Anna Wołowicz

In this study, poly(urethane methacrylate) (PUM)–lignin (Lig) polymeric adsorbent in the form of microspheres was synthesized and evaluated for the removal of metal ions such as Cu(II), Ni(II), Zn(II), and C.I. Basic Yellow 40 (BY40) dye from aqueous solutions. The performance of the PUM adsorbent without lignin was also described. PUM and PUM–Lig were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TG), attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT‐IR), scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS), to confirm the successful incorporation of lignin and to assess their thermal stability, chemical structure, morphology, and surface properties. Equilibrium uptake of Cu(II), Ni(II), Zn(II), and BY40 was described by the Freundlich isotherm model rather than the Langmuir, Temkin, or Dubinin–Radushkevich ones with the following affinity: Cu(II) > Zn(II) > BY40 > Ni(II). The experimental equilibrium sorption capacities ranged from 78.0 to 152.2 mg/g. The effect of NaCl, Na ₂ SO _4, and surfactants CTAB, TX100 on Cu(II), Ni(II), Zn(II), and BY40 was investigated. The effective desorption of Cu(II) and BY40 from adsorbents was performed using 1 M HCl, 1 M H ₂ SO ₄ , 1 M HNO _3, and 1 M HCl or 1 M NaCl in 50% v/v methanol.

Effective removal of organic and inorganic impurities by adsorption technique requires the preparation of new materials characterized by low production costs, significant sorption capacity, and reduced toxicity, derived from natural and renewable sources. To address these challenges, new adsorbents have been developed in the form of polymer microspheres based on ethylene glycol dimethacrylate (EGDMA) and vinyl acetate (VA) (EGDMA/VA) containing starch (St) modified with boric acid (B) and dodecyl-S-thiuronium dodecylthioacetate (DiTDTA) for the removal of dyes: C.I. Basic Blue 3 (BB3) and C.I. Acid Green 16 (AG16) and heavy metal ions (M(II)): Cu(II), Ni(II), and Zn(II) from water and wastewater. The adsorbents were characterized by ATR/FT-IR, DSC, SEM, BET, EDS, and pH_PZC methods. These analyses demonstrated the successful modification of microspheres and the increased thermal resistance resulting from the addition of the modified starch. The point of zero charge for EGDMA/VA was 7.75, and this value decreased with the addition of modified starch (pH_PZC = 6.62 for EGDMA/VA-St/B and pH_PZC = 5.42 for EGDMA/VA-St/DiTDTA). The largest specific surface areas (S_BET) were observed for the EGDMA/VA microspheres (207 m²/g), and S_BET value slightly decreases with the modified starch addition (184 and 169 m²/g) as a consquence of the pores stopping by the big starch molecules. The total pore volumes (V_tot) were found to be in the range from 0.227 to 0.233 cm³/g. These materials can be classified as mesoporous, with an average pore diameter (W) of approximately 55 Å (5.35–6.10 nm). The SEM and EDS analyses indicated that the EGDMA/VA microspheres are globular in shape with well-defined edges and contain 73.06% of carbon and 26.94% of oxygen. The microspheres containing modified starch exhibited a loss of smoothness with more irregular shape. The adsorption efficiency of dyes and heavy metal ions depends on the phases contact time, initial adsorbate concentration and the presence of competing electrolytes and surfactants. The equilibrium data were better fitted by the Freundlich isotherm model than by the Langmuir, Temkin, and Dubinin-Radushkevich models. The highest experimental adsorption capacities were observed for the BB3 dye which were equal to 193 mg/g, 190 mg/g, and 194 mg/g for EGDMA/VA, EGDMA/VA-St/B, EGDMA/VA-St/DiTDTA, respectively. The dyes and heavy metal ions were removed very rapidly and the time required to reach system equilibrium was below 20 min for M(II), 40 min for BB3, and 120 min for AG16. 50% v/v methanol and its mixture with 1 M HCl and NaCl for dyes and 1 M HCl for M(II) desorbed these impurities efficiently.

