Evaluation of waste biomasses and their biochars for removal of polycyclic aromatic hydrocarbons.

This work evaluates the use of biomasses and their biochars as adsorbents to remove polycyclic aromatic hydrocarbons from water. Coconut waste (CW) and orange waste (OW) were pyrolyzed at 350 °C to produce the corresponding biochars (BCW and BOW). Adsorption tests using a mixed solution of benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, and dibenzo(a,h)anthracene showed removal percentages of 30.33-83.43% (CW), 47.09-83.02% (BCW), 24.20-74.25% (OW), and 23.84-84.02% (BOW). The adsorption mechanisms appeared to involve π-π interactions of similar groups of the adsorbate and adsorbent, together with hydrophobic effects. There was no indication of competition between the PAHs for the adsorption sites, and there was evidence of cooperative adsorption. The PAHs could be desorbed from the adsorbents with efficiencies in the range 34.88-72.32%, and the reuse of the adsorbents in two further cycles demonstrated their potential for use in the removal of PAHs from water.

Removal of Cd, Cu, Pb, and Zn from aqueous solutions by biochars.

Sorption and desorption of heavy metals (Cd, Cu, Pb, and Zn) was evaluated in biochars derived from sugarcane bagasse (SB), eucalyptus forest residues (CE), castor meal (CM), green coconut pericarp (PC), and water hyacinth (WH) as candidate materials for the treatment of contaminated waters and soils. Solid-liquid distribution coefficients depended strongly on the initial metal concentration, with K d,max values mostly within the range 10(3)-10(4) L kg(-1). For all biochars, up to 95 % removal of all the target metals from water was achieved. The WH biochar showed the highest K d,max values for all the metals, especially Cd and Zn, followed by CE (for Cd and Pb) and PC (for Cd, Pb, and Zn). Sorption data were fitted satisfactorily with Freundlich and linear models (in the latter case, for the low concentration range). The sorption appeared to be controlled by cationic exchange, together with specific surface complexation at low metal concentrations. The low desorption yields, generally less than 5 %, confirmed that the sorption process was largely irreversible and that the biochars could potentially be used in decontamination applications.

Application of termite nest for adsorption of Cr(VI).

This work proposes the use of tree termite nest as an adsorbent for the reduction/removal of Cr(VI) present in aqueous solution. In laboratory experiments, adsorption of Cr(VI) was sensitive to pH in the range investigated (2-5), with maximum adsorption capacity achieved at pH 2 (3.70 ± 0.04 mg g(-1), representing 93.2% removal of Cr). The termite nest was characterized by off-line pyrolysis GC/MS (py-GC/MS), infrared spectroscopy (FTIR), and electron paramagnetic resonance spectroscopy (EPR). Pyrolysis of the adsorbent produced a complex mixture of aromatic compounds, including the guaiacyl and syringilic derivatives that are characteristic of lignocellulosic materials. Infrared spectroscopy revealed deprotonation of the carboxylic acid group of the biomass with increasing pH, which was associated with a decrease in the capacity for adsorption of Cr(VI). The EPR g-factor for the termite nest samples varied between 2.0037 and 2.0038, indicating the presence of organic free radicals that were responsible for the redox reaction. A second line with g-factor values of 1.9790, only observed for the samples after contact with Cr(VI) solutions at different pH values, was assigned to Cr(III)-Cr(III) exchange coupled pairs, which explained the capacity of the adsorbent to retain a large portion of the Cr(III) ions produced after reduction of Cr(VI) to Cr(III). Fixed-bed column experiments showed that the termite nest had a maximum adsorption capacity of 18.60 mg Cr g(-1), an adsorption efficiency varying between 60.8 and 97.4%, and a desorption efficiency varying between 54.5 and 91.4%, for three successive cycles. The adsorbent presented excellent performance in the removal of chromium under acidic conditions, with the advantage that it could be regenerated and reused.

Structural, vibrational and optical studies on an amorphous Se90P10 alloy produced by mechanical alloying.

We investigated some physicochemical properties of an amorphous Se(90)P(10) alloy produced by mechanical alloying through x-ray diffraction, Raman spectroscopy, optical absorption spectroscopy and EXAFS techniques. The total structure factor obtained from x-ray diffraction and the EXAFS χ(k) oscillations on the Se K edge were used in reverse Monte Carlo simulations to obtain structural information such as average coordination numbers and interatomic distances and the distribution of structural units present in the alloy. In addition, we also determined the vibrational modes and the optical band gap energy of the alloy.

