Two novel adsorbents Holarrhena antidysenterica (HA) and Citrullus colocynthis (CC) were collected from native Pakistan and treated with tartaric acid. The adsorbents were characterized by Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy, and their adsorptive behavior was studied against model cationic dye crystal violet (CV). Role of biosorbent dose, time of contact, temperature studies, agitation rates, and solution pH was investigated. Optimum conditions obtained for the removal of CV dye for H. antidysenterica-tartaric acid modified (HA-TA) were as follows: 0.8 g adsorbent dose, 35 minutes contact time, 5.0 pH, 40°C temperature, and 150 rpm agitation rates as compared to H. antidysenterica that gave 1.4 g adsorbent dose, 40 minutes time of contact, 6.0 pH, 50°C temperature, and 150 rpm agitation speed. C. colocynthis-tartaric acid modified (CC-TA) removed CV dye at 0.6 g adsorbent dose, 30 minutes contact interval, 4.0 pH, 40°C temperature, and 125 rpm agitation speed in contrast to C. colocynthis which gave 0.8 g adsorbent dose, 40 minutes time of contact, 6.0 pH, 50°C temperature, and 125 rpm agitation speed, respectively. Isothermal studies for both raw and modified biosorbents were compliant with the Langmuir model indicating monolayer, chemisorption. The maximum Langmuir capacities were up to 128.20 mg/g, 136.98 mg/g, 144.92 mg/g, and 166.66 mg/g for HA, CC, HA-TA, and CC-TA. Pseudo-second-order kinetic model well fitted the dye removal data. The rate-determining steps involved both surface and intraparticle diffusion mechanisms. Adsorption of dye molecules on active surfaces was governed by electrostatic attractions and chelating abilities. Thermodynamics research revealed the spontaneous and exothermic nature of the reaction. The adsorbents serve promising candidates for the effective removal of hazardous dyes from aqueous solutions.

The aim of the present work is to eradicate Congo red (CR) dye from aqueous solutions since the dye compounds are harmful to human life and the environment leading to detrimental results. For this purpose, Holarrhena antidysenterica (HA) and Citrullus colocynthis (CC) adsorbents were used for the adsorptive removal of Congo red dye from wastewaters. The unmodified adsorbents (U-HA and U-CC) were chemically modified using tartaric acid (TA). Morphological structures were examined by FTIR and SEM. Batch adsorption studies were tested at a variety of pH, time exposure, temperatures, and adsorbent dosages. Thermodynamic parameters such as Gibbs free energy ( ∆ G ° ), enthalpy ( ∆ H ° ), entropy changes ( ∆ S ° ), and energy of activation ( E a ) were also calculated. The results revealed that tartaric acid-Citrullus colocynthis (TA-CC) gave optimum conditions of time of contact (35 min), temperature conditions (40°C), pH (3), and dosage of adsorbent (1.6 g) for maximum dye removal. Tartaric acid-Holarrhena antidysenterica (TA-HA) gave equilibrium time of contact (30 min), temperature (40°C), and pH optimum (2) along with a 1.6 g dosage of adsorbent. Mechanistic understanding of adsorption isotherm provided that the Langmuir model was followed by raw and modified adsorbents. Maximum adsorption capacities Q max attained were 60.61 (mg g-1), 128.21 (mg g-1), 87.71 (mg g-1), and 131.57 (mg g-1), respectively, for U-HA, TA-HA, U-CC, and TA-CC. The results of kinetic modeling displayed a high value of R 2 (0.99) along with minimal error (RMSE) for dye removal showing that the pseudo-second-order kinetic model has acceptable accuracy. Fourier transform infrared proposed the electrostatic, pi-pi interactions, and hydrogen bonding as dominant adsorption mechanisms at acidic pH, respectively. Rate-determining steps comprise both surface and intraparticle diffusions. Thermodynamics indicated that the dye adsorption of CR is spontaneous, exothermic, and favorable in nature. These agricultural wastes due to specific points such as low cost, availability, and high removal rates of adsorption are highly competent for the expulsion of anionic dye like CR from wastewaters.