The surface characteristics of natural heulandites/clinoptilolites with different extra-framework cations

Natural tuff samples in western Anatolia (TÜrkiye) originating from Miocene rhyolitic-pyroclastic rocks with >80 wt.% heulandite/clinoptilolite zeolites were investigated for their surface characteristics determined according to nitrogen adsorption after degassing at 150°C (specific surface area, pore volume and pore diameter). Additionally, these surface characteristics were correlated with the cationic compositions of the heulandite/clinoptilolite group minerals. The examined samples were characterized by two main pore diameters that were not related to specific surface area and pore volume but were partially related to the types and occupancy of extra-framework cations. One set of samples has a pore diameter of ~24 Å, total cation content (Na + K + Ca + Mg) ranging from 3.46 to 4.40 and a (Na + K)/(Ca + Mg) ratio ranging from 0.34 to 0.92. The total cation contents and (Na + K)/(Ca + Mg) ratios of the remaining samples with a pore diameter of ~37 Å are 4.30-5.08 and 1.48-2.85, respectively. After degassing at 300°C, there is a slight difference in the pore diameters of these two sets of samples (~37 and 38 Å). The pore sizes of the samples with a (Na + K)/(Ca + Mg) ratio < 1 (heulandite composition) increased from 24 to 36-38 Å with increasing degassing temperature, whereas the pore sizes of the samples with a (Na + K)/(Ca + Mg) ratio > 1 (clinoptilolite composition) increased from 37 to only 38-39 Å. However, there is no correlation between the Si/Al ratios and the cation-exchange capacities of the samples and their surface characteristics obtained by degassing at the two temperatures.