The effect of adsorbent textural and functional properties on model naphthenic acid adsorption.

Naphthenic acids, NAs, are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters, OSPW. Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation. A deeper evaluation of the effect NA structural differences have on uptake affinity is warranted. Here we provide an in-depth exploration of NA adsorption including many more model NA species than have been assessed previously with evaluation of adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW. Uptake for the NA varied considerably regardless of the activated carbon used, ranging from 350 mg/g to near zero highlighting recalcitrant NAs. The equilibrium data was explored to identify structural features of these species and key physiochemical properties that influence adsorption. We found that certain NA will be resistant to adsorption when hydrophobic adsorbents are used. Adsorption isotherm modelling helped explore interactions occurring at the interface between NA and adsorbent surfaces. We identified the importance of NA hydrophobicity for activated carbon uptake. Evidence is also presented that indicates favorable hydrogen bonding between certain NA and surface site hydroxyl groups, demonstrating the importance of adsorbent surface functionality for NA uptake. This research highlights the challenges associated with removing NAs from OSPW through adsorption and also identifies how adsorbent surface chemistry modification can be used to increase the removal efficiency of recalcitrant NA species.

Insights into adsorption performance and mechanism of chitosan-bentonite biocomposites for removal of imazethapyr and imazamox.

In the present study, chitosan-bentonite biocomposites were synthesised by ultrasonication, characterized using spectral techniques and assessed for their effectiveness in removing imazethapyr and imazamox from aqueous solution. The response surface methodology based box behnken design was utilized to generate optimum conditions viz. pH (1 to 9), adsorbent dose (0.01 to 1.0 g), contact time (0.5 to 48 h) and temperature (15 to 55 °C) for adsorption of herbicides on biocomposites. Based on model predictions, 60.4 to 91.5 % of imazethapyr and 31.7 to 46.4 % of imazamox was efficiently removed under optimal conditions. Adsorption data exhibited a strong fit to pseudo-second-order kinetic (R2 > 0.987) and Freundlich isotherm (R2 > 0.979). The adsorption capacity ranged from 3.88 to 112 µg1-ng-1mLn and order of adsorption was: low molecular weight chitosan-bentonite> medium molecular weight chitosan-bentonite> high molecular weight chitosan-bentonite> bentonite. Thermodynamic experiments suggested a spontaneous, exothermic process, reducing the system randomness during adsorption. Desorption experiments revealed successful desorption ranging from 91.5 to 97.0 % using 0.1 M NaOH. The adsorption mechanism was dominated by synergistic electrostatic interactions and hydrogen bonding. These results collectively indicated the potential environmental remediation application of chitosan-bentonite biocomposites to adsorb imazethapyr and imazamox from wastewaters.

Zinc Oxide Nanoparticles and Their Application in Adsorption of Toxic Dye from Aqueous Solution.

Dye waste is one of the most serious types of pollution in natural water bodies, since its presence can be easily detected by the naked eye, and it is not easily biodegradable. In this study, zinc oxide nanoparticles (ZnO-NPs) were generated using a chemical reduction approach involving the zinc nitrate procedure. Fourier transform infrared (FTIR), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and UV-vis techniques were used to analyse the surface of ZnO-NPs. The results indicate the creation of ZnO-NPs with a surface area of 95.83 m2 g-1 and a pore volume of 0.058 cm3 g-1, as well as an average pore size of 1.22 nm. In addition, the ZnO-NPs were used as an adsorbent for the removal of Ismate violet 2R (IV2R) dye from aqueous solutions under various conditions (dye concentration, pH, contact time, temperature, and adsorbent dosage) using a batch adsorption technique. Furthermore, FTIR and SEM examinations performed before and after the adsorption process indicated that the surface functionalisation and shape of the ZnO-NP nanocomposites changed significantly. A batch adsorption analysis was used to examine the extent to which operating parameters, the equilibrium isotherm, adsorption kinetics, and thermodynamics affected the results. The results of the batch technique revealed that the best results were obtained in the treatment with 0.04 g of ZnO-NP nanoparticles at 30 °C and pH 2 with an initial dye concentration of 10 mg L-1, which removed 91.5% and 65.6% of dye from synthetic and textile industry effluents, respectively. Additionally, six adsorption isotherm models were investigated by mathematical modelling and were validated for the adsorption process, and error function equations were applied to the isotherm model results in order to find the best-fit isotherm model. Likewise, the pseudo-second-order kinetic model fit well. A thermodynamic study revealed that IV2R adsorption on ZnO-NPs is a spontaneous, endothermic, and feasible sorption process. Finally, the synthesised nanocomposites prove to be excellent candidates for IV2R removal from water and real wastewater systems.