Vibrational, optical and structural studies of an amorphous Se(0.90)S(0.10) alloy produced by mechanical alloying.

The local atomic order of an amorphous Se(0.90)S(0.10) alloy produced by mechanical alloying was studied by x-ray diffraction and extended x-ray absorption fine structure (EXAFS) data obtained at three temperatures, T = 300, 200 and 30 K. From the cumulant analysis of the EXAFS data, structural properties such as average interatomic distances, average coordination numbers, Debye-Waller factors and anharmonicity, given by the third cumulant, were obtained. The results found indicate that there is alloying at an atomic level, and Se-S pairs are more disordered and distorted than Se-Se ones due to the milling process.

Interruption of the MnO2 oxidative process on dopamine and L-dopa by the action of S2O3(2-).

The oxidation effects of Mn2+, Mn3+ or MnO2 on dopamine can be studied in vitro and, therefore, this offers a model of the auto-oxidation process that appears naturally in neurons causing Parkinson's disease. The use of MnO, as an oxidizer in aqueous solution at pH 7 causes the oxidation of catecholamines (L-dopa, dopamine, noradrenaline and adrenaline) to melanin. However, this work shows that, in water at pH 6-7, the oxidation of catecholamines by MnO2 in the presence of sodium thiosulphate (Na2S2O3) occurs by other mechanisms. For dopamine and L-dopa, MLCT complexes were formed with bands at 312, 350 (sh), 554 (sh) nm, and an intense band at 597 nm (epsilon approximately/= 4 x 10(3) M(-1) cm(-1)) and at ca. 336, 557 (sh) nm, and an intense band at 597 nm (epsilon approximately 6 x 10(3) M(-1) cm(-1)), respectively. The latter transitions were assigned to d(pi)-->pi*-SQ. Noradrenaline and adrenaline do not form this blue complex in solution, but generate soluble oxidized compounds. The resonance Raman spectra of these complexes in solution showed bands at 950, 1006, 1258, 1378, 1508 and 1603 cm(-1) for the complex derivation of L-dopa and at 948, 1010, 1255, 1373, 1510 and 1603 cm(-1) for the dopamine-derived compound. The most intense Raman band at ca. 1378 cm(-1) was assigned to C-O stretching with major C1-C2 characteristics and indicated that dopamine and L-dopa do not occur complexed with manganese in the catecholate or quinone form, but suggests an intermediate compound such as an anionic o-semiquinone (SQ-), forming a complex such as [Mn(II)(SQ-)3]-. All enhanced Raman frequencies are characteristic of the benzenic ring without the participation of the aminic nitrogen. A mechanism is proposed for the formation of the dopamine and L-dopa complexes and a computational simulation was performed to support it.

Complexes of arabinogalactan of Pereskia aculeata and Co2+, Cu2+, Mn2+, and Ni2+.

The main interest in the biopolymer arabinogalactan is that it is edible. Complementing its high protein percentage, when complexed to essential metal ions, widens the use in food and pharmacology industries and technologies. The binding constants of Co2+, Cu2+, Mn2+ and Ni2+ with arabinogalactan, extracted from the leaves of Pereskia aculeata from Brazil were determined by potentiometric titrations and also the speciation according to pH values. The complexed species proposed by potentiometric titrations and the unique complexing ability of galacturonic acid groups towards Cu2+ and Ni2+ in the tridimensional web structure of arabinogalactan were confirmed by IR and EPR spectroscopies. The thermal stability of the complexed species also varied with the metal ion employed in the complexation when compared to the biopolymer alone. These complexes are new sources of additives for the food and pharmacology industries and carriers of essential metal ions to animal and vegetal biochemistry.

A physicochemical study of the tetracycline coordination to oxovanadium(IV).

The interaction of tetracycline and oxovanadium(IV) in aqueous solution was studied by potentiometric and spectrophotometric methods. Oxovanadium(IV) ions form both a positively charged 1:1 and a neutral 2:1 metal-ligand complex with tetracycline. When a 1:1 ligand-to-metal ratio mixture is used at about pH 4.5 the 1:1 species predominates, being replaced at pH 6 by the binuclear complex. The binuclear complex has been isolated and fully characterised. Infrared and EPR studies suggest the existence of two distinct vanadyl binding sites. Our results indicate that the first vanadium coordinates to the BCD-ring system and the second one to the A-ring. Biological implications of the existence of a neutral complex at physiological pH are briefly discussed.