Kinetic Studies for the Remediation of Some Nutrients and Heavy Metals from Real Wastewater onto Carbon Nanotubes

The resistance of the intraparticle diffusion of different pollutants into CNTs is considered the main challenge in the wastewater treatment. Hence in this investigation, we discuss the kinetic parameters affecting the diffusion of different pollutants from municipal wastewater into the carbon nanotubes (CNTs) matrix. Different models (Pseudo first order, Pseudo second order, intraparticle diffusion, Avrami and mixed first and second order models) were studied to describe the adsorption characteristics of the reduction in chemical and biochemical oxygen demand of municipal wastewater in addition to the kinetic profile of some nutrients and heavy metals ions in the existence of CNTs. Finally, the mechanism of sorption of these main pollutants was proposed.

Adsorption and Desorption Behavior of Ectoine Using Dowex® HCR-S Ion-Exchange Resin

Dowex® HCR-S ion-exchange resin was used to adsorb ectoine in a batch system under varying operation conditions in terms of contact time, temperature, pH value, initial concentration of ectoine, and type of salt. Six adsorption isotherm models (Langmuir, Freundlich, Temkin, Dubinin–Radushkevich, Sips, and Redlich–Peterson) and three kinetic models (pseudo-first-order, pseudo-second-order, and intraparticle diffusion) were used to investigate the ectoine adsorption mechanism of ion-exchange resin. According to the experimental results, the mechanism of ectoine adsorption using an ion exchanger includes the ion-exchange reaction and physisorption. Both the Langmuir and Freundlich models were found to have a high fitting. For the kinetic analysis, the pseudo-second-order and intraparticle diffusion models were suitable to describe the ectoine adsorption. Dowex® HCR-S resin has an average saturated adsorption capacity of 0.57 g/g and 93.6% of ectoine adsorption at 25~65 °C, with an initial concentration of 125 g/L. By changing the pH of the environment using NaOH solution, the adsorbed ectoine on the ion-exchange resin can be desorbed to 87.7%.

Effect of Pyrolysis Temperature on Copper Aqueous Removal Capability of Biochar Derived from the Kelp Macrocystis pyrifera

Seaweed biochar is an efficient alternative bioadsorbent for Cu2+ removal due to its low cost and heavy metal removal capacity. Using the slow pyrolysis process, we produced biochars from Macrocystis pyrifera at 300 (BC300), 450 (BC450), and 600 °C (BC600). The physicochemical and structural properties of the biochar samples improved with increasing pyrolysis temperature from 300 to 450 °C, whereas no significant differences were observed with further increases in temperature to 600 °C. The yield ranged between 49% and 62% and had a high ash content (57.5–71.1%). BC450 and BC600 presented the highest surface areas and higher porosities. The FTIR spectra indicated that an increase of temperature decreased the acidic functional groups due to depolymerization and the dehydration processes, increasing the aromatic structures and the presence of calcium carbonate. The fittings of the kinetic models were different for the BCs: for the BC450 and BC600 samples, the Cu2+ adsorption was well-represented by a pseudo-first-order model; for BC300, a better fit was obtained with the pseudo-second-order model. The rate-limiting step of Cu2+ adsorption on BCs was represented by both models, liquid film diffusion and intraparticle diffusion, with surface diffusion being more important in BC300 and BC600, and intraparticle diffusion in BC450, in agreement with the pore size of the biochar samples. The adsorption isotherms of all BCs showed Langmuir behavior, representative of a chemisorption process, which was corroborated by the energy adsorption values determined by the D–R model. The maximum monolayer Cu2+ adsorption capacities were 93.55 and 58.0 mg g−1 for BC600 and BC450, respectively, whereas BC450 presented the highest affinity. Other mechanisms involved in controlling heavy metal removal from aqueous suspensions using these seaweed biochars remain to be explored. We conclude that BC450 and BC600 from M. pyrifera are the most efficient adsorbents for Cu2+ aqueous removal and are thus an appropriate alternative for bioremediation.

