Enhanced filtration membranes with graphene oxide and tannic acid for textile industry wastewater dye removal.

A novel modification technique employing a layer-by-layer (LbL) self-assembly method, integrated with a pressure-assisted filtration system, was developed for enhancing a commercial polyethersulfone (PES) microfiltration (MF) membrane. This modification involved the incorporation of tannic acid (TA) in conjunction with graphene oxide (GO) nanosheets. The effectiveness of the LbL method was confirmed through comprehensive characterization analyses, including ATR-FTIR, SEM, water contact angle (WCA), and mean pore size measurements, comparing the modified membrane with the original commercial one. Sixteen variations of PES MF membranes were superficially modified using a three-factorial design, with the deposited amount of TA and GO as key factors. The influence of these factors on the morphology and performance of the membranes was systematically investigated, focusing on parameters such as pure water permeability (PWP), blue corazol (BC) dye removal efficiency, and flux recovery rate (FRR). The membranes produced with the maximum amount of GO (0.1 mg, 0.55 wt%) and TA as the inner and outer layers demonstrated remarkable FRR and significant BC removal, exceeding 80%. Notably, there was no significant difference observed when using either 0.2 (1.11 wt%) or 0.4 mg (2.22 wt%) in the first layer, as indicated by the Tukey mean test. Furthermore, the modified membrane designated as MF/TA0.4GO0.1TA0.4 was evaluated in the filtration of a simulated dye bath wastewater, exhibiting a BC removal efficiency of 49.20% and a salt removal efficiency of 27.74%. In conclusion, the novel PES MF membrane modification proposed in this study effectively enhances the key properties of pressure-driven separation processes.

Modification of natural zeolite clinoptilolite and ITS application in the adsorption of herbicides.

The clinoptilolite natural zeolites (NZs) posses low herbicide adsorption capacity demanding acid-, alkali-, or salt chemical modifications that enhance its adsorption. However, this may affect the material structure and charge distribution. Alternatively, zeolites may be synthesized at a high cost and time-consuming process. Consequently, new methods, such as the hydrothermal method, for NZ modification needs to be studied. In this sense, a novel surface-modified zeolite (SMZ), using hexadecyltrimethylammonium bromide (CTAB), in acid media was produced by the hydrothermal method and applied for the adsorption of Atrazine (ATZ), Diuron (DIU) and 2,4-D. Commercial NZ and SMZ were characterized by SEM, XRD, TGA, FT-IR, AA spectroscopy, pHPZC, Zeta potential and N2-physisorption. The SMZ chosen for the adsorption experiments was the one with the highest modification yield and adsorption capacity obtained from a complete design of experiments (CTAB=0.74 ; D=12 Mesh; HCl=0.1 M; t=6 h and T=205 ºC). The adsorption experiments revealed that the SMZ adsorption capacity for the herbicide 2,4-D (qmax=9.02 mg/g) was greater than that obtained for ATZ (qmax=2.11 mg/g) and DIU (qmax=1.85 mg/g), which was explained by the presence of the hydroxyl group and by geometric characteristics of the 2,4-D. Adsorption models' fitting showed that the adsorption of 2,4-D onto SMZ were best described by pseudo-second order kinetic (k2=0.005-0.006 g/mg.min; qe,exp=7.122-8.614 mg/g) and Langmuir isothermal model (KL=0.283-0.499 L/mg; qm=7.167-7.995 mg/g). These results indicate that the hydrothermal method is a viable alternative to enable the use of NZs for the adsorption of emerging contaminants from wastewater.

A novel magnetic adsorbent from activated carbon fiber and iron oxide nanoparticles for 2,4-D removal from aqueous medium.

Carbonaceous materials have been widely applied as adsorbents, but there are some factors that affect their efficiency. In this context, advances in nanotechnology provide new and more efficient methodologies for water treatment. This study evaluated the efficiency of a novel carbon-based adsorbent developed from Brazilian polyacrylonitrile textile fiber and functionalized with iron oxide magnetic nanoparticles for the removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from the aqueous medium. The synthesized adsorbent (ACF-Fe3O4) was characterized by FTIR, XRD, VSM, Zeta potential, SEM, EDX, and TEM. The characterization techniques showed that the adsorbent has peaks characteristic of its precursors and superparamagnetic characteristics, confirming the efficiency of the synthesis method. The adsorption tests evaluated the influence of adsorbent dosage, pH of the contaminant solution, contact time and temperature on the removal of 2,4-D. The experimental data were better adjusted by the pseudo-second order kinetic model and by the Langmuir isothermal model. The thermodynamic parameters revealed that the process is exothermic, spontaneous and thermodynamically favorable. Under the best experimental conditions, the maximum adsorption capacity obtained was 51.10 mg g-1 with an adsorbent concentration of 0.33 g L-1, natural pH of the solution, temperature of 288 K at the equilibrium time of six hours. Adsorbent reusage was studied in four desorption cycles. The adsorption mechanism can be explained through π-π bonds, hydrogen bonds and electrostatic interactions. The prepared material presented high-efficiency adsorption capacity of 2,4-D compared to other carbonaceous materials present in the literature, demonstrating its viability for the removal of this contaminant from the aqueous medium.

