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Rina, K., Datta, P. S., Singh, C. K., & Mukherjee, S. (2013). Isotopes and ion chemistry to identify salinization of coastal aquifers of Sabarmati River Basin. Current Science, 104(3), 335–344.
Abstract: The lower reaches of the Sabarmati River Basin in Gujarat have intense agricultural and industrial activities and this part is affected by problems of groundwater salinity. Here we attempt to assess the processes governing the causes of groundwater salinity in the coastal alluvial aquifer, employing δ18O and δD isotopes in integration with ionic ratio. The different hydrochemical facies such Na–Mg–HCO3–Cl, Na–Cl–SO4, Na–Mg–Cl–HCO3–SO4 and Na–Cl of groundwater show the occurrence of complex geochemical phenomenon in the study area. Ionic ratio (such as Mg2+/Ca2+, Na+/Cl−, SO24/Cl-, K+/Cl−) and isotopic composition (δ18O and δD) of groundwater indicate that while in coastal areas seawater intrusion is taking place, in inland areas various anthropogenic activities and overexploitation have induced salinity in groundwater. Over-pumping of groundwater has also induced lateral intermixing of highly saline water in the vicinity of coastal areas with relatively fresh/low saline groundwater along specific flow pathways.
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Nadler, A., Magaritz, M., & Mazor, E. (1980). Chemical reactions of sea water with rocks and freshwater: Experimental and field observations on brackish waters in Israel. Geochimica et Cosmochimica Acta, 44(6), 879–886.
Abstract: Four major processes are observed to take place in the coastal aquifer of Israel, detectable even in the short times of water contact with the carbonate-containing host rocks. Three are chemical reactions, Ca2+-Mg2+ exchange, Na+-Ca2+ or Na+-Mg2+ base exchange, SO2−4 reduction and the fourth is dilution by freshwater. These reactions and their effects on the chemical composition of the waters were demonstrated experimentally. The range of chemical changes observed in the laboratory experiments overlap the range of the studied natural waters. This indicates that simulation of geologically long-term rock-water interaction could be achieved in laboratory experiments even at low temperatures.
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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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Hanshaw, B. B., & Back, W. (1979). Major geochemical processes in the evolution of carbonate—Aquifer systems. Journal of Hydrology, 43(1), 287–312.
Abstract: As a result of recent advances by carbonate petrologists and geochemists, hydrologists are provided with new insights into the origin and explanation of many aquifer characteristics and hydrologic phenomena. Some major advances include the recognition that: (1) most carbonate sediments are of biological origin; (2) they have a strong bimodal size-distribution; and (3) they originate in warm shallow seas. Although near-surface ocean water is oversaturated with respect to calcite, aragonite, dolomite and magnesite, the magnesium-hydration barrier effectively prevents either the organic or inorganic formation of dolomite and magnesite. Therefore, calcareous plants and animals produce only calcite and aragonite in hard parts of their bodies. Most carbonate aquifers that are composed of sand-size material have a high initial porosity; the sand grains that formed these aquifers originated primarily as small shells, broken shell fragments of larger invertebrates, or as chemically precipitated oolites. Carbonate rocks that originated as fine-grained muds were initially composed primarily of aragonite needles precipitated by algae and have extremely low permeability that requires fracturing and dissolution to develop into aquifers. Upon first emergence, most sand beds and reefs are good aquifers; on the other hand, the clay-sized carbonate material initially has high porosity but low permeability, a poor aquifer property. Without early fracture development in response to influences of tectonic activity these calcilutites would not begin to develop into aquifers. As a result of selective dissolution, inversion of the metastable aragonite to calcite, and recrystallization, the porosity is collected into larger void spaces, which may not change the overall porosity, but greatly increases permeability. Another major process which redistributes porosity and permeability in carbonates is dolomitization, which occurs in a variety of environments. These environments include back-reefs, where reflux dolomites may form, highly alkaline, on-shore and continental lakes, and sabkha flats; these dolomites are typically associated with evaporite minerals. However, these processes cannot account for most of the regionally extensive dolomites in the geologic record. A major environment of regional dolomitization is in the mixing zone (zone of dispersion) where profound changes in mineralogy and redistribution of porosity and permeability occur from the time of early emergence and continuing through the time when the rocks are well-developed aquifers. The reactions and processes, in response to mixing waters of differing chemical composition, include dissolution and precipitation of carbonate minerals in addition to dolomitization. An important control on permeability distribution in a mature aquifer system is the solution of dolomite with concomitant precipitation of calcite in response to gypsum dissolution (dedolomitization). Predictive models developed by mass-transfer calculations demonstrate the controlling reactions in aquifer systems through the constraints of mass balance and chemical equilibrium. An understanding of the origin, chemistry, mineralogy and environments of deposition and accumulation of carbonate minerals together with a comprehension of diagenetic processes that convert the sediments to rocks and geochemical, tectonic and hydrologic phenomena that create voids are important to hydrologists. With this knowledge, hydrologists are better able to predict porosity and permeability distribution in order to manage efficiently a carbonate—aquifer system.
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Han, D., Post, V. E. A., & Song, X. (2015). Groundwater salinization processes and reversibility of seawater intrusion in coastal carbonate aquifers. Journal of Hydrology, 531, 1067–1080.
Abstract: Seawater intrusion (SWI) has led to salinization of fresh groundwater reserves in coastal areas worldwide and has forced the closure of water supply wells. There is a paucity of well-documented studies that report on the reversal of SWI after the closure of a well field. This study presents data from the coastal carbonate aquifer in northeast China, where large-scale extraction has ceased since 2001 after salinization of the main well field. The physical flow and concomitant hydrogeochemical processes were investigated by analyzing water level and geochemical data, including major ion chemistry and stable water isotope data. Seasonal water table and salinity fluctuations, as well as changes of δ2H–δ18O values of groundwater between the wet and dry season, suggest local meteoric recharge with a pronounced seasonal regime. Historical monitoring testifies of the reversibility of SWI in the carbonate aquifer, as evidenced by a decrease of the Cl− concentrations in groundwater following restrictions on groundwater abstraction. This is attributed to the rapid flushing in this system where flow occurs preferentially along karst conduits, fractures and fault zones. The partially positive correlation between δ18O values and TDS concentrations of groundwater, as well as high NO3− concentrations (\textgreater39mg/L), suggest that irrigation return flow is a significant recharge component. Therefore, the present-day elevated salinities are more likely due to agricultural activities rather than SWI. Nevertheless, seawater mixing with fresh groundwater cannot be ruled out in particular where formerly intruded seawater may still reside in immobile zones of the carbonate aquifer. The massive expansion of fish farming in seawater ponds in the coastal zone poses a new risk of salinization. Cation exchange, carbonate dissolution, and fertilizer application are the dominant processes further modifying the groundwater composition, which is investigated quantitatively using hydrogeochemical models.
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