BIOSORPTION OF LEAD HEAVY METAL ON PRICKLY PEAR CACTUS BIOMATERIAL: KINETIC, THERMODYNAMIC AND REGENERATION STUDIES

The potential of Tunisian prickly pear cactus as a low-cost adsorbent for Pb(II) ions from aqueous solution was investigated in batch mode. To determine the optimum adsorption conditions, experiments were conducted varying the operating parameters, as follows: pH of the solutions (2-10), initial concentration of metal ions (0.98-2.4 mmol/L) and temperature (30-60 °C). The adsorption isotherm data were analyzed by applying the Langmuir, Freundlich, Dubinin–Raduskevich, Temkin and Redlich–Peterson models. The experimental results were better fitted by the Freundlish model. The pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion models were applied to the description of the kinetic data. The best fit was achieved for the pseudo-second order model, and the presence of both film and intraparticle diffusion mechanisms was demonstrated. Thermodynamic studies indicated that the biosorption on the cladode powder is an exothermic and chemical process. The desorption/regeneration process was also investigated. The obtained results revealed over 90% desorption of Pb(II) metal ions from the total metal-loaded mass of the adsorbent and good stability of the cactus adsorbent for four successive adsorption/desorption cycles.

Marble Waste Sludges as Effective Nanomaterials for Cu (II) Adsorption in Aqueous Media

This study evaluated the waste generated by a Spanish marble-producing company as adsorbent for the removal of copper (Cu [II]) from aqueous media. Six marble waste sludge samples were studied, and the following operational parameters were analyzed in discontinuous regime, including pollutant concentration, pH, temperature, nature of aqueous medium, and ionic strength. The applicability of the adsorbent material was assessed with experiments in both continuous and discontinuous regimes under close-to-real-life conditions. A pseudo-second order model yielded a better fit to the kinetic data. Application of the intraparticle diffusion model revealed two well-differentiated adsorption stages, in which the external material transfer is negligible and intraparticle diffusion is the controlling stage. The equilibrium study was better fitted to a Freundlich-type isotherm, predicting elevated maximum adsorption values (22.7 mg g−1) at a relatively low initial Cu (II) concentration (25 ppm), yielding a highly favorable chemisorption process (n >> 1). X-ray fluorescence study identified calcite (CaCO3) as the main component of marble waste sludges. According to X-ray diffraction analysis, Cu (II) ion adsorption occurred by intercalation of the metallic cation between CaCO3 layers and by the formation of surface complexes such as CaCO3 and Cu2(CO3)(OH)2. Cu (II) was more effectively removed at medium pH, lower temperature, and lower ionic strength of the aqueous medium. The salinity and dissolved organic matter in surface, ground-, and waste-waters negatively affected the Cu (II) removal process in both continuous and discontinuous regimes by competing for active adsorption sites. These findings demonstrate the applicability and effectiveness of marble-derived waste sludges as low-cost and readily available adsorbents for the treatment of waters polluted by Cu (II) under close-to-real-life conditions.

Preparation of Synthetic Clays to Remove Phosphates and Ibuprofen in Water

The main objective of this study consists in the synthesis of a layered double hydroxide (LDH) clay doped with magnesium and aluminum in order to test the removal of phosphates and ibuprofen in water. Two different LDH composites are assessed: oven-dried (LDHD) and calcined (LDHC). Single adsorptions of phosphate and ibuprofen showed up to 70% and 58% removal in water, when LDHC was used. A poorer performance was observed for LDHD, which presented adsorption efficiencies of 52% and 35%, respectively. The simultaneous removal of phosphate and ibuprofen in water showed that LDHC allows a greater reduction in the concentration of both compounds than LDHD. Phosphate adsorption showed a close agreement between the experimental and theoretical capacities predicted by the pseudo-second-order model, whereas ibuprofen fitted to a first-order model. In addition, phosphate adsorption showed a good fit to an intraparticle diffusion model and to Bangham model suggesting that diffusion into pores controls the adsorption process. No other mechanisms may be involved in ibuprofen adsorption, apart from intraparticle diffusion. Finally, phosphate desorption could recover up to 59% of the initial concentration, showing the feasibility of the recuperation of this compound in the LDH.

Two–three parameters isotherm modeling, kinetics with statistical validity, desorption and thermodynamic studies of adsorption of Cu(II) ions onto zerovalent iron nanoparticles

Adsorption of problematic copper ions as one of the endocrine disruptive substances from aqueous solution onto nanoscale zerovalent iron (nZVI) was studied. The high pore size 186.9268 Å, pore diameter 240.753 Å, and BET surface area 20.8643 m2 g−1 and pH(pzc) enlisted nZVI as an efficient nano-adsorbent for treatment of heavy metals from synthetic wastewater. SEM and EDX revealed the morphology and elemental distribution before and after adsorption. 98.31% removal efficiency was achieved at optimum adsorption operational parameters. Of all the thirteen isotherm models, equilibrium data were well fitted to Langmuir. Kinetics and mechanism data across the concentrations from 10 to 200 mg L−1 were analyzed by ten models. PSO best described kinetics data as confirmed by various statistical error validity models. The intraparticle diffusion model described that the intraparticle diffusion was not the only rate-limiting step. The adsorption mechanism was diffusion governed established by Bangham and Boyd models. Feasible, spontaneous, endothermic, and degree of randomness were reveal by the thermodynamic studies. Better desorption index and efficiency were obtained using HCl suggesting multiple mechanism processes. The performance of ZVI suggested it has a great potential for effective removal of endocrine disruptive cationic contaminant from wastewater.

