Lignin based microspheres for effective dyes removal: Design, synthesis and adsorption mechanism supported with theoretical study.

Multifunctional lignin bio-based adsorbent, b-LMS, was obtained via inverse copolymerization in the suspension of acryloyl modified kraft lignin (KfL-AA) and bio-based trimethylolpropane triacrylate (bio-TMPTA). Morphological and structural characterization of KfL-AA and b-LMS was performed using BET, FTIR, Raman, NMR, TGA, SEM, and XPS techniques. The b-LMS microspheres with 253 ± 42 µm diameters, 69.4 m2 g-1 surface area, and 59% porosity efficiently adsorb Malachite Green (MG), Tartrazine (T), and Methyl Red (MR) dye. The influence of pH, pollutant concentration, temperature, and time on the removal efficiency was studied in a batch mode. Favorable and spontaneous processes with high adsorption capacities e.g. 116.8 mg g-1 for MG, 86.8 mg g-1 for T, and 68.6 mg g-1 for MR indicate the significant adsorptive potential of b-LMS. Results from diffusional and single mass transfer resistance studies indicate that pore diffusion is a rate-limiting step. Theoretical calculations confirmed a higher affinity of b-LMS to cationic dye MG compared with an anionic and neutral one, i.e. T and MR, respectively. The data fitting from a flow system, using semi-empirical equations and Pore Surface Diffusion Modelling (PSDM) provided breakthrough point determination. The results from the desorption and competitive adsorption study proved the exceptional performance of b-LMS. Moreover, sulfation of b-LMS, i.e.production of b-LMS-OSO3H, introduced high-affinity sulfate groups with respect to cationic dye and cations. Developed methodology implements the principle of sustainable development and offers concept whose results contribute to the minimization of environmental pollution.

Hybrid material based on subgleba of mosaic puffball mushroom (Handkea utriformis) as an adsorbent for heavy metal removal from aqueous solutions.

The alkali treated subglebal tissue of the mosaic puffball (Handkea utriformis) (Sa) and Sa modified with hydroxyapatite (Sa-HAp), obtained by successive ionic layer adsorption and reaction (SILAR) method, were used for the removal of Pb2+, Cd2+ and Ni2+ from aqueous solution. The materials were characterized by FT-IR, Raman, SEM and EDS analysis and by determination of pHPZC. The adsorption performances of Sa and Sa-HAp were assessed in batch experiments at different pH, contact times, temperatures and mass of the adsorbent. Different models of adsorption isotherms were used, and the best fit was obtained with the Langmuir model. Maximum adsorption capacities of Sa towards Pb2+, Cd2+ and Ni2+ were 44.82, 15.54 and 17.21 mg g-1, while for Sa-HAp were 79.55, 52.59 and 45.01 mg g-1, respectively. Kinetic data were well fitted by a pseudo second-order model, while thermodynamic studies disclose spontaneous and endothermic adsorption process. The Sa-Hap was successfully regenerated with 1 M NaCl and after the fifth desorption cycle and 10 h achieved 82.9, 69.7 and 60.4 %, while for 0.5 M NaCl + 0.5 M NaOH and 1 h was 78.3, 64.1, 57.5 % of desorbed Pb2+, Cd2+ and Ni2+, respectively. The competitive study and results from a column system confirmed good applicability of Sa-HAp adsorbent.

Efficient multistep arsenate removal onto magnetite modified fly ash.

The modification of the fly ash (FA) by magnetite (M) was performed to obtain FAM adsorbent with improved adsorption efficiency for arsenate removal from water. The novel low cost adsorbents are characterized by liquid nitrogen porosimetry (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MB) and Fourier transform infrared (FTIR) spectroscopy. The optimal conditions and key factors influencing the adsorbent synthesis are assessed using the response surface method (RSM). The adsorption experiment was carried out in a batch system by varying the contact time, temperature, pH, and mass of the adsorbent. The adsorption capacity of the FAM adsorbent for As(V), calculated by Langmuir model, was 19.14 mg g-1. The thermodynamic parameters showed spontaneity of adsorption with low endothermic character. The kinetic data followed the pseudo-second-order kinetic model (PSO), and Weber-Morris model indicated intra-particle diffusion as rate limiting step. Alternative to low desorption capability of the FAM was found by five consecutive adsorption/magnetite precipitation processes which gave exhausted layered adsorbent with 65.78 mg g-1 capacity. This research also has shed light on the mechanism of As(V)-ion adsorption, presenting a promising solution for the valorization of a widely abundant industrial waste.