Continuous removal of pharmaceutical drug chloroquine and Safranin-O dye from water using agar-graphene oxide hydrogel: Selective adsorption in batch and fixed-bed experiments.

In this work, Chloroquine diphosphate, and the cationic dye Safranin-O were selectively removed from water using the agar-graphene oxide (A-GO) hydrogel, produced via simple one-step jellification process. The morphology of the A-GO biocomposite was characterized and batch experiments were performed, with adsorption isotherms satisfactorily fitting (R2 > 0.98) Sips (Safranin-O) and Freundlich (Chloroquine) isotherms. Driving force models and Fick's diffusion equation were applied to the modeling of kinetic data, and a satisfactory fit was obtained. Selective adsorption carried out in batch indicated that competitive adsorption occurs when both components are mixed in water solution - the adsorptive capacities dropped ∼10 mg g-1 for each component, remaining 41 mg g-1 for safranin-O and 31 mg g-1 for chloroquine. Fixed-bed breakthrough curves obtained in an adsorption column showed adsorption capacities over 63 mg g-1 and 100 mg g-1 for chloroquine and safranin-O, respectively, also exhibiting outstanding regenerative potentials. Overall, the biocomposite produced using graphene oxide proved to be a viable and eco-friendly alternative to continuously remove both contaminants from water.

Adsorption of Safranin-O dye by copper oxide nanoparticles synthesized from Punica granatum leaf extract.

The development of new technologies for water and wastewater treatment is a growing need due to the occurrence of micropollutants, such as dyes, in water resources. In this sense, green-synthesized nanoparticles are being extensively studied, due to their low cost, non-toxicity, and high efficiency in adsorption processes. Thus, the present study reports the green synthesis of copper oxide nanoparticles (CuO-NP), obtained from pomegranate (Punica granatum) leaf extract, employed for the removal of Safranin-O (SO) dye. CuO-NP was characterized by physicochemical analysis. These analyzes suggested that the redox process occurred efficiently. Also, the material presented interesting elements for the removal of cationic dyes such as negative surface charge, high specific surface area, and predominance of mesopores. The kinetic data fitted the pseudo-second-order model, reaching equilibrium in 480 min. The equilibrium study resulted in a maximum adsorption capacity of 189.54 mg g-1 at 298 K and the experimental data best fitted the Langmuir model. The effect of pH and ionic strength did not present significant changes, which demonstrates an advantage of this adsorbent over other materials. The regeneration study allowed to verify the possibility of reuse CuO-NP, since after 4 cycles the adsorption capacity was 44% of the initial value. Considering the results found, CuO-NP has a high potential for applicability in the treatment of water contaminated by dyes.

A tubular ceramic membrane coated with TiO2-P25 for radial addition of H2O2 towards AMX removal from synthetic solutions and secondary urban wastewater.

This work aims to integrate several hydrogen peroxide (H2O2) activation mechanisms, photolysis (UVC irradiation), chemical electron transfer (TiO2-P25 photocatalysis), and reaction with TiO2-P25 in dark conditions, for reactive oxygen species (ROS) generation towards the removal of contaminants of emerging concern (CECs), in a single unit operated in continuous-flow mode. An H2O2 stock solution is fed by the lumen side of a tubular ceramic membrane, delivering the oxidant to the (i) catalyst immobilized in the membrane shell-side and (ii) annular reaction zone (ARZ, space between membrane shell-side and outer quartz tube) where CECs contaminated water flows with a helix trajectory, being activated by UV light provided by four lamps placed symmetrically around the reactor. First, the effect of several parameters in the removal of a CEC target molecule, amoxicillin (AMX), was evaluated using a synthetic solution ([AMX]inlet = 2.0 mg L-1): (i) light source (UVA or UVC radiation), (ii) H2O2 dose, (iii) H2O2 injection method (radial permeation vs. upstream injection), and (iv) number of TiO2-P25 layers deposited on the membrane. The UVC/H2O2/TiO2 system with radial addition of H2O2 (20 mg L-1) and 9-TiO2-P25 layers provided the highest AMX removal efficiency (72.2 ± 0.5%) with a UV fluence of 45 mJ cm-2 (residence time of 4.6 s), due to the synergic effect of four mechanisms: (i) AMX photolysis, (ii) H2O2 photocleavage, (iii) TiO2-P25 photoactivation, and (iv) chemical reactions between H2O2 and TiO2-P25. The urban wastewater matrix showed a negative effect on AMX removal (~44%) due to the presence of ROS scavengers and light-filtering species.

