The aim of this study was to evaluate total mercury concentration and its lithogenic and exogenic fractions in some calcareous soils of western Iran, where water contamination and bioaccumulation of mercury have been reported in the bottomland’s reservoir. In particular, we investigated soil physico-chemical properties and weathering conditions related to lithogenic and exogenic fractions of mercury for two groups of calcareous soils with a known comparative pedological evolution and weathering condition that was evident in the presence or absence of underlying layers of accumulated clay. Our results showed that the total mercury content of the studied soils ranged from 45.40 to 830.36 with a mean of 486.81 μg kg−1. Furthermore, calculation of mercury fractions revealed that lithogenic and exogenic fractions vary slightly according to the three reference elements (Fe, U and Nb) used in the calculations for the two groups of studied soils. The results also illustrated that most of the mercury content is of exogenic origin; therefore, total mercury variations are closely related to the content of exogenic mercury, while the lithogenic fraction exhibited no relationship with total mercury concentration. Moreover, application of the weathering indexes of Parker and the CaO/ZrO2 molar ratio supported the dependence of lithogenic mercury accumulation on weathering intensity in the studied calcareous soils. However, the significance of this relationship is stronger for more weathered calcareous soils; in such cases, fine-particle fractions are more developed, which encourages carrier phases such as organic materials and iron oxyhydroxides to become involved in more efficient fixation of mercury. Nevertheless, the formation of underlying layers of accumulated clay, i.e. argillic horizons, may restrain fixation of exogenic mercury by limiting its atmospheric input.