Amino-modified hollow alumina spheres: effective adsorbent for Cd2+, Pb2+, As(V), and diclofenac removal.

A simple sol-gel method and external gelatinization method of hollow alumina spheres synthesis were developed in this study. The spheres were modified with polyethyleneimine (PEI) producing PEI-Al2O3 via (3-glycidyloxypropyl)trimethoxy-silane, GLYMO, linker. Characterization results, obtained using XRD and SEM microscopy revealed spherical geometry with a hollow core of PEI-Al2O3 adsorbent. Introduction of a large number of the amino group, 6.9 mmol g-1, contributes to achieving high adsorption capacities, qm, of 95.6, 124.9, 61.3, and 125.9 mg g-1 for Cd2+, Pb2+, As(V), and DCF, respectively, which is obtained by using the Langmuir model. Thermodynamic studies indicated feasible adsorption and higher spontaneity with temperature increase. The kinetic study conveniently modeled using pseudo-second-order (PSO) and Weber-Morris kinetic model, as well as single resistance mass transfer model, indicated a change of the contribution of diffusional processes during adsorption with a dominance of intra-particle diffusion. The fixed-bed column adsorption data, fitted using Bohart-Adams, Clark, Yoon-Nelson, and Thomas models, showed lower capacity in comparison to batch study, and thus clear potential applicability of PEI-Al2O3 was deduced even at a high loading of feed water.

Removal of Nickel Ions from Aqueous Solutions by 2-Hydroxyethyl Acrylate/Itaconic Acid Hydrogels Optimized with Response Surface Methodology.

The adsorption of Ni2+ ions from water solutions by using hydrogels based on 2-hydroxyethyl acrylate (HEA) and itaconic acid (IA) was studied. Hydrogel synthesis was optimized with response surface methodology (RSM). The hydrogel with the best adsorption capacity towards Ni2+ ions was chosen for further experiments. The hydrogel was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis before and after the adsorption of Ni2+ ions. Batch equilibrium experiments were conducted to investigate the influence of solution pH, hydrogel weight, ionic strength, adsorption time, temperature and initial concentration of nickel ions on the adsorption. Time-dependent adsorption fitted the best to the pseudo-second-order kinetic model. A thermodynamic study revealed that the adsorption was an exothermic and non-spontaneous process. Five isotherm models were studied, and the best fit was obtained with the Redlich-Peterson model. Consecutive adsorption/desorption studies indicated that the HEA/IA hydrogel can be efficiently used as a sorbent for the removal of Ni2+ ions from the water solution. This study develops a potential adsorbent for the effective removal of trace nickel ions.

Characterization of potential probiotic strain, L. reuteri B2, and its microencapsulation using alginate-based biopolymers.

In this study, Lactobacillus reuteri B2 was isolated from the feces of C57BL/6 mice and assessed on probiotic activity. L. reuteri B2 was identified by 16S rDNA sequencing, which the cell viability in acidic conditions at pH 2.0 was 64% after 2 h, and in the presents of 0.30% of the bile salts, after 6 h, was 37%. Antimicrobial assay with L. reuteri B2 showed maximum diameters against Klebsiela oxytoca J7 (12.5 ± 0.71 mm). We further hypothesized if L. reuteri B2 strain in the free form can survive all conditions in the gastrointestinal tract (GIT) then the utilization of the appropriate biomaterials would ameliorate its stability and viability in GIT. L. reuteri B2 was microencapsulated into sodium alginate-(Na-alg) and different content of Na-alg and sodium maleate (SM) beads. Characterization materials enveloped their thermal characteristics (TGA/DTA analysis) and structure using: scanning electron microscopy (SEM), FTIR, and particle size distribution. The high survival rate of L. reuteri B2 at low pH from 2.0 to 4.0 and in the presence of the bile salts, at concentrations up to 0.30%, was obtained. L. reuteri B2 showed strong antimicrobial activity and the best protection microencapsulated with Na-alg + SM in simulated gastric juices (SGJ).

