Emilio Custodio

Modeling of non-isothermal multi-component reactive transport in field scale porous media flow systems

Abstract A general 2-D finite element multi-component reactive transport code, TRANQUI, was developed, using a sequential iteration approach (SIA). It is well suited to deal with complex real-world thermo-hydro-geochemical problems for single-phase variably water saturated porous media flow systems. The model considers a wide range of hydrological and thermodynamic as well as chemical processes such as aqueous complexation, acid-base, redox, mineral dissolution/precipitation, gas dissolution/ex-solution, ion exchange and adsorption via surface complexation. Under unsaturated conditions only water flow is considered, although gas pressures are allowed to vary in space in a depth-dependent manner specified by the user. In addition to the fully iterative sequential approach (SIA), a sequential non-iterative approach (SNIA), in which transport and chemistry are de-coupled, was implemented and tested. The accuracy and numerical performance of SIA and SNIA have been compared using several test cases. The accuracy of SNIA depends on space and time discretization as well as on the nature of the chemical reactions. The capability of the code to model a real case study in the field is illustrated by its application to the modeling of the hydrochemical evolution of the Llobregat Delta aquitard in northeastern Spain over the last 3500 years during when fresh-water flow from a lower aquifer displaced the native saline aquitard waters. Manzano and Custodio carried out a reactive transport model of this case study by using the PHREEQM code and considering water flow, aqueous complexation, cation exchange and calcite dissolution. Their results compare favorably well with measured porewater chemical data, except for some of the cations. Our code is not only able to reproduce the results of previous numerical models, but leads to computed concentrations which are closer to measured data mainly because our model takes into consideration redox processes in addition to the processes mentioned above. A number of sensitivity runs were performed with TRANQUI in order to analyze the effect of errors and uncertainties on cation selectivities.

Inverse modelling of seawater intrusion in the Llobregat delta deep aquifer

Abstract A flow and mass transport mathematical model has been calibrated to simulate piezometric head and chloride evolution in the Llobregat delta confined aquifer. A twenty-year period (1965–1985) is simulated with monthly time steps. Automatic estimation of flow and transport parameters are obtained by means of a code that simulates flow and mass transport of constant density fluids. In this case, density differences owing to groundwater salinity changes by marine intrusion can be neglected because the aquifer thickness is relatively small and because both the horizontal density gradient and the aquifer dip are small. Calibration of the flow problem leads to an excellent fit between measured and computed heads, which, however, can be obtained with different transmissivity patterns. When switching to the transport problem, best results in terms of concentration fits are obtained by associating the seawater intrusion plumes with high transmissivity zones that can be attributed to palaeochannels. In short, transient head and concentration data have been used jointly for automatic calibration of a regional model, which has proven advantageous both because it facilitates model selection and because it has led to a model with an improved conceptual basis.

Exemple d'etude geochimique et isotopique de circulations aquiferes en terrain volcanique sous climat semi-aride (Amurga, Gran Canaria, Iles Canaries)

Abstract A hydrochemical and isotopic study of a groundwater flow system in volcanic media has been carried out in the southern part of Gran Canaria (Canary Islands). Monthly samples of precipitation were collected over a two year period at stations distributed all over the island. Sampling of groundwaters took place mainly from drillholes in the Amurga phonolitic massif but also from wells and springs discharging from the volcanic and related detrital formations. The δ 2 H vs. δ 18 O relationship of the precipitation is close to the “global meteoric water line”. Two distinct altitudinal isotopic gradients are observed. On the warm and dry southern slope, the combination of a contribution of saharan dusts and seasprays and of partial evaporation explains the high content of dissolved salts (Cl − , SO 2− 4 ) in precipitation. Additional processes may be invoked as sources of groundwater mineralization: leaching of silicate minerals during infiltration and/or from hydrolysis during the long residence time of the waters in the volcanic rocks. Salt content is increased through a concentration of the percolating solutions by evaporation, as shown by their stable isotope contents ( 18 O, 2 H). The groundwaters in the phonolitic aquifer are well differentiated from the deeper groundwaters, which are recharged at an altitude of about 1000m above sea level, or even less, if exceptional episodes of rain have a lower heavy isotope content. The interpretation of the 13 C contents of soil CO 2 , sampled throughout the area, and of the 13 C and 14 C contents of total dissolved inorganic carbon (TDIC) leads to the concept of an incorporation of pure biogenic carbon under open-system conditions in the Amurga waters. For these groundwaters, high estimates of residence time (ca. 11000 years) can be calculated from the low 14 C activities. In the neighbouring valleys, the input of deep “dead” volcanic carbon and the occurrence of mixing do not allow an exact quantification of residence time values. However, they seem to be shorter than those measured for the Amurga waters.