Isolation and Characterization of Magnetic Oil Palm Empty Fruits Bunch Cellulose Nanofiber Composite as a Bio-Sorbent for Cu(II) and Cr(VI) Removal.

In the present study, magnetic oil palm empty fruits bunch cellulose nanofiber (M-OPEFB-CNF) composite was isolated by sol-gel method using cellulose nanofiber (CNF) obtained from oil palm empty fruits bunch (OPEFB) and Fe3O4 as magnetite. Several analytical methods were utilized to characterize the mechanical, chemical, thermal, and morphological properties of the isolated CNF and M-OPEFB-CNF. Subsequently, the isolated M-OPEFB-CNF composite was utilized for the adsorption of Cr(VI) and Cu(II) from aqueous solution with varying parameters, such as pH, adsorbent doses, treatment time, and temperature. Results showed that the M-OPEFB-CNF as an effective bio-sorbent for the removal of Cu(II) and Cr(VI) from aqueous solution. The adsorption isotherm modeling revealed that the Freundlich equation better describes the adsorption of Cu(II) and Cr(VI) on M-OPEFB-CNF composite. The kinetics studies revealed the pseudo-second-order kinetics model was a better-described kinetics model for the removal of Cu(II) and Cr(VI) using M-OPEFB-CNF composite as bio-sorbent. The findings of the present study showed that the M-OPEFB-CNF composite has the potential to be utilized as a bio-sorbent for heavy metals removal.

ß-Cyclodextrin-chitosan biocomposites for synergistic removal of imazethapyr and imazamox from soils: Fabrication, performance and mechanisms.

The present study delineates to develop and explore the possibility of using chitosan-ß-cyclodextrin biocomposites as environmentally friendly decontamination agent for removal of imazethapyr and imazamox from soils. The biocomposites were synthesised using ultrasonic assisted technique and characterised by UV-Visible spectrophotometer. The quantification of imazethapyr and imazamox was done using liquid chromatography tandem mass spectrometry. The adsorption capacity for imazethapyr and imazamox ranged from 0.12 to 1.22 and 0.02 to 1.01 µg1-ng-1mLn, respectively in studied soils (p < .05) indicating strong influence of soil properties on adsorption. Desorption studies indicated that distilled water could desorb only 1.23 to 5.48 and 3.11 to 8.63% of adsorbed imazethapyr and imazamox, respectively at high concentrations (1.0 and 10 µg mL-1) whereas herbicides were not desorbed at low concentrations (0.01 and 0.1 µg mL-1). The removal of imazethapyr and imazamox from soils were carried out with ß-cyclodextrin, chitosan and their biocomposites and the influence of various parameters such as type and concentration of extractant, contact time, liquid to soil ratio, temperature and sequential extraction cycle was investigated. Under optimum conditions, herbicides were successfully desorbed from studied soils using low molecular weight chitosan-ß-cyclodextrin biocomposite (LCD) and removal rate varied from 59.42 to 99.44% at initial herbicide concentration of 0.01 to 10 µg mL-1. The highest removal rate of imazethapyr and imazamox was observed for inceptisol 3 followed by entisol, inceptisol 2, aridisol, inceptisol 1, vertisol and alfisol probably due to differential physico-chemical properties of soil which affected the herbicide-soil interactions. Based on these results, LCD can be regarded as effective and environmentally friendly in situ green extracting agent for remediating soils contaminated with imazethapyr and imazamox.

Application of EDTA modified Fe3O4/sawdust carbon nanocomposites to ameliorate methylene blue and brilliant green dye laden water.

