Quantitative imaging of the 3-D distribution of cation adsorption sites in undisturbed soil

Abstract. Several studies have shown that the distribution of cation adsorption sites (CASs) is patchy at a millimetre to centimetre scale. Often, larger concentrations of CASs in biopores or aggregate coatings have been reported in the literature. This heterogeneity has implications on the accessibility of CASs and may influence the performance of soil system models that assume a spatially homogeneous distribution of CASs. In this study, we present a new method to quantify the abundance and 3-D distribution of CASs in undisturbed soil that allows for investigating CAS densities with distance to the soil macropores. We used X-ray imaging with Ba²⁺ as a contrast agent. Ba²⁺ has a high adsorption affinity to CASs and is widely used as an index cation to measure the cation exchange capacity (CEC). Eight soil cores (approx. 10 cm³) were sampled from three locations with contrasting texture and organic matter contents. The CASs of our samples were saturated with Ba²⁺ in the laboratory using BaCl₂ (0.3 mol L⁻¹). Afterwards, KCl (0.1 mol L⁻¹) was used to rinse out Ba²⁺ ions that were not bound to CASs. Before and after this process the samples were scanned using an industrial X-ray scanner. Ba²⁺ bound to CASs was then visualized in 3-D by the difference image technique. The resulting difference images were interpreted as depicting the Ba²⁺ bound to CASs only. The X-ray image-derived CEC correlated significantly with results of the commonly used ammonium acetate method to determine CEC in well-mixed samples. The CEC of organic-matter-rich samples seemed to be systematically overestimated and in the case of the clay-rich samples with less organic matter the CEC seemed to be systematically underestimated. The results showed that the distribution of the CASs varied spatially within most of our samples down to a millimetre scale. There was no systematic relation between the location of CASs and the soil macropore structure. We are convinced that the approach proposed here will strongly aid the development of more realistic soil system models.