Lognormal kriging for the assessment of reliability in groundwater quality control observation networks

Abstract Groundwater quality observation networks are examples of discontinuous sampling on variables presenting spatial continuity and highly skewed frequency distributions. Anywhere in the aquifer, lognormal kriging provides estimates of the variable being sampled and a standard error of the estimate. The average and the maximum standard error within the network can be used to dynamically improve the network sampling efficiency or find a design able to assure a given reliability level. The approach does not require the formulation of any physical model for the aquifer or any actual sampling of hypothetical configurations. A case study is presented using the network monitoring salty water intrusion into the Llobregat delta confined aquifer, Barcelona, Spain. The variable chloride concentration used to trace the intrusion exhibits sudden changes within short distances which make the standard error fairly invariable to changes in sampling pattern and to substantial fluctuations in the number of wells.

Isotopic and hydrogeochemical characterization of high-altitude karst aquifers in complex geological settings. The Ordesa and Monte Perdido National Park (Northern Spain) case study

The Ordesa and Monte Perdido National Park, located in the Southern Pyrenees, constitutes the highest karst system in Western Europe. No previous studies regarding its geochemical and isotopic groundwater characterization are available in this area. This work presents the results of field and sampling campaigns carried out between July 2007 and September 2013. The groundwater presents high calcium bicarbonate contents due to the occurrence of upper Cretaceous and lower Paleocene-Eocene carbonate materials in the studied area. Other relevant processes include dissolution of anhydrite and/or gypsum and incongruent dissolution of Mg-limestone and dolomite. The water stable isotopes (δ(18)O, δ(2)H) show that the oceanic fronts from the Atlantic Ocean are responsible for the high levels of precipitation. In autumn, winter, and spring, a deuterium excess is found in the recharge water, which could be related to local atmospheric transport of low-altitude snow sublimation vapour and its later condensation on the snow surface at higher altitude, where recharge is mostly produced. The recharge zones are mainly between 2500m and 3200ma.s.l. The tritium content of the water suggests short groundwater transit times. The isotopic composition of dissolved sulphate points to the existence of regional fluxes mixed with local discharge in some of the springs. This work highlights the major role played by the altitude difference between the recharge and discharge zones in controlling the chemistry and the vertical variability of the isotopic composition in high-altitude karst aquifers.

Groundwater intensive use and mining in south-eastern peninsular Spain: Hydrogeological, economic and social aspects

Intensive groundwater development is a common circumstance in semiarid and arid areas. Often abstraction exceeds recharge, thus continuously depleting reserves. There is groundwater mining when the recovery of aquifer reserves needs more than 50years. The MASE project has been carried out to compile what is known about Spain and specifically about the south-eastern Iberian Peninsula and the Canary Islands. The objective was the synthetic analysis of available data on the hydrological, economic, managerial, social, and ethical aspects of groundwater mining. Since the mid-20th century, intensive use of groundwater in south-eastern Spain allowed extending and securing the areas with traditional surface water irrigation of cash crops and their extension to former dry lands, taking advantage of good soils and climate. This fostered a huge economic and social development. Intensive agriculture is a main activity, although tourism plays currently an increasing economic role in the coasts. Many aquifers are relatively high yielding small carbonate units where the total groundwater level drawdown may currently exceed 300m. Groundwater storage depletion is estimated about 15km(3). This volume is close to the total contribution of the Tagus-Segura water transfer, but without large investments paid for with public funds. Seawater desalination complements urban supply and part of cash crop cultivation. Reclaimed urban waste water is used for irrigation. Groundwater mining produces benefits but associated to sometimes serious economic, administrative, legal and environmental problems. The use of an exhaustible vital resource raises ethical concerns. It cannot continue under the current legal conditions. A progressive change of water use paradigm is the way out, but this is not in the mind of most water managers and politicians. The positive and negative results observed in south-eastern Spain may help to analyse other areas under similar hydrogeological conditions in a less advanced stage of water use evolution.