The adsorption capacities of ion exchangers with the primary amine (Lewatit^® VP OC 1065) and polyamine (Diaion™ CR20) functional groups relative to Pd(II) and Cu(II) ions were tested in a batch system, taking into account the influence of the acid concentration (HCl: 0.1–6 mol/L; HCl-HNO₃: 0.9–0.1 mol/L HCl—0.1–0.9 mol/L HNO₃), phase contact time (1–240 min), initial concentration (10–1000 mg/L), agitation speed (120–180 rpm), bead size (0.385–1.2 mm), and temperature (293–333 K), as well as in a column system where the variable operating parameters were HCl and HNO₃ concentrations. There were used the pseudo-first order, pseudo-second order, and intraparticle diffusion models to describe the kinetic studies and the Langmuir and Freundlich isotherm models to describe the equilibrium data to obtain better knowledge about the adsorption mechanism. The physicochemical properties of the ion exchangers were characterized by the nitrogen adsorption/desorption analyses, CHNS analysis, Fourier transform infrared spectroscopy, the sieve analysis, and points of zero charge measurements. As it was found, Lewatit^® VP OC 1065 exhibited a better ability to remove Pd(II) than Diaion™ CR20, and the adsorption ability series for heavy metals was as follows: Pd(II) >> Zn(II) ≈ Ni(II) >> Cu(II). The optimal experimental conditions for Pd(II) sorption were 0.1 mol/L HCl, agitation speed 180 rpm, temperature 293 K, and bead size fraction 0.43 mm ≤ f3 < 0.6 mm for Diaion™ CR20 and 0.315–1.25 mm for Lewatit^® VP OC 1065. The maximum adsorption capacities were 289.68 mg/g for Lewatit^® VP OC 1065 and 208.20 mg/g for Diaion™ CR20. The greatest adsorption ability of Lewatit^® VP OC 1065 for Pd(II) was also demonstrated in the column studies. The working ion exchange in the 0.1 mol/L HCl system was 0.1050 g/mL, much higher compared to Diaion™ CR20 (0.0545 g/mL). The best desorption yields of %D₁ = 23.77% for Diaion™ CR20 and 33.57% for Lewatit^® VP OC 1065 were obtained using the 2 mol/L NH₃·H₂O solution.

In the current study, iron-loaded dead leaf ash (Fe-DLA) was used as a novel catalyst in the heterogeneous catalytic ozonation process (HCOP) for textile wastewater containing Reactive Black 5 (RB-5). The research demonstrates a significant boost in removal efficiency, reaching 98.76% with 1.0 g/min O₃ and 0.5 g/L catalyst dose, by investigating key variables such as pH, ozone and catalyst doses, initial concentration, and the presence of scavengers in 1 L wastewater. The addition of tert-butyl alcohol (TBA) reduced RB-5 elimination, indicating the involvement of OH radicals. Catalyst reusability decreased slightly (2.05% in the second run; 4.35% in the third), which was attributed to iron leaching. A comparison of single ozonation (Fe-DLA) adsorption and catalytic ozonation processes (Fe-DLA/O₃) revealed that the combined process improved dye degradation by 25%, with removal rates ranking as Fe-DLA adsorption O₃ Fe-DLA/O₃, with an impressive 76.44% COD removal. These results strongly support RB-5 removal using Fe-DLA and HCOP at a basic pH, highlighting the catalyst’s utility in practical wastewater treatment.

The influence of co-ions on the adsorption properties of two surfactants: ABS (dodecylbenzene sulfonic acid) and its sodium salt ABSNa50 in the aqueous systems, has been studied and discussed. On the basis of experimental measurements of equilibrium and dynamic surface tension, a series of parameters were determined, such as critical micelle concentration (CMC), adsorption parameters, diffusion coefficients, and the micellar dissociation constant. It was proved that values of CMC vary according the contents of accompanying metal ions (zinc(II), copper(II), cobalt(II), nickel(II)) and hydrochloric acid in the system under discussion. Moreover, it was found that as the concentration of surfactant in the system increases, the estimated values of the diffusion coefficients decrease. The obtained results indicate the need to analyse the basic surface properties of surfactants in case of their application in the systems containing additional substances.

