Sorption of Chromium(VI), Cadmium(II) Ions and Methylene Blue Dye by Pristine, Defatted and Carbonized Nigella sativa L. Seeds from Aqueous Solution

Abstract

Present study reports on the sorption study of chromium(VI), cadmium(II) ions and methylene blue dye by pristine, defatted and carbonized Nigella sativa L. seeds from aqueous solution. The removal of oil from pristine Nigella sativa L. (PNS) seeds was carried out by defatting the Nigella sativa with acetone and N,N-dimethylformamide and then labelled ANS and DNS, respectively. Thereafter the defatted ANS and DNS adsorbents were carbonized at 600 ºC for 2 h under nitrogen and labelled as CANS and CDNS. The results of pristine, defatted and carbonized seeds were compared. The removal of Cr(VI), Cd(II) and methylene blue dye from aqueous solutions was investigated by varying adsorbate concentration, solution pH, reaction contact time and temperature of the solution. The SEM images indicated that the surface morphology of PNS was irregular, whilst ANS and DNS had pores and cavities. CANS and CDNS was heterogeneous and had pores and cavities. FTIR spectroscopy showed that the adsorbents surfaces had bands that indicated a lot of oxygen containing groups. The pH of the solution had an influence on the removal uptake of Cr(VI), Cd(II) and methylene blue. The sorption of Cr(VI) decreased when pH of the solution was increased due to different speciation of Cr(VI) ions whilst the removal of Cd(II) and methylene blue increased when solution pH was increased. Pseudo first order kinetic model well described the adsorption of Cr(VI), Cd(II) and methylene blue onto PNS. On the other hand, the kinetic data for ANS, CANS, DNS and CDNS was well described by pseudo second order. Furthermore, the removal mechanism onto PNS and ANS was better described by Freundlich multilayer model. The CANS, DNS and CDNS fitted Langmuir monolayer model. Thermodynamic parameters indicated that the sorption processes of Cr(VI), Cd(II) and methylene blue was endothermic and effective at high temperatures for all adsorbents. The ΔSº and ΔHº had positive values this confirmed that the sorption of Cr(VI), Cd(II) and methylene blue onto all adsorbents was random and endothermic, respectively. The values of ΔGº confirmed that the sorption of Cr(VI), Cd(II) and methylene blue on all adsorbents was spontaneous and predominated by physical adsorption process. The CANS had highest adsorption capacity of 99.82 mg/g for methylene blue, 96.89 mg/g for Cd(II) and 87.44 mg/g for Cr(VI) followed by CDNS with 93.90, 73.91 and 65.38 mg/g for methylene blue, Cd(II) and Cr(VI), respectively. The ANS capacities were 58.44, 45.28 and 48.96 mg/g whilst DNS capacities were 48.19, 32.69 and 34.65 mg/g for methylene blue, Cd(II) and Cr(VI), respectively. PNS had the lowest sorption capacities at 43.88, 36.01 and 19.84 mg/g for methylene blue, Cd(II) and Cr(VI), respectively.