RESUMO
This study reports the use of multivariate tools to optimize the synthesis of a new agricultural-based biosorbent derived from sugarcane bagasse (SB) for the removal of Cd(II) and Pb(II) from aqueous solutions, as well as to optimize the process of desorption of these ions from the spent biosorbent using an acidic solution. The effects of the reaction parameters temperature (T), time (t), and the ratio of 1,2,3,4-butanetetracarboxylic acid dianhydride (BTCAD) to raw SB (wBTCAD wraw SB-1) on the chemical modification of raw SB with BTCAD and on the equilibrium adsorption capacity (qe) for Cd(II) and Pb(II) were investigated by application of a 23 Doehlert experimental design (DED), followed by optimization using a statistical desirability tool to produce the best adsorbent in terms of performance and cost. The best reaction condition was wBTCAD wraw SB-1 of 4.0 g g-1, t of 1 h, and T of 70 ºC. The optimal synthesis condition resulted in a modified sugarcane bagasse (MSB) that provided qe values for Cd(II) and Pb(II) of 0.50 and 0.61 mmol g-1, respectively, obtained under the following conditions: 0.311 mmol Cd(II) L-1, 0.632 mmol Pb(II) L-1, pH 5.0, 4 h, 0.2 g L-1 MSB, 130 rpm, and 25 °C. The desorption of Cd(II) and Pb(II) from MSB was investigated by a 22 DED, with optimization using the desirability tool to obtain the best desorption condition in terms of HNO3 solution concentration ([Formula: see text]) and t. The desorption efficiencies for Cd(II) and Pb(II) were 90 ± 4% and 88 ± 3%, respectively, obtained using 0.7 mol L-1 HNO3, t of 42 min, and 1.0 g L-1 MSB-M(II) (M = Pb or Cd). Infrared spectroscopy was used to investigate the natures of the interactions involved in the adsorption of Cd(II) and Pb(II) on MSB, as well as possible changes in the chemical structure of MSB after desorption. The synthesis of MSB can be performed under mild reaction conditions (t = 1 h, T = 70 ºC), and the solvents used can be recovered by distillation. BTCA is commercially available at moderate cost and can alternatively be obtained employing microbial succinic acid, metal-free catalysis, and modest use of petrochemical feedstocks. Furthermore, MSB can be reused, which could contribute to increasing the economic feasibility of water and wastewater treatment processes.
Assuntos
Saccharum , Poluentes Químicos da Água , Celulose/química , Cádmio/análise , Chumbo , Poluentes Químicos da Água/análise , Ácido Succínico , Cinética , Concentração de Íons de Hidrogênio , Adsorção , Água , Íons , SolventesRESUMO
The treatment of pharmaceutical industrial wastewaters, containing the antibiotic amoxicillin (218.29â mg L-1), via some advanced oxidation processes (POA), was studied. The H2O2 photolysis process presented the highest percentage of mineralization (97%), after the total reaction time (180â min). However, the photo-Fenton process showed the highest organic carbon removal rate, mineralizing 65% of the initial concentration, in 30â min. Because of this fact, this process was studied in more detail. The initial concentration of ferrous ions (0.03-1.00â mmol L-1) did not affect the performance of the photo-Fenton process, possibly operating using concentrations of below 15â mg L-1 (0.27â mmol L-1), that is the iron content limit for discharging wastewaters established in the Brazilian environmental legislation. Furthermore, experiments were performed according to the composite experimental design technique (Doehlert matrix), analyzing the following variables: (i) the inlet molar flow rate of H2O2 (FH2O2 ) and (ii) the initial concentration of ferrous ions ([Fe2+]). Besides that, the initial mineralization rate and the total organic carbon removal percentages, measured at 5, 10, 15 and 30â min of reaction, were chosen as the response variables. It was observed that FH2O2 was the most important variable in relation to the initial degradation rate. In the optimal conditions (FH2O2 = 3.27â mmol min-1 and [Fe2+] = 0.27â mmol L-1), the photo-Fenton process achieved a percentage of organic carbon removal of 84%, in only 30â min of reaction, presenting an interesting potential for real industrial applications, combined, or not, with conventional technologies (as biological treatments, for example).
Assuntos
Preparações Farmacêuticas , Poluentes Químicos da Água , Amoxicilina , Antibacterianos , Peróxido de Hidrogênio , Oxirredução , Eliminação de Resíduos Líquidos , Águas ResiduáriasRESUMO
Zinc bacitracin (Zn-Bc) belongs to the group of nonribosomal peptide antibiotics (NRPA), comprising a mixture of non-biodegradable congeners characterized by complex structures containing cyclic, polycyclic, and branched chains. However, reports on the use of AOPs for the degradation of NRPA are non-existent. In this context, the present work investigated the photodegradation of Zn-Bc in aqueous solution by direct photolysis and the UVC/H2O2 process. The effects of the specific UVC photon emission rate and initial H2O2 concentration were studied following a Doehlert-design response surface approach. The results showed that all congeners photolyzed at the highest UVC doses in the absence of hydrogen peroxide, with a calculated quantum yield of 0.0141 mol Zn-Bc mol photons-1. However, no TOC removal was observed after 120 minutes of irradiation, suggesting the disruption of the peptide bonds in the antibiotic molecules without significant changes in the amino acid residues. The addition of H2O2 substantially accelerated Zn-Bc photodegradation, resulting in a remarkable removal of up to 71% of TOC. Most importantly, the antimicrobial activity against Staphylococcus aureus could be completely removed by both treatments. These findings point out that the UVC/H2O2 process can be straightly engineered for the treatment of metalloantibiotics-containing wastewater in pharmaceutical facilities.