Effect of metal oxide on surface area and pore size of water-dispersible colloids from three German silt loam topsoils

Abstract

The surface area and pore structure of easily dispersed soil particles <2μm in size (water-dispersible colloids, WDCs) are important for carbon sequestration and transport in soil, two processes which are essential for the terrestrial carbon cycling. In this work, we determine the effects of dithionite–citrate–bicarbonate (DCB) extractable metal oxides, and oxalate extractable metal oxides on the specific surface area (SSA) and pore structure of WDCs from silt loam topsoils of three TERENO test sites with a similar clay content (20%) in Germany (arable (Selhausen), grassland (Rollesbroich) and forest (Wuestebach) soils). The N2 gas-adsorption (−196°C), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and microelectrophoretic (ME) methods were used and compared. Results show that 1) the SSA of the WDCs from Selhausen, Rollesbroich, and Wuestebach decreased more after DCB treatment (27%, 35%, and 44%) than after oxalate treatment (5%, 14%, and 22%). DCB removed metal oxide nanoparticles from WDCs were found to have diameters (dp) ranging from 4nm to 8nm and the surface loading ratios on the surface of aluminosilicate residues in WDCs were estimated to be 11% to 22% for three soils where the highest value was found in the acidic forest soil. 2) Pore sizes in the mesopore range (2nm to 50nm) were analyzed in the WDC fractions. The results were discussed in terms of accessible open pores for the pristine WDCs and WDC samples from which metal oxide nanoparticles and organic carbon (OC) had been removed. The lower average pore radius (Rp) measured by the N2 gas-adsorption method based on the total volume (Vt) to SSA ratio variations in WDCs without metal oxides compared to WDC with metal oxides indicated a contraction of the porous structure of WDCs due to the presence of metal oxide nanoparticles. The pore size distribution (PSD) analysis showed a sensitive contribution of metal oxide nanoparticles in the low range of pore sizes (<25nm) of WDCs. In SAXS measurements, higher surface fractal dimensions (Ds) were observed in WDCs before the metal oxide's removal, which supports a roughness increase of the interfaces in the presence of nanoparticles. The colloidal characterization of WDCs by the DLS and ME methods shows, at a μm scale, the role of positively charged metal oxide nanoparticles in forming WDCs with a more compact structure by decreasing the particle size (dz) and the negative zeta potential (ζ). 3) The comparison of Rp, k, dz and dp results between different soils also indicates the dependence on the clay mineralogy of WDCs so that the heterocoagulation between kaolinite and illite (clay minerals of different aspect ratios) increases the size of soil mesopores (Rollesbroich). In conclusion, the results of this study clearly show that the combination of the N2 gas-adsorption, SAXS, DLS and ME methods allows the characterization of soil porosity in the nanometer range where metal oxide nanoparticles contribute to a more compact structure of WDC.