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Limestone beds of the Late Cretaceous Abiod formation (Campanian-Maastrichtian system) are fundamentally important for the economic growth of the raw material sector in Tunisia. However, little attention has been paid to the detailed physical and chemical properties of the Abiod limestone. Nine limestone samples collected from the Abiod formation outcropping in the areas of Bizerte, Gafsa and Gabes, Tunisia, as well as their separated clay fractions, were characterized using different techniques, such as XRF, XRD, FTIR and TG/DTA. XRF showed the chemical composition of the limestone in which calcium carbonate was the main constituent, and silica, iron and magnesium were the impurities. XRD also confirmed the presence of small amounts of clay minerals and quartz along with sharp peaks of calcite. FTIR spectra indicated that the limestone was mainly composed of CaCO 3 in the form of calcite, as identified by its main characteristic absorption bands. These data were in agreement with XRD and XRF analysis data. The TG/DTA curves of the limestone samples, showing a close similarity to that of pure calcium carbonate, exhibited an endothermic peak between 600 and 760°C, with the maximum near 750°C. Moreover, FTIR spectra of clay fraction samples indicated high silica content in some samples.Especially the samples SD1 and SD2 collected in the northern area showed higher amounts of silica compared with those of AS1, AS2, CHB, ZNC, SND, MKM and GBS collected from southern districts. However, among the latter seven samples, one could recognize two groups based on the clay mineral investigations: (1) limestone with minor amounts of smectite and mixed layer minerals of smectite/ illite (AS1 and 2, CHB, ZNC, SND and GBS) and (2) limestone with smectite, kaolinite and apatite (SND and MKM). Differences in these mineralogical and chemical characteristics should be considered when limestone from the Abiod formation is utilized as a medium for heavy metal removal from wastewater.

Calcareous and smectitic clay samples from the Coniacian-Lower Campanian system, Tunisia, were used as adsorbents for the removal of copper and zinc from aqueous solutions in single and binary systems. Calcareous clay sample was treated with acetic acid to obtain carbonate-free sample that was also used for metals removal. The adsorption of metal ions onto natural clay was tested in a batch method by mixing 1 g/L of each sample with a metal ion solution of zinc (300 lmol/L) and/or copper 600 lmol/L under the operating pH of 6, and agitation speed of 200 rpm within the equilibrium time of 60 min at 25°C for single and binary systems. Our results showed that natural clay samples were mainly composed of silica, alumina, iron, and magnesium oxides. Adsorption data showed that the studied clay samples removed substantial amounts of heavy metals in single and mixed systems. Initial solution pH and carbonates contents enhanced the removal capacities of the studied clay samples, confirming their strong influencing effects. Thermodynamic parameters indicated an endothermic adsorption for metals removal by calcareous clay, but exothermic process for the smectitic sample. These results suggest that the Late Cretaceous clays, Tunisia, can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.