Luis F. Auqué

Tufa sedimentation in changing hydrological conditions: the River Mesa (Spain)

The processes controlling tufa deposition along the River Mesa (NE Spain) were studied from April 2003 to September 2009, based on six-monthly monitoring of physical and chemical parameters of the river water and sedimentological characteristics, including deposition rates on tablets. With a mean annual discharge around 1.5m3/s, the sedimentation rate (mean 2mm/yr) recorded important spatial, seasonal and interannual variations. The river waters are of the calcium bicarbonate type. In this study, three distinct river stretches were distinguished based on the steady groundwater inputs, some of low-thermal nature. Groundwater discharges controlled the water chemical composition, and some sedimentation features too. At each stretch, an increase in pCO2 and conductivity was measured around the spring sites. Decreasing trends in conductivity or alkalinity with high enough saturation values with respect to calcite were only clearly observed in the intermediate stretch, which had higher tufa deposition rates than the other two. Tufa deposition rates were higher in cool (autumn+winter) than in warm (spring+summer) periods. In some low-rainfall warm periods, tufa deposition was inhibited or limited due to the low flow –mainly from groundwater inputs– and to the dryness of some river sites, which indeed favoured erosion during flooding. A decrease in yearly deposition rates from April 2006 onwards paralleled an important reduction in the river discharge. Groundwater inputs, drought periods and flood events should therefore be considered to understand fluvial tufa sedimentation in semi-arid conditions.

Hydrogeochemical characterization of an evaporite karst area affected by sinkholes (Ebro Valley, NE Spain)

The main processes controlling the hydrochemistry of an alluvium-covered evaporite karst area with high sinkhole risk (Ebro Valley, NE Spain) are examined by means of multivariate analyses (Principal Component Analysis and Hierarchical Cluster Analysis), ion correlations and geochemical speciation-solubility calculations. The hydrogeochemistry of the studied system seems to be governed by the interaction between the groundwater from the salt-bearing evaporitic karst aquifer and from the overlying Ebro River alluvial aquifer. The observed hydrochemical features in the alluvial-karst aquifer system are mainly determined by the relative contribution of gypsum/anhydrite and halite dissolution, showing a wide spectrum from relatively fresh recharge waters (mainly irrigation waters) to highly evolved groundwater from the evaporitic aquifer. The variability of these contributions is especially evident at sinkhole ponds which, in some cases, seem to be associated with discharge areas of the karst aquifer in the valley bottom alluvium. Calculated saturation indexes suggest that, in contrast to gypsum, the amounts of halite in the sampled portions of evaporitic aquifer are not large enough to attain equilibrium, which is consistent with the predominance of gypsum/anhydrite reported for these materials. Furthermore, the observed Na:Cl and Ca:SO4 correlations and stoichiometries suggest that other possible processes, such as glauberite dissolution or Na/Ca-exchange, generally play a minor role (compared to halite and gypsum dissolution) in this system. Another important process in the system is the dissolution of carbonate minerals (dolomite and, possibly, calcite) fostered by the input of CO2(g), which is probably produced by pedogenic processes. Dolomite dissolution seems to be particularly relevant in the evaporitic materials probably due to dedolomitisation triggered by gypsum/anhydrite dissolution.

Geochemical processes controlling water salinization in an irrigated basin in Spain: Identification of natural and anthropogenic influence

Salinization of water bodies represents a significant risk in water systems. The salinization of waters in a small irrigated hydrological basin is studied herein through an integrated hydrogeochemical study including multivariate statistical analyses and geochemical modeling. The study zone has two well differentiated geologic materials: (i) Quaternary sediments of low salinity and high permeability and (ii) Tertiary sediments of high salinity and very low permeability. In this work, soil samples were collected and leaching experiments conducted on them in the laboratory. In addition, water samples were collected from precipitation, irrigation, groundwater, spring and surface waters. The waters show an increase in salinity from precipitation and irrigation water to ground- and, finally, surface water. The enrichment in salinity is related to the dissolution of soluble mineral present mainly in the Tertiary materials. Cation exchange, precipitation of calcite and, probably, incongruent dissolution of dolomite, have been inferred from the hydrochemical data set. Multivariate statistical analysis provided information about the structure of the data, differentiating the group of surface waters from the groundwaters and the salinization from the nitrate pollution processes. The available information was included in geochemical models in which hypothesis of consistency and thermodynamic feasibility were checked. The assessment of the collected information pointed to a natural control on salinization processes in the Lerma Basin with minimal influence of anthropogenic factors.