Groundwater salinity and hydrochemical processes in the volcano-sedimentary aquifer of La Aldea, Gran Canaria, Canary Islands, Spain

The origin of the groundwater salinity and hydrochemical conditions of a 44km(2) volcano-sedimentary aquifer in the semi-arid to arid La Aldea Valley (western Gran Canaria, Spain) has been studied, using major physical and chemical components. Current aquifer recharge is mainly the result of irrigation return flows and secondarily that of rainfall infiltration. Graphical, multivariate statistical and modeling tools have been applied in order to improve the hydrogeological conceptual model and identify the natural and anthropogenic factors controlling groundwater salinity. Groundwater ranges from Na-Cl-HCO3 type for moderate salinity water to Na-Mg-Cl-SO4 type for high salinity water. This is mainly the result of atmospheric airborne salt deposition; silicate weathering, and recharge incorporating irrigation return flows. High evapotranspiration produces significant evapo-concentration leading to relative high groundwater salinity in the area. Under average conditions, about 70% of the water used for intensive agricultural exploitation in the valley comes from three low salinity water runoff storage reservoirs upstream, out of the area, while the remaining 30% derives from groundwater. The main alluvial aquifer behaves as a short turnover time reservoir that adds to the surface waters to complement irrigation water supply in dry periods, when it reaches 70% of irrigation water requirements. The high seasonality and intra-annual variability of water demand for irrigation press on decision making on aquifer use by a large number of aquifer users acting on their own.

Groundwater intensive exploitation and mining in Gran Canaria and Tenerife, Canary Islands, Spain: Hydrogeological, environmental, economic and social aspects.

Intensive exploitation and continuous consumption of groundwater reserves (groundwater mining) have been real facts for decades in arid and semiarid areas. A summary of experience in the hydrogeological, economic, social and ethical consequences of groundwater intensive and mining exploitation in Gran Canaria and Tenerife Islands, in the Canarian Archipelago, is presented. Groundwater abstraction is less than recharge, but a significant outflow of groundwater to the sea cannot be avoided, especially in Tenerife, due to its younger volcanic coastal formations. Consequently, the intensive aquifer groundwater development by means of wells and water galleries (tunnels) has produced a groundwater reserve depletion of about 2km(3). Should current groundwater abstraction cease, the recovery time to close-to-natural conditions is from decades to one century, except in the mid and high elevations of Tenerife, where this recovery is not possible as aquifer formations will remain permanently drained by the numerous long water galleries. The socio-economic circumstances are complex due to a long standing history of water resources exploitation, successive social changes on each island, and well-established groundwater water trading, with complex relationships that affect water governance and the resulting ethical concerns. Gran Canaria and Tenerife are in an advanced groundwater exploitation stage and have a large water demand. They are good examples that allow drawing guidelines to evaluate groundwater development on other small high islands. After presenting the hydrogeological background, the socio-economic results are discussed to derive general knowledge to guide on water governance.

Chapter 5.2:Groundwater Quality Background Levels

Groundwater forms complex, three-dimensional bodies in which recharge, flow conditions and interaction with the solid matrix are point dependent. This means that, in a given groundwater body, the chemical, radiochemical and biochemical characteristics of water vary both in space (horizontally and ve...

Groundwater flow in a closed basin with a saline shallow lake in a volcanic area: Laguna Tuyajto, northern Chilean Altiplano of the Andes

Laguna Tuyajto is a small, shallow saline water lake in the Andean Altiplano of northern Chile. In the eastern side it is fed by springs that discharge groundwater of the nearby volcanic aquifers. The area is arid: rainfall does not exceed 200mm/year in the rainiest parts. The stable isotopic content of spring water shows that the recharge is originated mainly from winter rain, snow melt, and to a lesser extent from some short and intense sporadic rainfall events. Most of the spring water outflowing in the northern side of Laguna Tuyajto is recharged in the Tuyajto volcano. Most of the spring water in the eastern side and groundwater are recharged at higher elevations, in the rims of the nearby endorheic basins of Pampa Colorada and Pampa Las Tecas to the East. The presence of tritium in some deep wells in Pampa Colorada and Pampa Las Tecas indicates recent recharge. Gas emission in recent volcanoes increase the sulfate content of atmospheric deposition and this is reflected in local groundwater. The chemical composition and concentration of spring waters are the result of meteoric water evapo-concentration, water-rock interaction, and mainly the dissolution of old and buried evaporitic deposits. Groundwater flow is mostly shallow due to a low permeability ignimbrite layer of regional extent, which also hinders brine spreading below and around the lake. High deep temperatures near the recent Tuyajto volcano explain the high dissolved silica contents and the δ(18)O shift to heavier values found in some of the spring waters. Laguna Tuyajto is a terminal lake where salts cumulate, mostly halite, but some brine transfer to the Salar de Aguas Calientes-3 cannot be excluded. The hydrogeological behavior of Laguna Tuyajto constitutes a model to understand the functioning of many other similar basins in other areas in the Andean Altiplano.