This paper details a successful synthesis and comparison of a range of tri-metal hydrotalcite-like layered double hydroxides (LDHs) using urea hydrolysis.

Hydrocalumite is a layered double hydroxide (LDH) that is finding increased application in numerous scientific fields. Typically, this material is produced through environmentally polluting methods such as co-precipitation, sol-gel synthesis and urea-hydrolysis. Here, the hydrothermal green (environmentally friendly) synthesis of hydrocalumite (CaAl-OH) from Ca(OH)₂ and Al(OH)₃ in water and the parameters that influence its formation are discussed. The parameters investigated include the reaction temperature, reaction time, molar calcium-to-aluminium ratio, the morphology/crystallinity of reactants used, mixing and the water-to-solids ratio. Hydrocalumite formation was favoured in all experiments, making up between approximately 50% and 85% of the final crystalline phases obtained. Factors that were found to encourage higher hydrocalumite purity include a low water-to-solids ratio, an increase in the reaction time, sufficient mixing, the use of amorphous Al(OH)₃ with a high surface area, reaction at an adequate temperature and, most surprisingly, the use of a calcium-to-aluminium ratio that stoichiometrically favours katoite formation. X-ray diffraction (XRD) and Rietveld refinement were used to determine the composition and crystal structures of the materials formed. Scanning electron microscopy (SEM) was used to determine morphological differences and Fourier-transform infrared analysis with attenuated total reflectance (FTIR-ATR) was used to identify possible carbonate contamination, inter alia. While the synthesis was conducted in an inert environment, some carbonate contamination could not be avoided. A thorough discussion on the topic of carbonate contamination in the hydrothermal synthesis of hydrocalumite was given, and the route to improved conversion as well as the possible reaction pathway were discussed.

Background: The insecticide dichloro-diphenyl-trichloroethane (DDT) is widely used in indoor residual spraying (IRS) for malaria control owing to its longer residual efficacy in the field compared to other World Health Organization (WHO) alternatives. Suitable stabilization to render these alternative insecticides longer lasting could provide a less controversial and more acceptable and effective alternative insecticide formulations than DDT. Methods: This study sought to investigate the reasons behind the often reported longer lasting behaviour of DDT by exposing all the WHO approved insecticides to high temperature, high humidity and ultra-violet light. Interactions between the insecticides and some mineral powders in the presence of an aqueous medium were also tested. Simple insecticidal paints were made using slurries of these mineral powders whilst some insecticides were dispersed into a conventional acrylic paint binder. These formulations were then spray painted on neat and manure coated mud plaques, representative of the material typically used in rural mud houses, at twice the upper limit of the WHO recommended dosage range. DDT was applied directly onto mud plaques at four times the WHO recommended concentration and on manure plaques at twice WHO recommended concentration. All plaques were subjected to accelerated ageing conditions of 40°C and a relative humidity of 90%. Results: The pyrethroids insecticides outperformed the carbamates and DDT in the accelerated ageing tests. Thus UV exposure, high temperature oxidation and high humidity per se were ruled out as the main causes of failure of the alternative insecticides. Gas chromatography (GC) spectrograms showed that phosphogypsum stabilised the insecticides the most against alkaline degradation (i.e., hydrolysis). Bioassay testing showed that the period of efficacy of some of these formulations was comparable to that of DDT when sprayed on mud surfaces or cattle manure coated surfaces. Conclusions: Bioassay experiments indicated that incorporating insecticides into a conventional paint binder or adsorbing them onto phosphogypsum can provide for extended effective life spans that compare favourably with DDT's performance under accelerated ageing conditions. Best results were obtained with propoxur in standard acrylic emulsion paint. Similarly, insecticides adsorbed on phosphogypsum and sprayed on cattle manure coated surfaces provided superior lifespans compared with DDT sprayed directly on a similar surface.

The presence of priority and emerging aromatic-based pollutants in water sources is of growing concern as they are not bioavailable and are present in reuse plant feed streams. These pollutants have known mutagenic and carcinogenic effects and must therefore be removed. Adsorption has been widely accepted as a suitable remediation technology due to its simplicity. Clay-based adsorbents have attracted significant attention due to their low cost, environmentally benign properties and regeneration potential. The present work focused on the thermal modification of a commercial Layered Double Hydroxide (LDH) clay and its subsequent effectiveness as an adsorbent in the removal of phenol from wastewater. Calcination of the neat clay resulted in the formation of metal oxides with varying phases and crystallinity depending on the treatment temperature. The BET surface area increased by 233% upon calcination at 500 °C. The highest phenol removal (85%) was observed in the clay calcined at 500 °C compared to 10% for the neat clay. Optimization studies revealed a maximum adsorption capacity of 12 mg/g at an adsorbent loading of 10 g/L at pH 7. Phenol adsorption was postulated to occur via a two-stage intercalation and surface adsorption mechanism. The equilibrium data were best fitted on the Freundlich isotherm model which describes heterogeneous adsorption. The adsorption kinetics followed a pseudo-second-order kinetic model with rate constants of 4.4 x 10⁻³ g/mg.h for the first 12h and 6.1 x 10⁻³ g/mg.h thereafter.