Major hydrogeochemical processes in an acid mine drainage affected estuary.

This study provides geochemical data with the aim of identifying and quantifying the main processes occurring in an Acid Mine Drainage (AMD) affected estuary. With that purpose, water samples of the Huelva estuary were collected during a tidal half-cycle and ion-ion plots and geochemical modeling were performed to obtain a general conceptual model. Modeling results indicated that the main processes responsible for the hydrochemical evolution of the waters are: (i) the mixing of acid fluvial water with alkaline ocean water; (ii) precipitation of Fe oxyhydroxysulfates (schwertmannite) and hydroxides (ferrihydrite); (iii) precipitation of Al hydroxysulfates (jurbanite) and hydroxides (amorphous Al(OH)3); (iv) dissolution of calcite; and (v) dissolution of gypsum. All these processes, thermodynamically feasible in the light of their calculated saturation states, were quantified by mass-balance calculations and validated by reaction-path calculations. In addition, sorption processes were deduced by the non-conservative behavior of some elements (e.g., Cu and Zn).

Characterisation and modelling of mixing processes in groundwaters of a potential geological repository for nuclear wastes in crystalline rocks of Sweden

This paper presents the mixing modelling results for the hydrogeochemical characterisation of groundwaters in the Laxemar area (Sweden). This area is one of the two sites that have been investigated, under the financial patronage of the Swedish Nuclear Waste and Management Co. (SKB), as possible candidates for hosting the proposed repository for the long-term storage of spent nuclear fuel. The classical geochemical modelling, interpreted in the light of the palaeohydrogeological history of the system, has shown that the driving process in the geochemical evolution of this groundwater system is the mixing between four end-member waters: a deep and old saline water, a glacial meltwater, an old marine water, and a meteoric water. In this paper we put the focus on mixing and its effects on the final chemical composition of the groundwaters using a comprehensive methodology that combines principal component analysis with mass balance calculations. This methodology allows us to test several combinations of end member waters and several combinations of compositional variables in order to find optimal solutions in terms of mixing proportions. We have applied this methodology to a dataset of 287 groundwater samples from the Laxemar area collected and analysed by SKB. The best model found uses four conservative elements (Cl, Br, oxygen-18 and deuterium), and computes mixing proportions with respect to three end member waters (saline, glacial and meteoric). Once the first order effect of mixing has been taken into account, water-rock interaction can be used to explain the remaining variability. In this way, the chemistry of each water sample can be obtained by using the mixing proportions for the conservative elements, only affected by mixing, or combining the mixing proportions and the chemical reactions for the non-conservative elements in the system, establishing the basis for predictive calculations.

Benthic bacterial diversity from freshwater tufas of the Iberian Range (Spain)

Aiming to characterize the bacterial diversity of modern tufa systems of the Iberian Range (Spain), we surveyed the 16S rRNA gene sequence diversity from 24 sites within three rivers (Añamaza, Mesa and Piedra). These tufas record substantial calcareous growth under different physicochemical conditions and are part of an important, regional landscape-building system. The bacterial community structure and composition, richness and diversity were quantified from denaturing gradient gel electrophoresis fingerprints. Retrieved DNA sequences could be assigned to 10 bacterial phyla and included a variety of phototrophic and heterotrophic groups. Cyanobacteria, mainly filamentous taxa, constituted 43% of all the retrieved sequences, followed by Firmicutes (11%), Gammaproteobacteria (10%), Alphaproteobacteria (7%), Acidobacteria (6%), Bacteroidetes (5%), Betaproteobacteria (4%), Planctomycetes (4%), Actinobacteria (3%) and Deltaproteobacteria (2%). Diatom and Xanthophyceae chloroplast sequences were also detected. Physicochemical variables measured at each site were modelled with multivariate statistics. Principal component analyses yielded the highest variance for salinity-related variables (conductivity; Na(+) , Cl(-) and SO4(2-) concentrations), which correlated negatively and significantly with diversity indices. However, the highest variance explained by individual principal components was relatively low (< 34%). Overall, we show that these young fluvial tufas are inhabited by a large variety of bacteria in diverse and widespread communities.

