Multivariate optimization applied to the synthesis and reuse of a new sugarcane bagasse-based biosorbent to remove Cd(II) and Pb(II) from aqueous solutions.

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.

Batch and continuous adsorption of Cu(II) and Zn(II) ions from aqueous solution on bi-functionalized sugarcane-based biosorbent.

A new one-pot synthesis method optimized by a 23 experimental design was developed to prepare a biosorbent, sugarcane bagasse cellulose succinate pyromellitate (SBSPy), for the removal of Cu(II) and Zn(II) from single-component aqueous solutions, in batch and continuous modes. The bi-functionalization of the biosorbent with ligands of different chemical structures increased its selectivity, improving its performance for removing pollutants from contaminated water. The succinate moiety favored Cu(II) adsorption, while the pyromellitate moiety favored Zn(II) adsorption. Sugarcane bagasse (SB) and SBSPy were characterized using several techniques. Analysis by 13C Multi-CP SS NMR and FTIR revealed the best order of addition of each anhydride that maximized the chemical modification of SB. The maximum adsorption capacities of SBSPy for Cu(II) and Zn(II), in batch mode, were 1.19 and 0.95 mmol g-1, respectively. Homogeneous surface diffusion, intraparticle diffusion, and Boyd models were used to determine the steps involved in the adsorption process. Isothermal titration calorimetry was used to assess changes in enthalpy of adsorption as a function of SBSPy surface coverage. Fixed-bed column adsorption of Cu(II) and Zn(II) was performed in three cycles, showing that SBSPy has potential to be used in water treatment. Breakthrough curves were well fitted by the Thomas and Bohart-Adams models.

A review on the use of lignocellulosic materials for arsenic adsorption.

In this review, bibliometric analysis was made of recent studies and current trends concerning the application of lignocellulosic materials as bioadsorbents for the removal of arsenic from aqueous systems. Evaluation was made of lignocellulosic adsorbents and their chemical characteristics, as well as interactions involved in the adsorption of arsenic, bioadsorbent reusage (desorption and re-adsorption), competition between co-existing ions in multi-element aqueous solutions, and applications of bioadsorbents in batch and continuous systems. Lignocellulosic biomass has been shown to be a promising source of new adsorbents, since it is a low-cost and renewable material. However, there seems to be no commercially available technology that uses bioadsorbents based on lignocellulosic biomass for arsenic removal. In addition, the structural modification of lignocellulosic biomass to improve its adsorption capacity and selectivity has proved to be a suitable strategy, with the service time and the selectivity of the bioadsorbent in the presence of co-existing ions the most critical aspects to be pursued. The competitive adsorption of co-existing anions (PO43-, SO42-, NO3-, and Cl-) by the adsorption sites, as well as life-cycle assessment and cost analysis are rarely reported. Complexation, electrostatic attraction, ion exchange and precipitation were the main interactions involved in the adsorption of arsenic on lignocellulosic materials. However, most studies have failed to prove the nature of the interactions. Macroscopic methods can be useful to evaluate the adsorption mechanism of arsenic on bioadsorbents of complex structure, such as lignocellulosic biomass (modified or not). Nevertheless, the elucidation of the adsorption mechanism requires experiments based on measurements at the microscopic level. The upscaling of biosorption technology for arsenic removal will only be possible through studies that investigate: i) the interactions involved in the adsorption process; ii) the transfer of bench-scale experiments to pilot-scale experiments with real contaminated water with low arsenic concentration; and iii) the life-cycle assessment of biosorbents produced from lignocellulosic biomass.

Aminated cellulose as a versatile adsorbent for batch removal of As(V) and Cu(II) from mono- and multicomponent aqueous solutions.

A bioadsorbent (CEDA) capable of adsorbing As(V) and Cu(II) simultaneously was prepared by tosylation of microcrystalline cellulose (MC) and nucleophilic substitution of the tosyl group by ethylenediamine. MC, tosyl cellulose, and CEDA were characterized by elemental C, H, N, and S analysis, infrared spectroscopy, and 13C solid-state nuclear magnetic resonance spectroscopy. The adsorption of As(V) and Cu(II) on CEDA was evaluated as a function of solution pH, contact time, and initial solute concentration. The maximum adsorption capacities of CEDA for As(V) and Cu(II) were 1.62 and 1.09 mmol g-1, respectively. The interactions of As(V) and Cu(II) with CEDA were elucidated using thermodynamic parameters, molecular quantum mechanics calculations, and experiments with ion exchange of Cd(II) by Cu(II), and As(V) by SO42-. Adsorption enthalpies were determined as a function of surface coverage of the CEDA, using isothermal titration calorimetry, with ΔadsH° values of -32.24 ± 0.07 and -93 ± 2 kJ mol-1 obtained for As(V) and Cu(II), respectively. The potential to reuse CEDA was evaluated and the interference of other ions in the adsorption of As(V) and Cu(II) was investigated. Multi-component experiments showed that Cd(II), Co(II), Ni(II), and Pb(II) did not interfere in the adsorption of Cu(II), while SO42- inhibited As(V) adsorption.

Accumulation and oxidation of elemental mercury in tropical soils.

The role of chemical and mineralogical soil properties in the retention and oxidation of atmospheric mercury in tropical soils is discussed based on thermal desorption analysis. The retention of gaseous mercury by tropical soils varied greatly both quantitatively and qualitatively with soil type. The average natural mercury content of soils was 0.08 ± 0.06 µg g(-1) with a maximum of 0.215 ± 0.009 µg g(-1). After gaseous Hg(0) incubation experiments, mercury content of investigated soils ranged from 0.6 ± 0.2 to 735 ± 23 µg g(-1), with a mean value of 44 ± 146 µg g(-1). Comparatively, A horizon of almost all soil types adsorbed more mercury than B horizon from the same soil, which demonstrates the key role of organic matter in mercury adsorption. In addition to organic matter, pH and CEC also appear to be important soil characteristics for the adsorption of mercury. All thermograms showed Hg(2+) peaks, which were predominant in most of them, indicating that elemental mercury oxidized in tropical soils. After four months of incubation, the thermograms showed oxidation levels from 70% to 100%. As none of the samples presented only the Hg(0) peak, and the soils retained varying amounts of mercury despite exposure under the same incubation conditions, it became clear that oxidation occurred on soil surface. Organic matter seemed to play a key role in mercury oxidation through complexation/stabilization of the oxidized forms. The lower percentages of available mercury (extracted with KNO3) in A horizons when compared to B horizons support this idea.