_SO4, δD, δ¹⁸O_H2O and δ¹³C_DIC) characterized. Diffuse- contamination reached values of 366 mg/L. Nearly 75% of the 37 sampled sites had higher concentrations than the 50 mg/L in limit for drinking water. To identify the source of pollution δ¹⁵N_NO3 and δ¹⁸O_NO3 were used with results, for most samples, in the range of pig manure . Nitrification processes were evaluated by means of the δ¹⁸O of and water. Isotopic data suggested that natural attenuation of was taking place. This process was confirmed using the δ¹⁸O_NO3 coupled with the ratio, avoiding the influence of continuous inputs. A further insight on denitrification processes was obtained by analyzing the ions involved in denitrification reactions. Although the role of organic matter oxidation could neither be confirmed nor discarded, this approach showed a link between denitrification and pyrite oxidation. Therefore, in areas with no adequate infrastructure (e.g. multipiezometers), such as the one studied, this approach could be useful for implementing better water management.     

Groundwater pollution in Quaternary aquifer of Vitoria – Gasteiz (Basque Country, Spain)

 As a result of diverse changes in land use and in water-resource management in the high basin of the Zadorra River (Basque Country), an important loss of water resources and an intense contamination by nitrogen compounds has taken place. The purpose of this paper is to detail the land transformations that have taken place on the aquifer since the 1950s: increase of drainage network, change from dry to irrigated farming, and diversion of rivers at the aquifer unit inlet. Furthermore, we analyze the impact of these transformations on the hydrodynamics and water quality of this aquifer system. Received: 12 January 1996 · Accepted: 10 March 1996     

Impact evaluation on groundwater of the infiltration of an urban wastewater geopurification system placed over a detrital aquifer in a semiarid region (Spain)

Over a period of 4 years and 4 months, the geopurification installations at Dehesas de Guadix (Granada, Spain) were monitored to determine the impact on soil and groundwater of the controlled discharge of urban wastewater, and also to identify the best indicators of the entry of the recharged water into the aquifer. The installations are located in an area where the climate is Mediterranean sub-arid, with an average precipitation of less than 287 mm/year, and a rate of evapotranspiration that is almost three times greater. The system was controlled by determining the balance of majority nutrients and boron in the soil and in the groundwater, both at the points affected directly by the wastewater discharge and at others. The quantity of mass discharged was relatively large (COD 14,656 g/m², NO₃ 85 g/m², NO₂ 4 g/m², NH₄ 2,425 g/m², PO₄ 1,143 g/m², K 1,531 g/m², B 63 g/m²). It was observed that the elimination of nutrients within the soil (COD 97.5%, PO₄ 94.4%, K 59.17%, N _total 18.8%, B 12.69%) was very efficient except for the nitrogen, which nevertheless did not reach the groundwater, as it was eliminated at deep levels of the unsaturated zone. Only 12.69% of the boron was removed, and appreciable, increasing amounts of this element did reach the groundwater. Unexpectedly, none of the majority nutrients behaved as a reliable indicator of the impact on groundwater; despite this, the boron and the bicarbonate did clearly reflect the arrival of the recharged water, and are proposed as the best indicators.     

Groundwater vulnerability assessment for the karst aquifer of Tanour and Rasoun springs catchment area (NW-Jordan) using COP and EPIK intrinsic methods

Groundwater vulnerability maps were constructed for the surface water catchment area of Tanour and Rasoun spring (north-west of Jordan) using the COP and EPIK intrinsic groundwater vulnerability assessment methods. Tanour and Rasoun springs are the main water resources for domestic purposes within the study area. A detailed geological survey was carried out, and data of lithology, karst features, precipitation, vegetation and soil cover, etc. were gathered from various sources for the catchment area in order to determine the required parameters for each method. ArcGIS software was used for map preparation. In the resulting COP vulnerability map, spatial distribution of groundwater vulnerability is as follows: (1) high (37%), (2) moderate (34.8%), (3) low (20.1%), and (4) very low (8.1%). In the EPIK vulnerability map, only two out of four vulnerability classes characterize the catchment area: very high vulnerable areas (38.4%) and moderately vulnerable areas (61.6%). Due to limited soil thickness, the low vulnerability class is absent within the catchment. The high percentage of very high to moderately vulnerable areas displayed by both the COP and EPIK vulnerability assessment methods are reflected by different pollution events in Tanour and Rasoun karst springs especially during the winter season. The high sensitivity of the aquifer to pollution can be explained by different factors such as: thin or absent soil cover, the high development of the epikarst and karst network, and the lithology and confining conditions of the aquifer.     

Potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs) in a sensitive bedrock aquifer (Canada)

It is necessary to understand the presence, movement, and persistence of contaminants in aquifers to develop adequate groundwater protection plans. Fractured bedrock aquifers with thin overburden cover are very sensitive to contamination, and little is known about transport processes from the ground surface to depth in this setting. This study was undertaken to investigate the potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs), which are flame retardants, in a natural fractured bedrock aquifer in Canada proven to be sensitive to contamination. PBDEs, which had not been previously measured in groundwater in detail, were detected in the study aquifer at concentrations greater than those observed in surface-water bodies. Potential sources include manure, septic tanks, and the atmosphere. From this scoping study, it is evident that additional surveys of PBDE concentrations in groundwater are warranted, especially in settings with high potential source concentrations coupled with sensitive aquifers.     

Environmental impact of heavy-metal dispersion in the Huerva River (Iberian Range,NE Spain)

In this study, the methodology of geochemical prospecting has been applied to the study of cadmium, lead, copper and zinc dispersion in the fine sediments of the upper course of the Huerva River (Iberian Range, NE Spain). The survey was organised in two stages: (1) general sampling along the river and its tributary channels, aimed at selecting the sections with the highest contents of the target elements, and (2) detailed study of those sections, aimed at an interpretation of possible positive geochemical anomalies and identification of their sources. The results of this study prove the existence of multiple and complex sources, with a significant influence of sources related to anthropogenic activity. However, the system shows a good ability to depurate itself under current conditions.     

Hydraulic evaluation of aquifer storage and recovery (ASR) with urban stormwater in a brackish limestone aquifer

A 5-year aquifer storage and recovery trial at Andrews Farm in South Australia involving the injection of more than 250 ML (250,000 m³) of fresh but turbid stormwater into a brackish limestone aquifer over 4 years and recovery of 150 ML in the fifth provided the opportunity to evaluate rates of clogging and unclogging and the potential to recover water suitable for irrigation supplies. Results reveal there is some clogging by injected sediment, but only to a relatively small degree considering the high suspended solid concentrations and moderate aquifer transmissivity. This clogging was offset by increased matrix porosity through calcite dissolution and by routine well redevelopments after each 40 ML of injection. No significant microbial clogging occurred. Breakthrough responses at three observation wells and the proportion of injectant in the recovered water were determined from chloride data. Temperature and caliper profiles clearly indicate the heterogeneous nature of the aquifer that is attributed, in part, to sand removal during the initial well development. The recovery efficiency was greater than 60%. The trial demonstrates that urban stormwater containing high and variable particulate levels, which receives only passive pre-treatment and is not disinfected, can be used to freshen a heterogeneous brackish aquifer to create a useful water resource.     

Spatial loyalty and territorial embeddedness in the multi-sector clustering of the Berguedà region in Catalonia (Spain)

The development of clusters of local growth is supported by different processes. Endogenous economic development produced by small and medium-sized enterprises (SMEs) is based on family firms in which local market characteristics influence the sectorial diversification that emerges within certain regions. In the Berguedà region (Catalonia, Spain), the formation of a successful network of SMEs in three main sectors (food, textile and machinery) in the 1990s demonstrated the importance of grass-roots prerequisites, including industrial tradition, social networks and a sense of spatial loyalty, one of the main concepts studied in this paper. The aim of this paper is to study how institutions, local economic networks and collective social agents generate a propitious economic space that constitutes favourable embedding in Berguedà. However, the key element in this industrial system is the loyalty that entrepreneurs and workers feel towards their industrial region. These two processes, territorial embeddedness and spatial loyalty, appear to be two of the major forces behind the economic dynamism of the region and have led to the formation of a new cluster of firms.