Características geoquímicas y pautas de evolución de las salmueras superficiales del Salar de Llamara, Chile

RESUMEN En este trabajo se estudia la evolucion hidroquimica de las salmueras superficiales del Salar de Llamara. El desmuestre sistematico de soluciones y sedimentos salinos ha permitido poner de manifiesto el estado continuo de saturacion de las salmueras respecto a calcita y yeso. La intensa evaporacion provoca la concentracion progresiva de las soluciones, que llegan a alcanzar una elevada fuerza ionica (proxima a 6 molal). Se ha identificado la existencia de un proceso de precipitacion de glauberita a partir del analisis mineralogico de las muestras solidas salinas y del tratamiento fisicoquimico de las soluciones; dicho proceso tiene lugar en la etapa de mayor concentracion de las salmueras y lleva asociada la disolucion simultanea de parte del yeso previamente precipitado. La viabilidad termodinamica de este proceso se ha confirmado ademas mediante una simulacion teorica del proceso de evaporacion realizada con el codigo PHRQPITZ.

Écoulements hypodermiques et transferts de solutés dans les placages éoliens du Sahel : étude par traçage isotopique et chimique sous pluies simulées

Aeolian microdunes are key elements of the ecology of the Sahel of Burkina Faso. The aim of the study is to observe the flow and magnitude of water and solutes through the microdunes by artificial isotope (oxygen 18) and chemical (chloride) tracing using demineralised water. It is shown that the quantity of sub-surface water flow is of secondary importance to that of surface runoff (about 5 %), although its importance with regard to solute transport is far from negligible (more than 20 %).

Low temperature geothermal systems in carbonate-evaporitic rocks: Mineral equilibria assumptions and geothermometrical calculations. Insights from the Arnedillo thermal waters (Spain)

Geothermometrical calculations in low-medium temperature geothermal systems hosted in carbonate-evaporitic rocks are complicated because 1) some of the classical chemical geothermometers are, usually, inadequate (since they were developed for higher temperature systems with different mineral-water equilibria at depth) and 2) the chemical geothermometers calibrated for these systems (based on the Ca and Mg or SO4 and F contents) are not free of problems either. The case study of the Arnedillo thermal system, a carbonate-evaporitic system of low temperature, will be used to deal with these problems through the combination of several geothermometrical techniques (chemical and isotopic geothermometers and geochemical modelling). The reservoir temperature of the Arnedillo geothermal system has been established to be in the range of 87±13°C being the waters in equilibrium with respect to calcite, dolomite, anhydrite, quartz, albite, K-feldspar and other aluminosilicates. Anhydrite and quartz equilibria are highly reliable to stablish the reservoir temperature. Additionally, the anhydrite equilibrium explains the coherent results obtained with the δ18O anhydrite - water geothermometer. The equilibrium with respect to feldspars and other aluminosilicates is unusual in carbonate-evaporitic systems and it is probably related to the presence of detrital material in the aquifer. The identification of the expected equilibria with calcite and dolomite presents an interesting problem associated to dolomite. Variable order degrees of dolomite can be found in natural systems and this fact affects the associated equilibrium temperature in the geothermometrical modelling and also the results from the Ca-Mg geothermometer. To avoid this uncertainty, the order degree of the dolomite present in the Arnedillo reservoir has been determined and the results indicate 18.4% of ordered dolomite and 81.6% of disordered dolomite. Overall, the results suggest that this multi-technique approach is very useful to solve some of the problems associated to the study of carbonate-evaporitic geothermal systems.

Geochemical characteristics and evolution paths of the superficial brines in the Llamara Salar (Chile).

En este trabajo se estudia la evolucion hidroquimica de las salmueras superficiales del Salar de Llamara. El desmuestre sistematico de soluciones y sedimentos salinos ha permitido poner de manifiesto el estado continuo de saturacion de las salmueras respecto a calcita y yeso. La intensa evaporacion provoca la concentracion progresiva de las soluciones, que llegan a alcanzar una elevada fuerza ionica (proxima a 6 molal). Se ha identificado la existencia de un proceso de precipitacion de glauberita a partir del analisis mineralogico de las muestras solidas salinas y del tratamiento fisicoquimico de las soluciones; dicho proceso tiene lugar en la etapa de mayor concentracion de las salmueras y lleva asociada la disolucion simultanea de parte del yeso previamente precipitado. La viabilidad termodinamica de este proceso se ha confirmado ademas mediante una simulacion teorica del proceso de evaporacion realizada con el codigo PHRQPITZ.