U-isotopes and (226)Ra as tracers of hydrogeochemical processes in carbonated karst aquifers from arid areas.

Sierra de Gádor is a karst macrosystem with a highly complex geometry, located in southeastern Spain. In this arid environment, the main economic activities, agriculture and tourism, are supported by water resources from the Sierra de Gádor aquifer system. The aim of this work was to study the levels and behaviour of some of the most significant natural radionuclides in order to improve the knowledge of the hydrogeochemical processes involved in this groundwater system. For this study, 28 groundwater and 7 surface water samples were collected, and the activity concentrations of the natural U-isotopes ((238)U, (235)U and (234)U) and (226)Ra by alpha spectrometry were determined. The activity concentration of (238)U presented a large variation from around 1.1 to 65 mBq L(-1). Elevated groundwater U concentrations were the result of oxidising conditions that likely promoted U dissolution. The PHREEQC modelling code showed that dissolved U mainly existed as uranyl carbonate complexes. The (234)U/(238)U activity ratios were higher than unity for all samples (1.1-3.8). Additionally, these ratios were in greater disequilibrium in groundwater than surface water samples, the likely result of greater water-rock contact time. (226)Ra presented a wide range of activity concentrations, (0.8 up to about 4 × 10(2) mBq L(-1)); greatest concentrations were detected in the thermal area of Alhama. Most of the samples showed (226)Ra/(234)U activity ratios lower than unity (median = 0.3), likely the result of the greater mobility of U than Ra in the aquifer system. The natural U-isotopes concentrations were strongly correlated with dissolution of sulphate evaporites (mainly gypsum). (226)Ra had a more complex behaviour, showing a strong correlation with water salinity, which was particularly evident in locations where thermal anomalies were detected. The most saline samples showed the lowest (234)U/(238)U activity ratios, probably due to fast uniform bulk mineral dissolution, which would minimize the impact of solubility-controlled fractionation processes. Furthermore, the high bulk dissolution rates promoted greater groundwater (226)Ra/(234)U ratios because the Ra has a comparatively much greater mobility than U in saline conditions.

Geostatistical analysis to identify hydrogeochemical processes in complex aquifers: a case study (Aguadulce unit, Almeria, SE Spain).

The Aguadulce aquifer unit in southeastern Spain is a complex hydrogeological system because of the varied lithology of the aquifer strata and the variability of the processes that can take place within the unit. Factorial analysis of the data allowed the number of variables to be reduced to 3 factors, which were found to be related to such physico-chemical processes as marine intrusion and leaching of saline deposits. Variographic analysis was applied to these factors, culminating in a study of spatial distribution using ordinary kriging. Mapping of the factors allowed rapid differentiation of some of the processes that affect the waters of the Gador carbonate aquifer within the Aguadulce unit, without the need to recur to purely hydrogeochemical techniques. The results indicate the existence of several factors related to salinity: marine intrusion, paleowaters, and/or leaching of marls and evaporitic deposits. The techniques employed are effective, and the results conform to those obtained using hydrogeochemical methods (vertical records of conductivity and temperature, ion ratios, and others). The findings of this study confirm that the application of such analytical methods can provide a useful assessment of factors affecting groundwater composition.

A monitoring programme for 1,3-dichloropropene and metabolites in groundwater in five EU countries.

BACKGROUND: 1,3 Dichloropropene (1,3-D) is a preplanting soil fumigant for the control of cyst and free-living nematodes and is currently undergoing a resubmission under Annex 1 listing of Directive 91/414/EEC. The characteristics of 1,3-D are such that the risk of it or its soil metabolites leaching through the soil profile cannot be excluded. As such, groundwater monitoring programmes were established in five EU countries representing a wide range of agricultural, climatic and hydrogeological situations, covering a range of groundwater vulnerability scenarios. All monitoring was conducted in areas where there has been historical use of 1,3-D. RESULTS: Over 5000 groundwater samples were analysed for the presence of 1,3-D and its metabolites over a 2 year period. Almost all analyses (for parent and metabolites) yielded concentrations of <0.1 microg L(-1). There were just two detections of >0.1 microg L(-1) (0.12 microg L(-1) and 0.4 microg L(-1)) for the 3-chloroacrylic acid metabolite in shallow groundwater samples of the alluvial gravels of the River Tiétar in the Caceres region of Spain. CONCLUSION: Groundwater monitoring programmes have been conducted in the EU in five countries. These have demonstrated that there is negligible contamination of groundwater with 1,3-D or its metabolites across a range of agroclimatic regions where 1,3-D is known to have been used for a number of years. Local scientific knowledge of geological features, hydrology, agricultural practice and specific local issues was essential to the conduct of the study.

Assessment of groundwater quality by means of self-organizing maps: application in a semiarid area.

The Kohonen neural network was applied to hydrochemical data from the Detritic Aquifer of the Lower Andarax, situated in a semiarid zone in the southeast of Spain. An activation map was obtained for each of the sampling points, in which the spatial distribution of the activated neurons indicated different water qualities. To extract the information contained in the activation maps, they were divided into nine quadrats. Cartesian coordinates were assigned to each quadrant ( x, y), and for each sampling point, three derived variables were selected, which were assigned the values x and y of the corresponding quadrat. A classification was defined based on this simple matrix system which allows an easy and rapid means of evaluating the water quality. This assessment highlights the various processes that affect groundwater quality. The method generates output that is easier to interpret than from traditional statistical methods. The information is extracted from the activation maps without significant loss of information. The method is proposed for assessing water quality in hydrogeochemically complex areas, where large numbers of observations are made.

Identification of the origin of salinization in groundwater using minor ions (Lower Andarax, Southeast Spain).

The study of salinization of groundwater in the Detrital Aquifer of the Lower Andarax is highly complex due to the semiarid climate, the presence of evaporites, proximity to the sea and localized geothermal manifestations in the area. The salinization has been characterized by jointly studying the content of various minor ions (B, Br and Li) and a series of ionic relationships (B/Li, SO4/Cl, Na/Cl, Cl/B). The combined analysis of B and Li enabled the areas with a marked marine influence to be distinguished from those with an evaporite or geothermal influence. Lithium is directly related to water temperature whilst B content increases in more saline areas, since it is associated with the presence of evaporitic and/or marine influences. Bromine analysis enabled the identification of the principal processes that determine the salinity of the water along the coastal zone: the presence of Quaternary marine sediments and present-day marine intrusion. The brackish groundwaters that are related to old raised beaches showed a low Cl/Br ratio. Areas affected by marine intrusion had Cl/Br ratios similar to seawater and higher than in other areas along the coastal zone. At some points on the delta, a mixture of brackish water and recharge water was detected--the recharge water has a sulfate facies, which causes a drop in the Cl/Br ratio and changes the general character of the water in the coastal zone. The coastal zone contains silty-clay intercalations that favor processes of ion exchange, anthropogenic pollution also occurs and together these processes hamper the interpretation of all the processes.