The electrical conductivity at 25 • C (EC 25 ) of soil solutions or irrigation waters is the standard property for assessing salinity. Many models for soil salinity prediction calculate the major ion composition of the soil solution. The electrical conductivity of a solution can be determined from its composition through several different empirical equations. An assessment of these equations is necessary to incorporate the most accurate and precise equations in such models. Twelve different equations for the EC 25 calculation were calibrated by means of regression analyses with data from 133 saturation extracts and another 135 1:5 soil-to-water extracts from a salt-affected agricultural irrigated area. The equations with better calibration parameters were tested with another data set of 153 soil solutions covering a wide range of salt concentrations and compositions. The testing was conducted using the standardized difference t-test, which is a rigorous validation test used in this study for the first time. The equations based on the ionic conductivity decrement given by Kohlrausch's law presented the poorest calibration parameters. The equations founded on the hypothesis that EC 25 is proportional to analytical concentrations had worse calibration and validation parameters than their counterparts based on free-ion concentrations and ionic activities. The equations founded on simpler mathematical relationships generally gave improved validation parameters. The three equations based on the specific electrical conductivity definition presented a mean standardized difference between observations and predictions indistinguishable from zero at the 95% confidence level. The inclusion of the charged ion-pair concentrations in the equation based on free-ion concentrations improved its predictions, particularly at large electrical conductivities. This equation can be reliably used in conjunction with chemical speciation software to assess EC 25 from the ion composition of soil solutions.
Soil salinity is an important issue constraining the productivity of irrigation agriculture around the world. The standard method for soil salinity assessment is based on a laboratory method that is cumbersome and gives rise to limitations for data-intensive works. The use of sensors for the assessment of the apparent electrical conductivity (EC) of soils offers a way to overcome these constraints. These sensors are based on three electromagnetic phenomena, namely, electrical resistivity, electromagnetic induction, and reflectometry. Each class of sensors presents its own advantages and drawbacks. In the following chapter, these are presented along with the most popular commercial EC sensors used in nowadays agriculture, equations for the assessment of soil salinity on basis sensor measurements, some examples of application, and present and future development trends.
Calcite and gypsum are salts of major ions characterized by poor solubility compared with other salts that may precipitate in soils. Knowledge of calcite and gypsum solubility products in water-saturated soil samples substantially contributes to a better assessment of processes involved in soil salinity. The new SALSOL-CHEMIS code for chemical equilibrium assessment was parameterized with published analytical data for aqueous synthetic calcite and gypsum-saturated solutions. Once parameterized, SALSOLCHEMIS was applied to calculations of the ionic activity products of calcium carbonate and calcium sulphate in 133 water-saturated soil samples from an irrigated salt-affected agricultural area in a semi-arid Mediterranean climate. During parameterization, sufficiently constant values for the ionic activity products of calcium carbonate and calcium sulphate were obtained only when the following were used in SALSOLCHEMIS: (i) the equations of Sposito & Traina for the free ion activity coefficient calculation, (ii) the assumption of the non-existence of the Ca(HCO 3 ) + and CaCO 3 o ion pairs and (iii) a paradigm of total ion activity coefficients. The value of 4.62 can be assumed to be a reliable gypsum solubility product (pKs) in simple aqueous and soil solutions, while a value of 8.43 can only be assumed as a reliable calcite solubility product (pKs) in simple aqueous solutions. The saturated pastes and saturation extracts were found to be calcite over-saturated, with the former significantly being less so (pIAP = 8.29) than the latter (pIAP = 8.22). The calcite over-saturation of saturated pastes increased with the soil organic matter content. Nevertheless, the inhibition of calcite precipitation is caused by the soluble organic matter from a dissolved organic carbon threshold value that lies between 7 and 12 mm. The hypothesis of thermodynamic equilibrium is more adequate for the saturated pastes than for the saturation extracts.
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