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The spatial distribution of major ion concentrations limits the pre‐dictability of solute transport processes in field soils. Therefore, it is important to analyze solute transport with chemical reactions based on results obtained from field soils and numerical simulation. A simulation model with cation‐exchange reactions was developed and applied to solute‐transport analysis of an undisturbed field soil. Chemical reaction terms in the convective‐dispersive equation were estimated by the Levenberg‐Marquardt nonlinear least‐squares regression technique to satisfy physical and chemical processes simultaneously. The reliability of the model was tested with liquid‐phase and solid‐phase concentrations of measured spatial distributions of Ca2+, Mg2+, Na+, and K+ after continuous infiltration of KCl solution into an undisturbed soil column. The experimental results revealed that the selectivity coefficients for Ca‐Na and Ca‐Mg exchange could be kept constant, while those for Ca‐K exchange increased with the equivalent fraction of K+ in the solid phase. The effects of the exchange selectivity coefficient on reactive solute transport are discussed based on the simulation results. When a constant selectivity coefficient was used, the model failed to predict the spatial distributions of cation concentrations in the solid phase. Thus, model predictions can be improved by use of variable instead of constant selectivity coefficients.

Probable sources and mechanisms of arsenic (As) release in shallow aquifer in eastern Bangladesh are evaluated using statistical analysis of groundwater compositions. Dissolved As in 39 samples ranged from 8.05 to 341.5 microg/L with an average of 95.14 microg/L. Ninety seven percent of wells exceed the WHO limit (10 microg/L) for safe drinking water. Principal component analysis is applied to reduce 16 measured compositional variables to five significant components (principal components--PCs) that explain 86.63% of the geochemical variance. Two component loadings, namely PC 1 and PC 2 (45.31% and 23.05%) indicate the natural processes within the aquifers in which organic matter is a key reactant in the weathering reactions. Four groups of wells are defined by the PCA and each group of wells represents distinct physicochemical characteristics. Among them, group III groundwater shows higher As concentration together with high concentrations of Fe, Mn, dissolved organic carbon, PO4(3-) and HCO3(-) than groups I and II. Speciation calculations suggest that only wells of group III are saturated with respect to siderite, and all groups of samples are supersaturated with respect of rhodochrosite. The relationship of As with these parameters in the different groups of wells of the study area suggests that reductive dissolution of Fe-Mn oxyhydroxides with microbially mediated degradation of organic matter is considered to be the dominant processes to release As in groundwater.