Modified Moringa oleifera Lam. Seed husks as low-cost biosorbent for atrazine removal.

Atrazine is an herbicide which is widely applied in sugarcane and corn crops. Its frequent use has resulted in environmental impacts, and its traces have been verified in surface and groundwater. Thus, it is necessary to remove this pollutant, and an alternative is the adsorption due to its universal nature, low-cost and ease of operation. Therefore, the objective of the present work was to study the adsorption capacity of atrazine by modified Moringa oleifera Lam. seed husks, a low-cost adsorbent. The biosorbent was subjected to c hemical and thermal treatment and was characterised by structural, morphological and textural analysis, which showed porous and heterogeneous characteristics, with a specific surface area of 5.77 m2 g-1. The kinetic study demonstrated equilibrium at 1200 min, with an adsorption capacity of 1.90 mg g-1 and the best fit was for the pseudo-second-order model. The isotherms were obtained at 298, 308 and 318 K. The Freundlich, Temkin and Langmuir models were applied to the experimental data, the latter being the best. The values of the thermodynamic parameters indicated that the biosorption was spontaneous, endothermic and reversible. The highest adsorption capacity obtained was 10.32 mg g-1, which was higher than several values found in the literature. The biosorbent was regenerated over three cycles, indicating its potential of atrazine removal from surface water.

Deposition of graphene nanoparticles associated with tannic acid in microfiltration membrane for removal of food colouring.

A modified microfiltration (MF) membrane was prepared by flow-through coating method. First the sulfuric acid solution was vacuum filtered on the polyethersulfone (PES) MF membrane, providing the introduction of a sulfonic acid group to the backbone of PES. Sequentially, the polyethyleneimine solution was vacuum filtered to provide amine groups on the membrane surface. Finally, the graphene oxide solution, functionalized with different masses of tannic acid, was vacuum filtered on the membrane surface, producing the cross-linked modified membranes. These were efficient in the removal of anionic food colouring, achieving high removal rates and low fouling, compared to unmodified membrane. The best membrane in terms of bright blue dye removal was the MF PEI5GO1TA4, capable of removing all the feed solution, and demonstrating its possibility of reuse in five cycles of operation.

Application of magnetic coagulant based on fractionated protein of Moringa oleifera Lam. seeds for aqueous solutions treatment containing synthetic dyes.

The aim of the present study was to evaluate the efficiency of a new magnetic coagulant, obtained from Moringa oleifera seeds protein functionalized with iron oxide nanoparticles to remove four anionic synthetic dyes with coagulation/flocculation assays followed by magnetic sedimentation. The results showed that the presence of a magnetic field during sedimentation considerably accelerates the separation and increases the dye removal efficiency. Amaranth dye removal increased from 45 to 86% and Sunset Yellow from 15 to 69% with the presence of magnetic field, while Reactive Black 5 and Brilliant Blue reached 94% and 52% removal, respectively. For AM and SY dyes, the best protein concentration is 150 mg L-1, for RB5 dye is 115 mg L-1, and for BB dye is 75 mg L-1. The sedimentation time decreased from 30 to 5 min with magnetic sedimentation. The residual value of AM dye decreased from 10.76 mg L-1 to approximately 2.71 mg L-1, and with SY the residual concentration decreased from approximately 16.79 mg L-1 to 6.36 mg L-1. The removal of BB and RB5 dyes reached an approximate final value of 48.2 mg L-1 (52%) and 1.18 mg L-1 (94%).

Mathematical modelling applied to the rate-limiting mass transfer step determination of a herbicide biosorption onto fixed-bed columns.

The herbicide removal of Diuron in a fixed-bed column packed with the Moringa oleifera bark biosorbent was investigated experimentally and through phenomenological mathematical modelling. To understand the physical phenomena involved, the steps of external mass transfer resistance, internal mass transfer resistance and the adsorption phenomenon itself were considered as possible limiting steps in the herbicide mass transfer from the liquid to the solid phase. In the developing process of the internal mass transfer resistance model, two hypotheses were considered: constant mass transfer coefficient and mass transfer coefficient as a function of the herbicide concentration in the biosorbent. The experimental breakthrough curves were obtained for different flow rates and feed concentrations, in order to evaluate the model's predictive capacity. The mass transfer parameter values of the mathematical models were estimated using the simplex downhill optimization method. The model that considers the resistance a mass transfer internal with parameter Ks variable represented effectively the dynamic behaviour of the herbicide biosorption process in fixed-bed column, in the various evaluated conditions, indicating that this mechanism controls the biosorption process. Thus, the phenomenological mathematical modelling proved to be an analysis important tool, understanding and the herbicide adsorption systems design in a fixed-bed column.

