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Moral, F., Cruz-Sanjulián, J. J., & Olías, M. (2008). Geochemical evolution of groundwater in the carbonate aquifers of Sierra de Segura (Betic Cordillera, southern Spain). Journal of Hydrology, 360(1), 281–296.
Abstract: Sierra de Segura (Betic Cordillera), with a total area of over 3000km2, is the source of the two principal rivers in southern Spain, the Guadalquivir and the Segura. Due to the orographic effect of these mountains, precipitations are considerably more abundant than in nearby lowland areas, where the climate is semi-arid. Sierra de Segura is constituted of Mesozoic and Cenozoic sedimentary rocks, among which there are thick limestone–dolomitic formations which have given rise to extensive outcrops of permeable materials. In geomorphological terms, there is a large plateau intensively karstified that constitutes the main recharge area. Discharge takes place via a large number of springs, of which the 50 most important add up to a mean spring flow of about 13,500l/s. The active geochemical processes in aquifers of Sierra de Segura, with their corresponding time sequence, are: dissolution of CO2, dissolution of calcite, incongruent dissolution of dolomite, dedolomitization, exsolution of CO2, and precipitation of calcite. More evolved water has higher temperature, magnesium content and Mg/Ca ratio; therefore, these parameters can be utilised as indicators of the degree of hydrochemical evolution. In addition, a good correlation between water temperature and magnesium concentration (or Mg/Ca ratio) indicates that an increase in temperature accelerates the kinetics of the dissolution of dolomite. Finally, the distribution of the temperatures in the vadose zone, determined by atmospheric thermal gradient, implies an apparent stratification of the predominant hydrochemical processes and of the groundwater physical and chemical characteristics.
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Nogueira, G., Stigter, T. Y., Zhou, Y., Mussa, F., & Juizo, D. (2019). Understanding groundwater salinization mechanisms to secure freshwater resources in the water-scarce city of Maputo, Mozambique. Science of The Total Environment, 661, 723–736.
Abstract: In this study hydrochemical, isotopic and multivariate statistical tools are combined with a recharge analysis and existing geophysical data to improve understanding of major factors controlling freshwater occurrence and the origins of high salinities in the multi-layered coastal aquifer system of the Great Maputo area in Mozambique. Access to freshwater in this semi-arid area is limited by an inefficient public supply network, scarce surface waters, long droughts and an increasing population growth. Groundwater has a large potential to enhance water security, but its exploitation is threatened by both coastal and inland salinization mechanisms that are poorly understood. A GIS approach is utilized to classify potential recharge zones based on hydrogeological properties and land use/cover, whereas potential recharge rates are estimated through a root zone water balance method. In combination with water stable isotope data results reveal that extreme rainfall events provide the most relevant contributions to recharge, and interception and evaporation play an important role in the low recharge areas. Hierarchical clustering of hydrochemical and isotopic data allows the classification of six water groups, varying from fresh to brackish/salt waters. Corresponding scatter plots and PHREEQC modelling show evaporation and mixing with seawater (up to 5%) as major processes affecting salinity in the area. The co-occurrence of high alkalinity and Cl concentrations, in combination with piezometric and geo-electrical data, suggests that: 1) inland brackish/salt groundwater is caused by mixing with seawater trapped within clay layers; and 2) brackish/salt surface waters result from seepage of brackish groundwater into rivers and wetlands, followed by evaporation, hence increasing salinity and δ18O values. Mixing with small fractions of trapped seawater as main salinity source, rather than halite dissolution, is further corroborated by Br/Cl ratios of brackish/salt water samples near the ocean ratio. Cation exchange upon salinization is mainly observed in the semi-confined aquifer, while freshening takes place in the phreatic aquifer, particularly in areas presenting high recharge rates.
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Stigter, T. Y., van Ooijen, S. P. J., Post, V. E. A., Appelo, C. A. J., & Carvalho Dill, A. M. M. (1998). A hydrogeological and hydrochemical explanation of the groundwater composition under irrigated land in a Mediterranean environment, Algarve, Portugal. Journal of Hydrology, 208(3), 262–279.
Abstract: In the Campina de Faro, in the south of Portugal, agricultural practices have a large impact on groundwater composition. These practices involve pumping of water for irrigation from combinations of large diameter, shallow wells (noras) and small diameter, deep boreholes (furos). Excess irrigation water returns to the aquifer and mixes with water from the regional groundwater flow system. This irrigation return flow is concentrated by strong evapotranspiration and by flushing of fertilisers. The concentration increase induces cation exchange, whereby Ca on the soil exchanger is replaced by Na. The mixing in the aquifer allows application of a mixing cell model which may then be used to calculate transmissivities from the Cl mass balance. The calculations are complicated by the time-variant behaviour of Cl and the method is adjusted to calculate the change of chloride in time. Results from the calculations appear to be in good agreement with hydrochemical observations.
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Wigley, T. M. L., & Plummer, L. N. (1976). Mixing of carbonate waters. Geochimica et Cosmochimica Acta, 40(9), 989–995.
Abstract: When mineral solutions of different compositions are mixed, the molalities and activities of individual ions in the mixture are often non-linear functions of their end-member values. This non-linearity is particularly significant in determining mineral saturation levels. Mixtures of saturated solutions may be either undersaturated or supersaturated depending on the end-member compositions and the physical conditions in which end-members and their mixtures exist. In carbonate solutions important non-linear effects occur due to redistribution of carbonate species. In extreme cases this causes mixture pH to be below both the end-member pH values. A simple but precise computer program (WATMIX) has been developed for calculating mixture composition for closed and open system mixing of arbitrary end-members. A number of mixing examples are considered which allow one to isolate three important processes leading to non-linear behaviour: the algebraic effect, the δPCO2 effect, and the ionic strength effect.
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Alexakis, D., Gotsis, D., & Giakoumakis, S. (2015). Evaluation of soil salinization in a Mediterranean site (Agoulinitsa district—West Greece). Arabian Journal of Geosciences, 8(3), 1373–1383.
Abstract: Soil salinization is an environmental problem having
significant impacts on the soil–water–plant system. This
problem is more frequent in coastal areas due to seawater
intrusion into the land. Assessing the soil salinization is a
critical issue for the agricultural areas situated in the
Mediterranean basin. This paper examines the deterioration
of soil quality in the cultivated land of a Mediterranean site
(Agoulinitsa district—West Greece). Soil samples were collected
in both pre-irrigation and post-irrigation seasons.
Electrical conductivity (EC), pH and the ions Br−, Ca2+, Cl−,
F−, K+, Li+, Mg2+, Na+, NH4
+, NO2
−, NO3
−, PO4
3− and SO4
2−
were determined by the 1:2 (soil/water ratio on weight basis)
method. The salts which were present in both seasons in the
soils of the area studied are KCl, MgCl2, NaCl, CaSO4 and
K2SO4. The wide spatiotemporal variation of EC in the cultivated
land in both seasons demonstrates that soil salinity is
controlled mainly by seawater intrusion and anthropogenic
factors such as the application of salt-rich water which is
directly pumped from the drainage ditches. Seawater intrusion
provides the affected soil with elevated contents of Ca2+, Cl−,
K+, Mg2+, Na+ and SO4
2−. Classification of the soils by using
criteria given by the literature is discussed. Practices to prevent,
or at least ameliorate, salinization in the cultivated land
of Agoulinitsa district are proposed.
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