Competitive adsorption of acetaminophen and caffeine onto activated Tingui biochar: characterization, modeling, and mechanisms.

Tingui biochar (TB) activated with potassium hydroxide (TB-KOH) was synthesized in the present study. The adsorption capacity of TB-KOH was evaluated for the removal of acetaminophen and caffeine in monocomponent and bicomponent solutions. As a result, the study of the TB-KOH characterization as well as the adsorption kinetics, isotherm, thermodynamics, and a suggestion of the global adsorption mechanism are presented. TB-KOH was characterized through physical-chemical analysis to understand its surface morphology and how it contributes to the adsorption of these drugs. Furthermore, modelling using advanced statistical physical models was performed to describe how acetaminophen and caffeine molecules are adsorbed in the active sites of TB-KOH. Through the characterizations, it was observed that the activation with KOH contributed to the development of porosity and functional groups (-OH, C-O, and C = O) on the surface of TB. The monocomponent adsorption equilibrium was reached in 90 min with a maximum adsorption capacity of 424.7 and 350.8 mg g-1 for acetaminophen and caffeine, respectively. For the bicomponent solution adsorption, the maximum adsorption capacity was 199.4 and 297.5 mg g-1 for acetaminophen and caffeine, respectively. The isotherm data was best fitted to the Sips model, and the thermodynamic study indicated that acetaminophen removal was endothermic, while caffeine removal was exothermic. The mechanism of adsorption of acetaminophen and caffeine by TB-KOH was described by the involvement of hydrogen bonds and π-π interactions between the surface of TB-KOH and the molecules of the contaminants.

Valorisation of spent tire rubber as carbon adsorbents for Pb(II) and W(VI) in the framework of a Circular Economy.

Spent tire rubber-derived chars and their corresponding H3PO4 and CO2-activated chars were used as adsorbents in the recovery of Pb(II) ion and (W(VI)) oxyanion from synthetic solutions. The developed chars (both raw and activated) were thoroughly characterized to have insight about their textural and surface chemistry properties. H3PO4-activated chars presented lower surface areas than the raw chars and an acidic surface chemistry which affected the performance of these samples as they showed the lowest removals of the metallic ions. On the other hand, CO2-activated chars presented increased surface areas and increased mineral content compared to the raw chars, having presented higher uptake capacities for both Pb(II) (103-116 mg/g) and W(VI) (27-31 mg/g) ions. Cation exchange with Ca, Mg and Zn ions was appointed as a mechanism for Pb removal, as well as surface precipitation in the form of hydrocerussite (Pb3(CO3)2(OH)2). W(VI) adsorption might have been ruled by strong electrostatic attractions between the negatively charged tungstate species and the highly positively charged carbons' surface.The results shown in this work allow concluding that the valorisation of spent tire rubber through pyrolysis and the subsequent activation of the obtained chars is an alternative and a feasible option to generate adsorbent materials with a high uptake capacity of critical metallic elements.

Study of the removal mechanism of aquatic emergent pollutants by new bio-based chars.

This work is dedicated to study the potential application of char byproducts obtained in the gasification of rice husk (RG char) and rice husk blended with corn cob (RCG char) as removal agents of two emergent aquatic contaminants: tetracycline and caffeine. The chars presented high ash contents (59.5-81.5%), being their mineral content mainly composed of silicon (as silica) and potassium. The samples presented a strong basic character, which was related to its higher mineral oxides content. RCG char presented better textural properties with a higher apparent surface area (144 m2 g-1) and higher micropore content (V micro = 0.05 cm3 g-1). The alkaline character of both chars promoted high ecotoxicity levels on their aqueous eluates; however, the ecotoxic behaviour was eliminated after pH correction. Adsorption experiments showed that RG char presented higher uptake capacity for both tetracycline (12.9 mg g-1) and caffeine (8.0 mg g-1), indicating that textural properties did not play a major role in the adsorption process. For tetracycline, the underlying adsorption mechanism was complexation or ion exchange reactions with the mineral elements of chars. The higher affinity of RG char to caffeine was associated with the higher alkaline character presented by this char.