The kinetics of the adsorption of Pb²⁺ and Cd²⁺ by sodium tetraborate (NTB)-modified kaolinite clay adsorbent was studied. A one-stage and two-stage optimization of equilibrium data were carried out using the Langmuir and time-dependent Langmuir models, respectively. Increasing temperature was found to increase the pseudo-second order kinetic rate constant and kinetic data for Pb²⁺ adsorption were found to fit well with the pseudo-second order kinetic model (PSOM) while that for Cd²⁺ were found to show very good fit to the modified pseudo-first order kinetic model (MPFOM). Binary solutions of Pb²⁺ and Cd²⁺ reduced the adsorption capacity of the modified adsorbent for either metal ion with increased initial sorption rate due to competition of metal ions for available adsorption sites. The use of NTB-modified kaolinite clay adsorbent reduces by approximately 72.2% and 96.3% the amount of kaolinite clay needed to adsorb Pb²⁺ and Cd²⁺ from wastewater solutions. From the two-stage batch adsorber design study, the minimum operating time to determine a specified amount of Pb²⁺ and Cd²⁺ removal was developed. The two-stage batch adsorption process predicted less than half the minimum contact time to reach equilibrium in the one-stage process for the adsorption of Pb²⁺ and Cd²⁺ by NTB-modified kaolinite clay adsorbent and requires 0.05 times the mass of the adsorbent for the single-stage batch adsorption at the same operating conditions.

Background, aim and scope One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.