Adsorption abilities of weakly (Purolite A830), weakly basic/chelating (Purolite S984), and strongly basic (Lewatit MonoPlus SR7, Purolite A400TL, Dowex PSR2, Dowex PSR3) ion exchange resins of different functional groups and microporous Lewatit AF5 without functional groups towards vanadium(V) ions were studied in batch and column systems. In the batch system, the influence of the sorbent mass (0.01–0.1 g), pH (2–10), the phase contact time (1–1440 min),and the initial concentration (5–2000 mg/L) were studied, whereas in the column system, the initial concentrations (50, 100, and 200 mg/L) with the same bed volume and flow rate (0.4 mL/min) were studied. Desorption agents HCl and NaOH of 0.1–1 mol/L concentration were used for loaded sorbent regeneration. The pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models as well as the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models were used to describe kinetic and equilibrium data to acquire improved knowledge on the adsorption mechanism. The desorption efficiency was the largest using 0.5 mol/L NaOH for all sorbents under discussion. Purolite S984, Purolite A830, and Purolite A400TL, especially Purolite S984, are characterized by the best removal ability towards vanadium(V) from both model and real wastewater.

The selective removal of Cu(II) in the presence of sodium dodecylobenzene sulfonate from acidic effluents was made using the adsorption and micellar-enhanced ultrafiltration methods. Lewatit MonoPlus TP220 showed the best adsorption behavior in the systems containing Cu(II) in the presence of ABSNa50 surfactant compared to the other adsorbents (removal efficiency ≈ 100%, sorption capacity ≈ 10 mg/g). The kinetics followed the pseudo-second order kinetic equation. The Langmuir adsorption capacities were 110 mg/g (the system with ABSNa50 above CMC) and 130.38 mg/g (the system with ABSNa50 below CMC). The working ion exchange capacities were C_w = 0.0216 g/mL and C_w = 0.0135 g/mL. The copper removal by the micellar-enhanced ultrafiltration method was 76.46% (0.1 mol/L HCl).

The adsorption ability of Lewatit S5528 (S5528) resin for C.I. Acid Green 16 (AG16), heavy metals (Zn(II), Cu(II) and Ni(II)) and phenol removal from single-component aqueous solutions is presented in this study to assess its suitability for wastewater treatment. Kinetic and equilibrium studies were carried out in order to determine adsorption capacities, taking into account phase contact time, adsorbates’ initial concentration, and auxiliary presence (NaCl, Na₂SO₄, anionic (SDS) and non-ionic (Triton X100) surfactants). The pseudo-second-order kinetic model described experimental data better than pseudo-first-order or intraparticle diffusion models. The adsorption of AG16 (538 mg/g), phenol (14.5 mg/g) and Cu(II) (5.8 mg/g) followed the Langmuir isotherm equation, while the uptake of Zn(II) (0.179 mg^1−1/nL^1/n/g) and Ni(II) (0.048 mg^1−1/nL^1/n/g) was better described by the Freundlich model. The auxiliary’s presence significantly reduced AG16 removal efficiency, whereas in the case of heavy metals the changes were negligible. The column studies proved the good adsorption ability of Lewatit S5528 towards AG16 and Zn(II). The desorption was the most effective for AG16 (>90% of dye was eluted using 1 mol/L HCl + 50% v/v MeOH and 1 mol/L NaCl + 50% v/v MeOH solutions).

Pure compounds extracted and purified from medical plants are crucial for preparation of the herbal products applied in many countries as drugs for the treatment of diseases all over the world. Such products should be free from toxic heavy metals; therefore, their elimination or removal in all steps of production is very important. Hence, the purpose of this paper was purification of an extract obtained from Dendrobium officinale Kimura et Migo and cadmium removal using thermoplastic starch (S1), modified TPS with poly (butylene succinate); 25% of TPS + 75% PBS (S2); 50% of TPS + 50% PLA (S3); and 50% of TPS + 50% PLA with 5% of hemp fibers (S4), as well as ion exchangers of different types, e.g., Lewatit SP112, Purolite S940, Amberlite IRC747, Amberlite IRC748, Amberlite IRC718, Lewatit TP207, Lewatit TP208, and Purolite S930. This extract is used in cancer treatment in traditional Chinese medicine (TCM). Attenuated total reflectance-Fourier transform infrared spectroscopy, thermogravimetric analysis with differential scanning calorimetry, X-ray powder diffraction, gel permeation chromatography, surface analysis, scanning electron microscopy with energy dispersive X-ray spectroscopy, and point of zero charge analysis were used for sorbent and adsorption process characterization, as well as for explanation of the Cd(II) sorption mechanism.