This work explored the potential of magnetic sawdust carbon nanocomposites for cationic dyes removal from aqueous medium. EDTA modified magnetic sawdust carbon nanocomposites (EDTA@Fe3O4/SC ncs) were prepared by biogenic green reduction and precipitation approach. The surface properties, structure and composition of nanocomposites were characterized by HRTEM, FESEM, XRD, EDX, BET, FTIR etc. The Fe3O4 nanoparticles were 10-20 nm in diameters and having 14 m2/g surface area. Removal of Methylene blue (MB) and Brilliant green (BG) dyes from aqueous medium was studied in batch mode experiments. The maximum removal was achieved at neutral pH 7.0 with in 30 min. Adsorption capacity of EDTA@Fe3O4/SC for MB and BG dyes was 227.3 mg/g and 285.7 mg/g, respectively. Dye adsorption behaviour is well explained by Freundlich model. The rate of cationic dye adsorption is explained by pseudo-second order model. The value of thermodynamic parameters confirmed that adsorption process was spontaneous and favourable. Desorption and reusable efficiency of nanocomposites was also evaluated.

Burkholderia tropica as a Potential Microalgal Growth-Promoting Bacterium in the Biosorption of Mercury from Aqueous Solutions.

The use of microalgal biomass is an interesting technology for the removal of heavy metals from aqueous solutions owing to its high metal-binding capacity, but the interactions with bacteria as a strategy for the removal of toxic metals have been poorly studied. The goal of the current research was to investigate the potential of Burkholderia tropica co-immobilized with Chlorella sp. in polyurethane discs for the biosorption of Hg(II) from aqueous solutions and to evaluate the influence of different Hg(II) concentrations (0.041, 1.0, and 10 mg/l) and their exposure to different contact times corresponding to intervals of 1, 2, 4, 8, 16, and 32 h. As expected, microalgal bacterial biomass adhered and grew to form a biofilm on the support. The biosorption data followed pseudo-second-order kinetics, and the adsorption equilibrium was well described by either Langmuir or Freundlich adsorption isotherm, reaching equilibrium from 1 h. In both bacterial and microalgal immobilization systems in the coimmobilization of Chlorella sp. and B. tropica to different concentrations of Hg(II), the kinetics of biosorption of Hg(II) was significantly higher before 60 min of contact time. The highest percentage of biosorption of Hg(II) achieved in the co-immobilization system was 95% at pH 6.4, at 3.6 g of biosorbent, 30 ± 1°C, and a mercury concentration of 1 mg/l before 60 min of contact time. This study showed that co-immobilization with B. tropica has synergistic effects on biosorption of Hg(II) ions and merits consideration in the design of future strategies for the removal of toxic metals.

Chemically activated carbon from lignocellulosic wastes for heavy metal wastewater remediation: Effect of activation conditions.

Chemical activation is known to induce specific surface features of porosity and functionality which play a definite role in enhancing the adsorptive potential of the developed activated carbons. Different conditions of temperature, time, reagent type and impregnation ratio were applied on sawdust precursor and their effect on the physical, surface chemical features and finally on the adsorption potential of the developed activated carbons were analysed. Under activation conditions of 600°C, 1hr, 1:0.5 ratio, ZnCl2 impregnated carbon (CASD_ZnCl2) resulted in microporosity while KOH impregnation (CASD_KOH) yielded a carbon having a wider pore size distribution. The surface chemistry revealed similar functionalities. At same pH, temperature and adsorbate concentrations, CASD_KOH demonstrated better adsorption potential (1.06mmoles/g for Cd2+ and 1.61mmoles/g for Ni2+) in comparison to CASD_ZnCl2 (0.23mmoles/g and 0.33mmoles/g for Cd2+ and Ni2+ respectively). Other features were a short equilibrium time of 60mins and an adsorbent dose of 0.2g/L for the CASD_KOH in comparison to CASD_ZnCl2 (equilibrium time of 150min and dosage of 0.5g/L). The nature of interactions was physical for both adsorbents and pore diffusion mechanisms were operative. The results reveal the potentiality of chemical activation so as to achieve the best physico-chemical properties suited for energy efficient, economical and eco-friendly water treatment.