Novel amino-functionalized lignin microspheres: High performance biosorbent with enhanced capacity for heavy metal ion removal.

Novel highly effective amino-functionalized lignin-based biosorbent in the microsphere geometry (A-LMS) for removal of heavy metal ions, was synthesized via inverse suspension copolymerization of kraft lignin with poly(ethylene imine) grafting-agent and epoxy chloropropane cross-linker. Optimization of A-LMS synthesis, performed with respect to the quantity of sodium alginate emulsifier (1, 5 and 10 wt%), provides highly porous microspheres A-LMS_5, using 5 wt% emulsifier, with 800 ± 80 µm diameter, 7.68 m2 g-1 surface area and 7.7 mmol g-1 of terminal amino groups. Structural and surface characteristics were obtained from Brunauer-Emmett-Teller method, Fourier Transform-Infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and porosity determination. In a batch test, the influence of pH, A-LMS_5 dose, temperature, contact time on adsorption efficiency of Ni2+, Cd2+, As(V) and Cr(VI) ions were studied. The adsorption is spontaneous and feasible with maximum adsorption capacity of 74.84, 54.20, 53.12 and 49.42 mg g-1 for Cd2+, Cr(VI), As(V) and Ni2+ ions, respectively, obtained by using Langmuir model. Modeling of kinetic data indicated fast adsorbate removal rate with pore diffusional transport as rate limiting step (pseudo-second order model and Weber-Morris equations), thus further confirming high performances of produced bio-adsorbent for heavy metal ions removal.

Arsenic removal by copper-impregnated natural mineral tufa part II: a kinetics and column adsorption study.

This batch and column kinetics study of arsenic removal utilized copper-impregnated natural mineral tufa (T-Cu(A-C)) under three ranges of particle size. Non-competitive kinetic data fitted by the Weber-Morris model and the single resistance mass transfer model, i.e., mass transfer coefficient kfa and diffusion coefficient (Deff) determination, defined intra-particle diffusion as the dominating rate controlling step. Kinetic activation parameters, derived from pseudo-second-order rate constants, showed low dependence on adsorbent geometry/morphology and porosity, while the diffusivity of the pores was significant to removal efficacy. The results of competitive arsenic adsorption in a multi-component system of phosphate, chromate, or silicate showed effective arsenic removal using T-Cu adsorbents. The high adsorption rate-pseudo-second-order constants in the range 0.509-0.789 g mg-1 min-1 for As(V) and 0.304-0.532 g mg1 min1 for As(III)-justified further application T-Cu(A-C) in a flow system. The fixed-bed column adsorption data was fitted using empirical Bohart-Adams, Yoon-Nelson, Thomas, and dose-response models to indicate capacities and breakthrough time dependence on arsenic influent concentration and the flow rate. Pore surface diffusion modeling (PSDM), following bed-column testing, further determined adsorbent capacities and mass transport under applied hydraulic loading rates.

The removal of Zn2+, Pb2+, and As(V) ions by lime activated fly ash and valorization of the exhausted adsorbent.

This study focuses on the use of raw fly ash (FA) and modified fly ash - activated by lime (MFA), as effective and low-cost adsorbents for the removal of heavy metals (Zn2+, Pb2+ and As(V)), followed by the revalorization of the exhausted adsorbent. The granulometric, elemental analysis, point of zero charge (pHPZC), radiochemical and structural characterization were conducted using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and gamma spectrometry techniques. The optimal conditions and key factors influencing the adsorption process were assessed using the response surface method (RSM). The adsorption capacity of the MFA adsorbent for Zn2+, Pb2+ and As(V) removal, calculated by the Langmuir model, was found to be 33.13, 26.06, and 29.71 mg g-1, respectively. The kinetic and thermodynamic parameters indicated that the adsorption process is spontaneous and endothermic. Due to their low desorption potential of the exhausted adsorbents, their effective reuse was established to be feasible. For this reason, the valorization of this material as an additive in construction materials was thereafter studied, where testing its toxicity leaching (TCLP) as well as the mechanical properties of construction material containing exhausted MFA confirmed its safe use. Hence, this study points to a possible "two-in-one" reuse of coal ash, initially as an adsorbent and later as an additive in a construction material.