Adsorption studies of toxic metal ions (Co(II), Ni(II), Cu(II), Cr(VI) and Pb(II)) and methylene blue using black cumin (Nigella sativa L.) seeds

Abstract

High levels of pollutants in water are found to have poisonous effects on human health. Due to increasing awareness about the environment and strict environmental regulations, wastewater treatment has become a very important aspect of research. Thus, this makes the adsorption of pollutants an urgent matter. The aim of this research was to investigate the adsorption capacity of black cumin seeds in the removal of cobalt-Co(II), nickel-Ni(II), copper-(II), chromium-Cr(VI), lead-Pb(II), and methylene blue (MB) dye from aqueous solution. In this research work the black cumin seeds were reacted with sodium hydroxide (NaOH), hydrochloric acid (HCl), phosphoric acid (H3PO4), potassium permanganate (KMnO4) and sulfuric acid (H2SO4). Thereafter it was carbonized at 200 and 300 °C and functionalized with magnetite-sucrose nanoparticles and further carbonized at 600 °C to improve the adsorption capacity of the materials towards different pollutants. The seeds were characterized by scanning electron microscopy (SEM), thermogravimetric analyser (TGA), X-ray diffractometer (XRD), Brunauer, Emmett and Teller (BET) and Fourier transformed infrared (FTIR) spectroscopy. The SEM images showed that the surface morphology of the treated adsorbents was more porous and had cavities more than the starting material. The TGA profile showed a major weight loss between 198-487 °C which was due to disintegration of cellulose, lignin and hemicellulose. The XRD spectra of adsorbents showed broad peaks at 2θ value of 21° associated crystalline lignocellulose content. FTIR results showed that the adsorbents had functional groups such as hydroxyl (-OH), carboxyl (-COOH), amide (-NH) and carbonyl (-C=O). The BET surface area of pristine black cumin seeds was 2.7 m2/g and increased after treatment with KMnO4 and H3PO4 to 10.1 and 9.3 m2/g respectively. The surface area of the carbon black cumin seeds was 11.67 m2/g whilst the activation of carbon from black cumin seeds with 10 and 20% H2SO4 gave the surface area of 20.14 and 21.54 m2/g respectively. The seeds activated with 20% H2SO4 showed larger pore width of 7.13 nm compared to 6.81 and 3.78 nm after treatment with 10% H2SO4 and carbon black cumin seeds respectively. The results show that there is an increase in surface area and pore size for both 10 and 20% H2SO4 in comparison with carbon black cumin seeds. The adsorption of Co(II), Ni(II), Cu(II), Cr(VI) and Pb(II) and MB in the solution was investigated by studying the effect of initial concentration, contact time, temperature and pH. The batch adsorption experiments were conducted using different ion solution concentrations of 20, 40, 60, 80 and 100 mg/L, contact time was determined at intervals of 1, 5, 10, 15, 20, 30, 60, 90 and 120 min, while temperature was studied at 298, 303, 313, 333 and 353 K. On the other hand, the effect of pH on all solutions was studied at pH 1, 3,5,7 and 9. The results showed that the acid treated black cumin seeds (AT-BCS) and base treated black cumin seeds (BT-BCS) were successfully used for quaternary adsorption study of Cu(II), Co(II), Pb(II) and Ni(II) ions from aqueous solution. The results for the adsorbents indicated that the BT-BCS adsorbed more metals than AT-BCS and the UT-BCS. The maximum capacity for BT-BCS was 190.7 mg/g for Cu(II) whilst AT-BCS and UT-BCS showed capacities of 180.1 and 135 mg/g respectively for Pb(II). The uptake of Cr(VI) and Cd(II) ions onto pristine black seeds (PBS), KMnO4 black seeds (KMBS) and H3PO4 black seeds (H3BS) treated adsorbents showed that the trend for Cr(VI) ions was KMBS>H3BS>PBS with capacities of 16.12, 15.98 and 10.15 mg/g respectively. Meanwhile the adsorption of Cd(II) ions showed maximum capacities of 19.15, 19.09 and 16.80 mg/g for KMBS, H3BS and PBS respectively. Carbon from black cumin (CBC) seeds was modified with 10 % and 20 % sulfuric acid (H2SO4) then carbonized at 200 °C to obtain the activated adsorbents of ACBC-10 and ACBC-20. The new adsorbents were used for the adsorption of Cd(II) and methylene blue (MB). The adsorbents maximum trend for Cd(II) was ACBC-10>ACBC-20>CBC meanwhile the trend for methylene blue (MB) dye was ACBC-20>ACBC-10>CBC. The overall capacities showed that the prepared materials adsorbed more MB dye (16.42 mg/g) than Cd(II) ions (13.65 mg/g). The preparation of carbon from black cumin seeds (BCC) and activation with 10 and 20 % sulfuric acid (H2SO4) at 300 °C to obtain new adsorbents namely (BCAC-10) and (BCAC-20) respectively was used for the adsorption of Pb(II) ions and MB dye from aqueous solution. The maximum adsorption of Pb(II) ions was 17.19, 17.71 and 17.98 mg/g onto BCC, BCAC-10 and BCAC-20 respectively. Whilst for MB dye it was 11.63, 12.71 and 16.85 mg/g onto BCC, BCAC-10 and BCAC-20 respectively. The utilization of pristine Nigella Sativa (PNS) and magnetite-sucrose functionalized Nigella Sativa (FNS) seeds as the adsorbents for the uptake of Cr(VI) and Pb(II) ions from synthetic wastewater revealed that the maximum adsorption capacities for Cr(VI) were 15.6 and 13.0 mg/g onto PNS and FNS composites respectively at pH 1. On the hand, the maximum sorption capacities for Pb(II) ions were 39.7 and 37.9 mg/g onto PNS and FNS respectively at pH 5. The sorption study of Cr(VI), Cd(II) ions and MB dye by pristine Nigella Sativa (PNS) seeds, defatted and carbonized Nigella Sativa seeds from aqueous solution was investigated. The PNS seeds were treated using acetone (then named ANS) and N,N dimethylformamide (named DNS). The defatted ANS and DNS adsorbents were carbonized at 600 °C and named CANS and CDNS. The results of pristine, defatted and carbonized seeds maximum capacities were compared with each other and found that CANS had highest adsorption capacity of 99.82 mg/g for MB, 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 MB, Cd(II) and Cr(VI) respectively. 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 MB, Cd and Cr(VI) respectively. PNS had the lowest sorption capacities at 43.88, 36.01 and 19.84 mg/g for MB, Cd and Cr(VI) respectively. Therefore, this makes black cumin seeds a promising material for use in wastewater treatment to mitigate metal ions and dye pollution.