Efficient removal of crystal violet dye from aqueous solutions using sodium hydroxide modified avocado shells: kinetics and isotherms modeling

The main objective of this study is to optimize a new composite for the depollution of contaminated water. The sodium hydroxide-modified Avocado shells (NaOH-AS) were firstly prepared, characterized by field-emission-scanning-electron-microscopy (FE-SEM), X-ray energy dispersive spectroscopy (EDS) and Fourier transforms infrared (FT-IR) spectroscopy, and applied for efficient removal of Crystal violet dye (CV) in wastewater. In addition, the adsorption in a batch system of CV dye on the NaOH-AS material was studied. Therefore, we accomplished a parametric study of the adsorption by studying the effect of several important parameters on the decolorizing power of the used material, namely, initial pH, contact time, initial CV dye concentration, temperature, and the ionic strength effect on the CV dye adsorption process were systematically assessed. The highest adsorption efficiency of CV dye (>96.9%) by NaOH-AS was obtained at pH >8. The pseudo-second-order kinetic model gave the best description of the adsorption kinetic of CV dye on the AS and NaOH-AS adsorbents. Besides, the mass transfer of CV dye molecules from the solution to the adsorbent surface occurred in three sequential stages (boundary layer diffusion, intraparticle diffusion and adsorption equilibrium). The adsorption isotherm data were best fitted with the Freundlich model. The adsorption capacity of AS increased from 135.88 to 179.80 mg g−1 after treatment by 1 M NaOH. The thermodynamic study showed that CV dye adsorption onto NaOH-AS was an exothermic and feasible process. The electrostatic interactions acted as the only forces governing the CV adsorption mechanism. The NaOH-AS demonstrated a satisfactory reusability. Therefore, we can state that the as-developed NaOH-AS material has a potential application prospect as an efficient adsorbent for CV dye from wastewaters.

Formation of Nickel(II)Porphyrin and Its Interaction with DNA in Aqueous Medium

In this work, kinetics of the reaction between 5,10,15,20-tetrakis(N-methylpyridium-4-yl)porphyrin and Ni2+ species were investigated in aqueous solution at 25 ±1 ºC in I = 0.10 M (NaNO3). Speciation of Ni2+ was carried out in I = 0.10 M (NaNO3) in order to provide the distribution of the Ni2+ species with different solution pH. The experimental data have been compared with the speciation diagram constructed from the values of hydrolysis constants of Ni2+ ion. Speciation data showed that the hexaaquanickel(II), [Ni(H2O)6]2+, ions take place in hydrolysis reactions through formation of [Ni(OH2)6-n(OH)n]2-n species with solution pH. Based on the speciation of Ni2+ and pH dependent rate constants, rate expression can be written as: d[Ni(TMPyP)4+]/dt = (k1[Ni2+(aq)] + k2[Ni(OH)+(aq)] + k3[Ni(OH)2o(aq)] + k4[Ni(OH)3-(aq)])[H2TMPyP4+], where k1, k2, k3 and k4 were found to be k1 = (0.62 ± 0.22) × 10-2; k2 = (3.60 ± 0.40) × 10-2; k3 = (2.09 ± 0.52) × 10-2, k4 = (0.53 ± 0.04) × 10-2 M-1s-1 at 25 ±1 °C, respectively. Kinetic results showed that monohydroxo, [Ni(H2O)5(OH)]+, is the most reactive among the [Ni(OH2)6-n(OH)n]2-n species. The enhanced reactivity has been ascribed to the formation of hydrogen bonding between oxygen atom of hydroxyl group of the [Ni(H2O)5(OH)]+ species and the pyrrolic hydrogen atom of the [H2TMPyP]4+. The rate of formation of [Ni(II)TMPyP]4+ complex was to be 3.99 × 10-2 M-1s-1 in I = 0.10 M, NaNO3 (25 ± 1 ºC). Ionic strength effect on the reaction rate is suggested that the net charge of the tetracationic porphyrin is to be +3.6 on the basis of Brønsted-Bjerrum equation. The UV-Vis and fluorescence data revealed that [Ni(II)TMPyP]4+ and H2(TMPyP)4+ interact with DNA, and UV-Vis results suggest that Ni(II)-porphyrin and free base porphyrin interact with DNA via outside binding with self-stacking and intercalation, respectively. Mechanism of kinetics of formation of the [Ni(II)TMPyP]4+ complex in aqueous medium is discussed. An investigation of application of the [Ni(II)TMPyP]4+ complex along with other metalloporphyrins such as Zn2+-, Ru2+-, Pt2+-, [Au(III)TMPyP]5+ as anti-COVID-19 agents is now in progress under international collaboration.

Mobility of Cellulose Nanocrystals in Porous Media: Effects of Ionic Strength, Iron Oxides, and Soil Colloids

Understanding the dispersivity and migration of cellulose nanocrystals (CNCs) in porous media is important for exploring their potential for soil and water remediation. In this study, a series of saturated column experiments were conducted to investigate the coupled effects of ionic strength, iron oxides (hematite), and soil colloids on the transport of CNCs through quartz sand and natural soils (red earth and brown earth). Results showed that CNCs had high mobility in oxide-free sand and that iron oxide coating reduced the mobility of CNCs. An analysis of Derjaguin-Landau-Verwey-Overbeek interactions indicated that CNCs exhibited a deep primary minimum, nonexistent maximum repulsion and secondary minimum on hematite-coated sand, favorable for the attachment of CNCs. The maximum effluent percentage of CNCs was 96% in natural soils at 5 mM, but this value decreased to 4% at 50 mM. Soil colloids facilitated the transport of CNCs in brown earth with larger effect at higher ionic strength. The ionic strength effect was larger in natural soils than sand and in red earth than brown earth. The study showed that CNCs can travel 0.2 m to 72 m in porous media, depending on soil properties, solution chemistry, and soil colloids.