A white calcium bentonite (CaB) from the Kütahya region, Turkey, contains 35 wt. % opal-CT and 65 wt. 9c Ca-rich montmorillonite (CaM). Samples were heated at various temperatures between 100–1300°C for 2 h. Thermal gravimetric (TG), derivative thermal gravimetric (DTG), and differential thermal analysis (DTA) curves were determined. Adsorption and desorption of N2 at liquid N2 temperature for each heat-treated sample was determined. X-ray diffraction (XRD) and cation-exchange capacity (CEC) data were obtained. The change in the <d(001) value and the deformation of the crystal structure of CaM depend on temperature. Deformation is defined here as changes of the clay by dehydration, dehydroxylation, recrystallization, shrinkage, fracture, etc. The activation energies related to the dehydration and dehydroxylation of CaB calculated from the thermogravimetric data are 33 and 59 kJ mol−1, respectively. The average deformation enthalpies, in the respective temperature intervals between 200–700°C and 700–900°C, were estimated to be 25 and 205 kJ mol−1 using CEC data and an approach developed in this study. The specific surface area (S) and the specific micropore-mesopore volume (V) calculated from the adsorption and desorption data, respectively, show a “zig zag” variation with increasing temperature to 700°C, but decrease rapidly above this temperature. The S and V values were 43 m2 g−1 and 0.107 cm3 g−1, respectively, for untreated bentonite. They reach a maximum at 500°C and are 89 m2 g−1 and 0.149 cm3 g−1 respectively. The XRD data clearly show that, at 500°C, where the irreversible dehydration is completed without any change in the crystal structure, the porosity of CaM reaches its maximum.

A series of organoclays with monolayers, bilayers, pseudotrilayers, paraffin monolayers and paraffin bilayers were prepared from montmorillonite by ion exchange with hexadecyltrimethylammonium bromide (HDTMAB). The HDTMAB concentrations used for preparing the organoclays were 0.5, 0.7, 1.0, 1.5, 2.0 and 2.5 times the montmorillonite cation exchange capacity (CEC). The microstructural parameters, including the BET-N2 surface area, pore volume, pore size, and surfactant loading and distribution, were determined by X-ray diffraction, N2 adsorption-desorption and high-resolution thermogravimetric analysis (HRTG). The BET-N2 surface area decreased from 55 to 1 m2/g and the pore volume decreased from 0.11 to 0.01 cm3/g as surfactant loading was increased from Na-Mt to 2.5CEC-Mt. The average pore diameter increased from 6.8 to 16.3 nm as surfactant loading was increased. After modifying montmorillonite with HDTMAB, two basic organoclay models were proposed on the basis of HRTG results: (1) the surfactant mainly occupied the clay interlayer space (0.5CEC-Mt, 0.7CEC-Mt, 1.0CEC-Mt); and (2) both the clay interlayer space and external surface (1.5CEC-Mt, 2.0CEC-Mt, 2.5CEC-Mt) were modified by surfactant. In model 1, the sorption mechanism of p-nitrophenol to the organoclay at a relatively low concentration involved both surface adsorption and partitioning, whereas, in model 2 it mainly involved only partitioning. This study demonstrates that the distribution of adsorbed surfactant and the arrangement of adsorbed HDTMA+ within the clay interlayer space control the efficiency and mechanism of sorption by the organoclay rather than BET-N2 surface area, pore volume, and pore diameter.

Porous carbons rich in mesopores and with large pore volumes have been prepared by polymerization and carbonization of a carbon precursor, sucrose, within a matrix of the natural clay, halloysite. The carbon precursor was impregnated into the pores of halloysite and mostly deposited on the external surface of the halloysite rods during impregnation. The inorganic matrix was removed by washing the carbon-mineral composite with HF and HCl. The resultant carbons were characterized by nitrogen adsorption analysis and were found to possess a large specific surface area, a large total pore volume and significant mesoporosity, without an activation process being involved. The pore volume and mesoporosity were up to 1.86 cm3/g and 78%, respectively, even at low carbonization temperatures (500°C). The size of the mesopores of the resultant carbons is mainly between 3 and 30 nm and the dominant pore size is ∼3.7 nm. The carbonization temperature has significant effects on the pore-size distribution and structure of the resultant carbons and carbon-mineral composites, respectively. This process is relatively simple and expected to cost less than the high-temperature carbonization process in the preparation of mesoporous carbons with total pore volume and large specific surface areas.

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.

Allophane-related aluminium silicates with various chemical compositions were synthesized using a hydrothermal reaction with inorganic reagents as starting solutions. The X-ray diffraction traces of the synthesized allophanes showed broad reflections centred at 0.34 and 0.23 nm, which were attributed to the imogolite-like structure of the allophanes. Energy-dispersive X-ray measurements confirmed that the Al-rich materials were synthesized as targeted. The specific surface area of the synthesized allophanes was 313–500 m2 g–1, which is greater than that of a natural allophane (248 m2 g–1). The amount of nitrate adsorbed on the synthesized allophanes tended to increase as the Al content increased. The maximum amount of nitrate adsorbed was 2.07 mmol g–1 at pH ~2, which was comparable to that of a common anion-exchange material. A possible adsorption mechanism for nitrate at lower pH levels is the weak NO3– interaction of the positively charged surface of Al-OH2+ sites.

Laboratory studies were conducted to determine the effect of rainfall timing and antecedent moisture on atrazine leaching through intact soil cores taken from no-till and conventional-till corn fields. Simulated rainfall was applied to no-till and conventional-till cores 1 to 14 d after atrazine application and, in a second study, one d after atrazine was applied to no-till and conventional-till cores at 1 to 800 kPa soil moisture. Increasing the lag time between atrazine application and rainfall from one to 14 d reduced the amount of atrazine leached by about 50% for both no-till and conventional-till soil cores. During the same time period, the amount of atrazine adsorbed to soil increased by about 30% for both tillages. Soil dryness (antecedent moisture) at the time of atrazine application had no effect on the amount of atrazine leached through conventional-till cores. However, leaching decreased in no-till cores as antecedent moisture decreased from 1 to 33 kPa; drying to 800 kPa had no further effect. The leaching rate of atrazine was much higher for the initial 0.5 pore volume than for the next 1.5 pore volume at all rainfall timing and antecedent moisture levels. This behavior is indicative of preferential transport.