Sulfamethoxazole Leaching from Manure-Amended Sandy Loam Soil as Affected by the Application of Jujube Wood Waste-Derived Biochar

Vertical translocation/leaching of sulfamethoxazole (SMZ) through manure-amended sandy loam soil and significance of biochar application on SMZ retention were investigated in this study. Soil was filled in columns and amended with manure spiked with 13.75 mg kg−1 (S1), 27.5 mg kg−1 (S2), and 55 mg kg−1 (S3) of SMZ. Jujube (Ziziphus jujube L.) wood waste was transformed into biochar and mixed with S3 at 0.5% (S3-B1), 1.0% (S3-B2), and 2.0% (S3-B3) ratio. Cumulative SMZ leaching was lowest at pH 3.0, which increased by 16% and 34% at pH 5.0 and 7.0, respectively. A quicker release and translocation of SMZ from manure occurred during the initial 40 h, which gradually reduced over time. Intraparticle diffusion and Elovich kinetic models were the best fitted to leaching data. S3 exhibited the highest release and vertical translocation of SMZ, followed by S2, and S1; however, SMZ leaching was reduced by more than twofold in S3-B3. At pH 3.0, 2.0% biochar resulted in 99% reduction in SMZ leaching within 72 h, while 1.0% and 0.5% biochar applications reduced SMZ leaching to 99% within 120 and 144 h, respectively, in S3. The higher SMZ retention onto biochar could be due to electrostatic interactions, H-bonding, and π-π electron donor acceptor interactions.

A Sustainable Solution to Obtain P-K-Mn Glass Fertilizers from Cheap and Readily Available Wastes

The sustainable economy framework imposes the adoption of new ways for waste reuse and recycling. In this context, this paper proposes a new alternative to obtain glass fertilizers (agriglasses) by reusing two cheap and easily available wastes, wood ash and manganese rich sludge resulting from drinking water treatment processes for groundwater sources. Glasses were obtained using different amounts of wastes together with (NH4)2HPO4 and K2CO3 as raw materials. The P-K-Mn nutrient solubilization from the obtained glasses was investigated using a citric acid solution. The kinetics of the leaching process was studied after 1, 7, 14, 21 and 28 days, respectively. The intraparticle diffusion model was used to interpret kinetic data. Two distinct stages of the ion leaching process were recorded for all of the studied compositions: first through intraparticle diffusion (the rate-controlling stage) and second through diffusion through the particle–medium interface. The fertilization effect of the obtained agriglasses was studied on a barley crop. The specific plant growth parameters of germination percentage, average plant height, biomass and relative growth rate were determinate. The positive impact of the agriglasses upon the plants biomass and relative growth rate was highlighted. The effects of agriglasses can be tuned through glass compositions that affect the solubility of the nutrients.

Design and development of a biotreatment of E. crassipes for the decontamination of water with Chromium (VI)

The use of cellulose materials for the adsorption of heavy metals has increased in favorable results to comply with the removal of these contaminants from water, such as the case of Chromium (VI), being one of the most dangerous heavy metals for the environment and human health. The objective of this research is to design and develop a biotreatment with dry and crushed biomass of E. crassipes for the continuous treatment of Chromium (VI), determining through mathematical modeling the Fick diffusion constant (Kf), based on this constant Fick will establish the performance of the biotreatment and the intraparticle diffusion constant (Ks). The diffusion speed (Kf) of the biomass of E. crassipes chemisorbing Cr (VI) of 0.30 cm/min, also it got the constant of the adsorption capacities (Ks) was 0.0198 s. With (Kf) it can design the treatment systems according to caudal or load greatly contaminated, calibrating the parameters how caudal, volume, or area of contact of the system of treatment. Also with (Ks) will be possible the design and modeling of a treatment system to improve the capacity of adsorptions calibrating the density of the particle and the density of the contact bed of the treatment system. Based on Fick's second law, an equation was designed to determine the reliability and performance of water treatment systems through the E. crassipes plant.