RESUMO

In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.

Assuntos

RESUMO

Wastes of Araucaria angustifolia (named pinhão) natural (PW) and also loaded with Congo red (CRP) were tested as low-cost adsorbents for Cu(II) removal from aqueous solutions. In order to reduce the total number of experiments to achieve the best conditions of the batch adsorption procedure, three sets of statistical designs of experiments were carried-out for each adsorbent. Initially, a full 2(4) factorial design for each adsorbent with two central points (18 experiments) were performed, to optimize the following factors: mass of adsorbent (m), pH, time of contact (t) and initial metallic ion concentration (Co). These results indicated that almost all the main factors and its interactions were significant. It was verified for both adsorbents, that a mass of 30.0mg leaded to higher Cu(II) uptake and that the best pH for Cu(II) adsorption was 5.6. In order to continue the batch adsorption optimization of the systems, a central composite surface analysis design with two factors (Co, t) containing 13 experiments, divided in to four cube points, four axial points and five centre points was carried-out for each adsorbent. By performing these two sets of statistical design of experiments, the best conditions for Cu(II) uptake using pinhão wastes (PW) and pinhão wastes loaded with Congo red (CRP) using batch adsorption system, where: m=30.0mg of adsorbent; pH 5.6; t=2.5h. After optimizing the batch adsorption system by statistical design of experiments, isotherms for Cu(II) uptake using PW and CRP were performed. These isotherms fitted to the linear Langmuir and Freundlich models.

Assuntos

RESUMO

In order to reduce the total number of experiments for achieving the best conditions for Cr(VI) uptake using Araucaria angustifolia (named pinhão) wastes as a biosorbent, three statistical design of experiments were carried out. A full 2(4) factorial design with two blocks and two central points (20 experiments) was experimented (pH, initial metallic ion concentration-C(o), biosorbent concentration-X and time of contact-t), showing that all the factors were significant; besides, several interactions among the factors were also significant. These results led to the performance of a Box-Behnken surface analysis design with three factors (X, C(o) and t) and three central points and just one block (15 experiments). The performance of these two statistical designs of experiments led to the best conditions for Cr(VI) biosorption on the pinhão wastes using a batch system, where: pH 2.0; C(o) = 1200 mg l(-1) Cr(VI); X = 1.5 g l(-1) of biosorbent; t = 8 h. The maximum Cr(VI) uptake in these conditions was 125 mg g(-1). After evaluating the best Cr(VI) biosorption conditions on pinhão wastes, a new Box-Behnken surface analysis design was employed in order to verify the effects of three concomitant ions (Cl(-), NO(3)(-) and PO(4)(3-)) on the biosorption of Cr(VI) as a dichromate on the biosorbent (15 experiments). These results showed that the tested anions did not show any significant effect on the Cr(VI) uptake by pinhão wastes. In order to evaluate the pinhão wastes as a biosorbent in dynamic system, a glass column was fulfilled with pinhão wastes (4.00 g) as biosorbent, and it was fed with 25.0 mg l(-1) Cr(VI) at pH 2.0 and 2.5 ml min(-1). The breakpoint was attained when concentrations of effluent of the column attained the value of 0.05 mg l(-1) Cr(VI) using 5550 ml of the metallic ion solution. In these conditions, the biosorbent was able to remove completely Cr(VI) from aqueous solution with a ratio of Cr(VI) effluent volume/biosorbent volume of 252.3.

Assuntos

RESUMO

The 1,3-diaminepropane-3-propyl-anchored silica gel (DAPPS) was successfully employed as a sorbent in a spectrophotometric flow system for the preconcentration of Cu(2+) in digests of biological materials (maize powder, soybean, citrus leaves, corn stalks) as well as water samples (river, stream, streamlet, springwater and well). The system presented a minicolumn packed with DAPPS, where the sample solution was passed through it for a period of time, and subsequently, an eluent solution, stripped-out the retained analyte which was further determined with DDTC at 460 nm. The better preconcentration conditions utilized were: 120s loading, 60s elution, 30s regeneration of the column, loading flow rate 6.5 ml min(-1), buffer solution for the preconcentration and regeneration of the column-borate buffer pH 8.5, elution flow rate 2.3 ml min(-1), time of elution 60s, eluent composition, 0.4 mol l(-1) HNO(3). Under these conditions, the preconcentration factor obtained was 36, and the detection limit achieved was 8.4 ng ml(-1) in water samples and 0.84 microg g(-1) in biological material. The maximum adsorption capacity of DAPPS to Cu(2+) was 0.49 mmol g(-1) (31.1 mg g(-1)) obtained in a batch system. The recovery of copper in the water samples ranged from 96.9 to 102.4% and in the biological materials ranged from 97.0 to 102.6%.

Assuntos

RESUMO

A new sorbent was synthesized by anchoring 7-amino-4-azaheptyltrimetoxisilane, freshly prepared, to silica gel, producing 7-amino-4-azaheptyl anchored silica gel (AAHSG). This material was characterized by infrared spectroscopy (IR), elemental analysis (CHN), and nitrogen adsorption-desorption isotherms. Isotherms of the adsorption of Fe3+, Fe2+ and Cu2+ on AAHSG were recorded, which indicated that Fe3+ presents a higher affinity by the sorbent. Therefore, AAHSG was successfully employed as a sorbent in a simple flow system for the preconcentration of Fe3+ in natural water samples, such as, river water, lagoonwater, springwater, stream water, well water and two water reference materials (NIST-SRM 1640, NIST-SRM 1643d). The obtained preconcentration factor was 82.2, and the detection limit achieved was 5.9 ng ml(-1). The recovery of spiked water samples ranged from 95.0 - 103.1%.

RESUMO

Single noble metal permanent modifiers such as, Rh, Ir, and Ru, as well as mixed tungsten plus noble metal (W-Rh, W-Ru, W-Ir) permanent modifiers thermally deposited on the integrated platform of transversally heated graphite atomizer were employed for the determination of arsenic in sludges, soils, sediments, coals, ashes and waters by electrothermal atomic absorption spectrometry. Microwave digests of solid samples and water samples were employed for obtaining the analytical characteristics of the methods with different permanent modifiers. The performance of the modifiers for arsenic determination in the real samples depended strongly on the type of permanent modifier chosen. The single noble metal (Rh, Ir and Ru) permanent modifiers were suitable for the analyte determinations in simpler matrices such as waters (recoveries of certified values 95-105%), but the analyte recoveries of certified values in sludges, soils, sediments, coals, and ashes were always lower than 90%. On the other hand, for the determination of arsenic, using W-Rh, W-Ru, and W-Ir permanent modifiers presented recoveries of certified values within 95-105% for all the samples. Long-term stability curves obtained for the determination of arsenic in environmental samples with different permanent modifiers (Rh, Ir, Ru, W-Rh, W-Ir, W-Ru) showed that the improvement in the tube lifetime depends on the tungsten deposit onto the platform. The tungsten plus noble metal permanent modifier presents a tube lifetime of at least 35% longer when compared with single permanent modifier. The results for the determination of As employing different permanent modifiers in the samples were in agreement with the certified reference materials, since no statistical differences were found after applying the paired t-test at the 95% confidence level.