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.

Novel activated carbon from Magonia pubescens bark: characterization and evaluation of adsorption efficiency.

In this work, the synthesis of activated carbon from the bark of the Magonia pubescens (known as Tingui) and its efficiency in the removal of diclofenac sodium through batch adsorption tests and physical-chemical characterizations were investigated. The phytotoxicity of this material was also evaluated through germination and root growth of Lactuca sativa seeds. According to the experimental design performed for the synthesis of Tingui carbon, the optimized temperature and residence time for the production of this adsorbent were 550 °C and 120 min, respectively. The equilibrium time was reached in 600 min and the theoretical model that best fitted the kinetic data was the Elovich model. The BET was the best fit for the adsorption isotherm dataThis indicates that the adsorption process of sodium diclofenac by activated carbon can occur by two different mechanisms, monolayer and/or multilayer adsorption, depending on the conditions employed in the process, such as temperature and adsorbate concentration. The thermodynamic study showed that the process was favourable and spontaneous in the temperature range evaluated. Furthermore, the characterizations showed by TG/DTG and FTIR analyses that the temperature throughout the process had a marked impact on the degradation of the organic constituents of the biomass and the appearance of distinct functional groups that contributed to the adsorption process of diclofenac sodium. Finally, the toxicity tests recognized that this adsorbent does not affect the germination of L. sativa species. Thus, this adsorbent may become a novel and viable option to be used in the removal of sodium diclofenac.

Nanogreen is the new future: the conversion of lignin and lignocellulosic wastes into nanomaterials.

The lignocellulose biorefinery industry has assumed an important role within the current scenario. Lignin is an abundant and available biopolymer and one of the compounds present in the lignocellulosic waste. Therefore, processing lignin into new materials and nanomaterials, such as nanolignin, has attracted the attention of the scientific community. Lignin nanoparticles are materials that have excellent properties, such as biodegradability and non-toxicity, and have great potential as chelating agents, antimicrobials agents, UV protectors, nanofillers, adsorbents, catalysts, supercapacitors, emulsion stabilizers, delivered systems, drugs, and gene carriers. This review article covers the emergent scenario of nanolignin and the main aspects of scientific interest, such as the conversion and functionalization of lignin, the valorization of lignocellulose waste, and nanoparticle synthesis. A techno-economic evaluation of the biorefinery model of the nanolignin synthesis is presented based on the simulation of the process on the experimental and commercial databases available and reported by some authors. Finally, the techno-economic assessment is complemented by the life cycle assessment of various nanolignin synthesis pathways reported to evaluate the environmental implications and support this emergent technology development.

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.

Synthesis of a biobased resin and its screening as an alternative adsorbent for organic and inorganic micropollutant removal.

The sol-gel route was used to synthesize a biophenolic resin from a blend of Kraft black liquor and condensed tannin. The biobased resin has an amorphous structure and diversified surface functional groups. The biomaterial thermal stability was improved by Kraft black liquor, which increased the fixed carbon yield by 19.78% in an oxidant medium and 9.07% in an inert medium. Moreover, the presence of fixed carbon and char is positively related to the material flame retardant property. Additionally, impedance measurements were used to understand the physical phenomena occurring at the polymeric matrix's interface and the material's final properties. The biobased resin characterization and the considerable increase in the presence of micropollutants in surface and water bodies suggest the new biomaterial application in the adsorption process. Thus, its adsorption capacity toward several organic and inorganic micropollutants and its effectiveness in complex water matrices were evaluated. Methylene blue was used as a model compound to assess the influence of the resin composition on the adsorption capacity, and the type H isotherm indicates the high affinity of the biobased resin toward the micropollutant. The adsorption occurs in multilayer by intermolecular interaction and electrostatic forces. The amount of Kraft black liquor favored the adsorption, and the adsorption capacity was greater than 1250 mg g-1. When inorganic compounds were evaluated, the carboxyl and phenol groups favor the biomaterial affinity toward metal ions. Cu2+ and Ni2+ were completely removed from the contaminated water, and the adsorption capacity of the other inorganic compounds was: Pb2+ (36.97 mg g-1), Al3+ (22.17 mg g-1), Ba2+ (12.76 mg g-1), Ag1+ (33.85 mg g-1), and Fe2+ (19.44 mg g-1). In contrast, the adsorption capacity of the organic micropollutants was: 2,4-D (3.09 mg g-1), diuron (5.89 mg g-1), atrazine (2.71 mg g-1), diclofenac (2.04 mg g-1), caffeine (5.79 mg g-1), acetaminophen (4.80 mg g-1), methylene Blue (106.66 mg g-1), and methyl orange (30.48 mg g-1). The results pointed that the adsorption efficiency of organic micropollutants increases with the distribution coefficient (logD), indicating the biobased resin affinity toward more lipophilic compounds and ionized species.