Development of an activated carbon impregnation process with iron oxide nanoparticles by green synthesis for diclofenac adsorption.

The objective of this study was to impregnate the surface of palm coconut activated carbon with nanoparticles of iron compounds using Moringa oleifera leaf extracts and pomegranate leaf by a green synthesis method and to evaluate its adsorption capacity for sodium diclofenac. The adsorbent material was characterized by zeta potential, X-ray diffraction (XRD), N2 adsorption/desorption (BET method), transmission electronic microscopy (TEM), and scanning electronic microscopy (SEM) coupled to dispersive energy spectrometry X-ray (EDX) methods. To evaluate the adsorption capacity of sodium diclofenac, the influence of pH, kinetics, isotherms, and thermodynamic properties were analysed. The impregnated adsorbents showed efficiency in the adsorption of sodium diclofenac. The kinetic model that best fit the experimental data was the pseudo-second-order model, and the equilibrium model was the Langmuir model. As for the thermodynamic study, it was verified that the adsorption reaction for all adsorbents occurs in a spontaneous, favourable way, and it is endothermic by physisorption. Therefore, this process is promising because it is a clean and non-toxic method when compared with chemical methods for the synthesis of nanoparticles.

Water decontamination containing nitrate using biosorption with Moringa oleifera in dynamic mode.

This study was conducted to assess the feasibility of using Moringa oleifera Lam. (MO) seeds in the biosorption of nitrate present in aqueous solutions by means of batch and fixed-bed column biosorption processes. The batch assays showed that nitrate biosorption is enhanced under experimental conditions of pH 3 and a biosorbent mass of 0.05 g. For the experiments in dynamic mode, the results obtained from the statistical parameters showed that lesser pH, lesser feed flow rate, and higher initial concentration will result in an increase of the maximum capacity of the bed. These conditions were confirmed by experimental analysis. The best experimental conditions, according to the values for percentage removal (91.09%) and maximum capacity (7.69 mg g-1) of the bed, were those used in assay 1, which utilized pH 3, feed flow rate of 1 mL min-1, and initial nitrate concentration of 100 mg L-1.

Activated carbon of Babassu coconut impregnated with copper nanoparticles by green synthesis for the removal of nitrate in aqueous solution.

The present study was conducted to impregnate the surface of a carbon of vegetable origin with copper nanoparticles by the green synthesis method with the aqueous extract of Hibiscus sabdariffa flowers, rich in phenolic compounds, which are responsible for the reduction and impregnation of metal nanoparticles. Batch adsorption assays were conducted aimed at nitrate removal with pure (GAC) and impregnated (IGAC) carbon, for comparative purposes. It was found that impregnation increases the efficiency of the carbon by four times in terms of the maximum adsorption capacity, which was 10.13 mg g-1 at 45°C for GAC and 45.01 mg g-1 at 15°C for IGAC, indicating that this is a promising material for the removal of nitrate in waters with an excess of this ion.

Environmentally friendly biosorbents (husks, pods and seeds) from Moringa oleifera for Pb(II) removal from contaminated water.

Lead is a heavy metal considered highly toxic, responsible for causing several health problems as well as being extremely harmful to fauna and flora. Given this fact, several techniques have been studied for the removal of this metal from contaminated water, in which stands out adsorption. In this sense, the objective of this study was to evaluate the potential of lead(II) biosorption from contaminated water by seed husks, seeds and pods of Moringa oleifera Lam (moringa). Biomass was characterized by energy-dispersive X-ray spectroscopy, Scanning Electron Microscopy and Fourier transform infrared spectroscopy analyses. From the studied parameters, the optimal conditions obtained for the three analyzed biosorbents are: 30 min to equilibrium, pH 6 and 25°C temperature. The pseudo-second-order kinetic model was the best fitted to the experimental data for the three evaluated biosorbents. Regarding the adsorption isotherms, the model that best fitted to the experimental data for seed and seed husk was that proposed by Freundlich, and for the pod the Langmuir model. The analysis of the obtained thermodynamic data showed that the adsorption process is favorable and of exothermic nature. Through the results it was concluded that the evaluated biosorbents are efficient in lead(II) biosorption.